CN108296492A - The manufacturing method of alloy nano particle - Google Patents
The manufacturing method of alloy nano particle Download PDFInfo
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- CN108296492A CN108296492A CN201711163170.1A CN201711163170A CN108296492A CN 108296492 A CN108296492 A CN 108296492A CN 201711163170 A CN201711163170 A CN 201711163170A CN 108296492 A CN108296492 A CN 108296492A
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- cosb
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/45—Others, including non-metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
Abstract
Crystallite grain size is manufactured as 100nm homogeneous skutterudite compound CoSb below using easy synthetic method the subject of the invention is to provide a kind of3Method.The method is by reducing agent by Co from the solution comprising compound containing Co and the compound containing Sb2+And Sb3+Co is reverted to respectively0And Sb0, to manufacture CoSb3, adjust the discharge quantity of compound containing Co and the compound containing Sb so that by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed become 1:2.9~1:3.1.
Description
Technical field
The present invention relates to the manufacturing methods of alloy nano particle.
Background technology
Thermo-electric converting material is based on 2 kinds of basic pyroelectric effects i.e. Seebeck (Seebeck) effect and Peltier
(Peltier) effect carries out the semi-conducting material of thermal energy and electric energy directly converted.
As such thermo-electric converting material, have for example with crystal structure as Fig. 1, by MX3(M be cobalt (Co),
Rhodium (Rh), iridium (Ir) etc., X are phosphorus (P), arsenic (As), antimony (Sb) etc.) skutterudite compound (skutterudite that indicates
Compound), various discussions have been carried out for the thermo-electric converting material comprising skutterudite compound.
For example, patent document 1 is described using average grain diameter of hot soap (hot soap) method manufacture with 2~100nm
Skutterudite compound CoSb3Method.
Patent document 2 describes using high-temperature high-pressure state, subcritical or postcritical reaction dissolvent
The alloy nano particle CoSb of Co and Sb3Method.
The method that patent document 3 describes manufacture nano-composition thermo-electric converting material, the nano-composition thermoelectricity turn
Conversion materials are made of the parent phase of thermo-electric converting material is dispersed with the nano-particle of dispersant, and in the thermo-electric converting material
Parent phase and the dispersant nano-particle interface have 0.1nm or more interface roughness.
Citation
Patent document 1：Japanese Unexamined Patent Publication 2005-325419 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2011-184723 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2010-114419 bulletins
Invention content
The index of performance as evaluation thermo-electric converting material, uses power factor PF=S2σ or dimensionless performance index
(also referred to as conversion efficiency of thermoelectric) (in formula, S is Seebeck coefficient to ZT=(PF/ κ) × T, and σ is conductivity, and κ is pyroconductivity, T
It is absolute temperature).In thermo-electric converting material, good pyroelecthc properties are obtained, preferably ZT is big.That is, it is preferred that Seebeck coefficient S
High with conductivity σ, preferably pyroconductivity κ is low.
Conductivity σ is improved, the impurity in thermo-electric converting material is preferably reduced, obtains that there is desirable form with single-phase
The semiconducting crystal of ratio.
Reduce pyroconductivity κ, preference as shown in Fig. 2, reduce crystal grain (crystallite grain size), can be by heat in nanocrystal
Interface is blocked.
Such semi-conducting material for making heat to electricity conversion performance improve, it is desirable that using productivity, economy, safe
Method manufactures.
Method recorded in patent document 1 has the following problems：The surface-active used as dispersant in hot soap method
Agent or the impurity (hereinafter also referred to Organic impurity) for coming from surfactant, can remain in the skutterudite as product
It closes in object, conductivity σ is made to decline.As the method for solving this problem, there is the skutterudite compound that will be obtained in Organic
The temperature of impurity decomposition/volatilization, carry out at a temperature of such as 700 DEG C~800 DEG C for a long time, heat treatment in such as 3~30 hours
Method.But this method can cause the coarsening of the crystallite grain size of skutterudite compound particle due to heat treatment, as a result,
Cause the rising of pyroconductivity κ, finally causes the decline of heat to electricity conversion performance.
In method recorded in patent document 2, high-temperature high-pressure state, subcritical or postcritical reaction dissolvent is used.
In order to make reaction dissolvent be in subcritical or supercriticality, need that the equipment comprising synthesising container is made to be resistant to high temperature and pressure
State (temperature：200 DEG C or more, pressure：4.0MPa or more).Therefore, the method recorded in patent document 2, equipment cost are non-
Chang Gao, therefore economy is low, and higher consideration is also required to for safety.In addition, in general, needing to be set as high pressure
The productivity of technique is low, is not suitable for a large amount of synthesis.In addition, in the method for continous way (flow type), also easily cause with pipe plug
Plug, therefore have to improve the frequency safeguarded, productivity is low.
In addition, in the compound produced using the 2nd process of patent document 3, including the particle of each constitution element simple substance,
And/or the compound that ratio of components is different from desirable ratio of components (hereinafter also referred to as inorganic nature impurity).In order to make such nothing
Machine impurity becomes target skutterudite product, and the processing for needing the inorganic impurity that will be obtained to be heat-treated and homogenizing will
So-called hydro-thermal process in high temperature, such as 240~380 DEG C carry out for a long time, such as 24~72 hours.Under high temperature, long-time
Hydro-thermal process can make particle coarsening while homogenizing due to thermal diffusion, as a result, causing that pyroconductivity κ's is upper
It rises, finally causes the decline of heat to electricity conversion performance.Therefore, being additionally required makes the very small nano-particle side of being homogeneously dispersed in cobalt
The technology controlling and process of Composite is carried out in mine base material.
Therefore, the subject of the invention is to provide a kind of manufacturing methods of alloy nano particle, using easy synthetic method, system
It is 100nm homogeneous skutterudite compound CoSb below to make crystallite grain size3, i.e. skutterudite compound CoSb3Alloy nanoparticle
Son.
The present inventor has carried out various discussions to means for solving the problem, as a result, it has been found that, passing through reducing agent
Each metal ion is reduced to each metal to manufacture CoSb from the solution comprising compound containing Co and the compound containing Sb3Side
In method, the discharge quantity of compound containing Co and the compound containing Sb is adjusted so that by Co2+It is reduced to Co0Speed and by Sb3+Reduction
For Sb0The ratio between speed close to after particular value, in obtained CoSb3X-ray diffraction analysis in, CoSb3Skutterudite crystal structure
With single-phase appearance, and obtained CoSb3With 100nm crystallite grain sizes below, so as to complete the present invention.
That is, the purport of the present invention is as described below.
(1) a kind of CoSb3Manufacturing method, by reducing agent from the solution comprising compound containing Co and the compound containing Sb
By Co2+And Sb3+It is reduced to Co respectively0And Sb0To manufacture CoSb3, wherein under adjustment compound containing Co and compound containing Sb
Doses so that by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed be 1：2.9~1：3.1.
(2) according to the CoSb described in (1)3Manufacturing method, adjustment includes the blanking of compound containing Co and the compound containing Sb
Amount so that by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed be 1：3.
(3) according to the CoSb described in (1) or (2)3Manufacturing method, as by Co2+And Sb3+It is reduced to Co respectively0And Sb0
Reducing agent, use at least one kind of weak reductant in oxalic acid, ascorbic acid and citric acid.
(4) according to any one of them CoSb of (1)~(3)3Manufacturing method, 250~320 DEG C of reaction temperatures,
And implement under 1~10 hour reaction time.
(5) according to any one of them CoSb of (1)~(4)3Manufacturing method, [Co2+] and [Sb3+] it is total a concentration of
0.140~0.770mol/l.
(6) according to the CoSb described in (5)3Manufacturing method, [Co2+] and [Sb3+] total a concentration of 0.350~
0.770mol/l。
The method of the present invention, particle and the composition for not generating each constitution element simple substance in obtained particle are different from target
Particle, or even if generate less than in the past, the composition of each interparticle constitution element is uniform, therefore need not made
Dispersant the reason of being likely to become Organic impurity is used when making.Therefore, in the present invention, high temperature, long-time need not be carried out
Organic impurity remove processing and/or hydro-thermal process.As a result, the CoSb that method using the present invention obtains3, substantially not
Including Organic impurity and inorganic nature impurity, have single-phase skutterudite crystal structure, and CoSb3The crystallite grain size of particle can
It is maintained at 100nm or less.In addition, [Co2+] and [Sb3+] total concentration it is bigger, CoSb3The crystallite grain size of particle is with regard to smaller.
In addition, the present invention method in, hydro-thermal process need not be carried out, that is to say, that also need not use be resistant to
The synthesis device of high pressure.Therefore, the present invention can use easy synthesis device and method to implement, productivity, economy, safety
Property is excellent.
Description of the drawings
Fig. 1 shows skutterudite compound MX3Crystal structure.
Fig. 2 indicates the state of the crystallite in thermo-electric converting material.
Fig. 3 indicates the schematic diagram of the present invention.
Fig. 4 indicates the schematic diagram of the present invention.
Fig. 5 indicates the XRD diffraction patterns of the powder modulated in comparative example 1 and 2 and embodiment 1 and 6.
Fig. 6 indicates CoSb in the powder modulated in Examples 1 to 6, obtaining3The crystallite grain size of particle relative to
[Co2+] and [Sb3+] total concentration relationship.
Specific implementation mode
Hereinafter, the preferred embodiment of the present invention is described in detail.
In this specification, the feature of the description of the drawings present invention is suitably referred to.In attached drawing, in order to make clear and by each section
Size and shape are exaggerated, and do not describe actual size and shape accurately.Therefore, technical scope of the invention is not limited to this
The size and shape of each section shown by a little attached drawings.Furthermore skutterudite compound CoSb of the invention3Alloy nano particle
Manufacturing method be not limited to following embodiments, without departing from the scope of the subject in the invention, can be to be applied with this field
The various forms of change, the improvement that technical staff can carry out etc. are implemented.
The present invention as shown in figure 3, be will be each from the solution comprising compound containing Co and the compound containing Sb by reducing agent
Metal ion is reduced to each metal to manufacture CoSb3Method, in the method, adjust compound containing Co and compound containing Sb
Discharge quantity so that by Co2+It is reduced to Co0Speed (hereinafter also referred to RCo) and by Sb3+It is reduced to Sb0Speed (below
Referred to as RSb) the ratio between (hereinafter also referred to RCo：RSb) close to particular value.
In the present invention, as compound containing Co, Co is formed2+And the compound dissolved in a solvent, though it is not limited to
Hereinafter, but the acylate, such as tartaric acid cobalt, citric acid cobalt, cobalt acetate etc. that have such as cobaltous dichloride, cobalt, in a solvent for
Insoluble compound can carry out dissolving use by acid appropriate etc..As the compound containing Co used in the present invention, preferably
It is difficult to generate skutterudite compound CoSb3The cobalt acetate of by-product in addition.
In the present invention, as compound containing Sb, Sb is formed3+And the compound dissolved in a solvent, though it is not limited to
Hereinafter, but the acylate, such as antimony acetate, potassium antimony tartrate etc. that have such as antimony trichloride, antimony, it is insoluble in a solvent
Compound can carry out dissolving use by acid appropriate etc..As the compound containing Sb used in the present invention, preferably it is difficult to generate
Skutterudite compound CoSb3The antimony acetate of by-product in addition.
In the present invention, as in order to modulate the solvent for including the solution of compound containing Co and the compound containing Sb and using,
It is to make Co2+And Sb3+Stabilized solvent, though it is not limited to hereinafter, such as polar solvent can be used, such as protic is molten
Agent, such as water, alcohol, polyalcohol, their mixture etc..As the solvent used in the present invention, preferably tetraethylene glycol
(tetraethylene glycol)。
Comprising in the method for the solution of compound containing Co and the compound containing Sb, the addition of each compound is suitable for the modulation of the present invention
Sequence, addition temperature, mixed method, incorporation time etc. do not limit, and dissolve each compound in a solvent, and it is made equably to mix.
It, can be in 1~30 DEG C of room temperature for example, in the method for solution of the modulation comprising compound containing Co and the compound containing Sb of the present invention
Under, the tetraethylene glycol as solvent is added into reaction vessel, is then stirred by blender, and sequentially add conduct
The cobalt acetate of the compound containing Co, the antimony acetate as the compound containing Sb, each compound are dissolved in tetraethylene glycol, until solution is equal
Until matter, mixes such as 0.2~1 hour, be modulated.
In the present invention, the dissolved oxygen concentration in solvent and solution does not limit, but preferably low, for example, being generally adjusted to
10mg/l is hereinafter, be more preferably adjusted to 5mg/l or less.
Here, in order to reduce dissolved oxygen concentration, previous degassing method etc. can be used, though do not limit, for example with
Toward degassing method in the case of, can in the solution or solvent as object, by the inert gases such as nitrogen, argon gas with 1~
30 DEG C, usually blister with 50~500ml/ point, preferably with 50~100ml/ points of flow.
In the present invention, the discharge quantity of compound containing Co and the compound containing Sb is adjusted so that RCo：RSbClose to particular value.
Here, so-called particular value, is desirable semiconductor i.e. skutterudite compound CoSb in the present invention3Co and Sb
Ratio of components (molar ratio) (Co：Sb), i.e., 1：3.
Therefore, in the present invention, the discharge quantity of compound containing Co and the compound containing Sb is adjusted so that RCo：RSbIt is 1：2.9~
1：3.1, it is preferably 1：2.93~1：3.07, it is more preferably 1：2.96~1：3.04, it is particularly preferably 1：3.
In the present invention, RCoIt can be expressed from the next.
RCo=kCo[Co2+]
In formula, kCoIt is by Co2+It is reduced to Co0Reaction in rate constant, [Co2+] it is Co in solution2+It is dense
Degree.
In the present invention, RSbIt can be expressed from the next.
RSb=kSb[Sb3+]
In formula, kSbIt is by Sb3+It is reduced to Sb0Reaction in rate constant, [Sb3+] it is Sb in solution3+It is dense
Degree.
By handling above, RCo：RSbIt can be expressed as RCo：RSb=kCo[Co2+]：kSb[Sb3+]。
Therefore, in the present invention, the discharge quantity of compound containing Co and the compound containing Sb is from above-mentioned RCo：RSbRelationship from the point of view of, quilt
It is adjusted to kCo[Co2+]：kSb[Sb3+] it is 1：2.9~1：3.1, preferably 1：2.93~1：3.07, more preferably 1：2.96~1：
3.04, particularly preferably 1：3.
In the present invention, kCoAnd kSbThe value pass that passes through measured in advance respective blanking concentration of metal ions and reduction rate
System, and calculated to acquire.Also, the value is used, the blanking concentration of metal ions as desirable reduction rate is acquired.
In the present invention, [Sb3+] it is usually 0.015~0.1mol/l, preferably 0.03~0.1mol/l, more preferably 0.06
~0.1mol/l, [Co2+] it is usually 0.006~0.04mol/l, preferably 0.012~0.04mol/l, more preferably 0.024~
0.04mol/l。
In the present invention, [Co2+] and [Sb3+] total concentration the upper limit be compound containing Co and the compound containing Sb dissolving
The upper limit of degree.[Co2+] and [Sb3+] total concentration be preferably 0.140~0.770mol/l, more preferably 0.350~
0.770mol/l.In addition, [Co2+] and [Sb3+] total concentration be preferably regulated as more than 0.020mol/l, such as 0.030mol/
L or more.
By adjusting the discharge quantity of compound containing Co and the compound containing Sb as described above, in obtained CoSb3In particle,
The particle of each constitution element simple substance and the particle that composition is different from target will not be generated, or generating less than in the past, respectively
The composition of interparticle constitution element becomes uniform.In addition, by by [Co2+] and [Sb3+] total concentration be adjusted to be more than
0.020mol/l, the particle of constitution element simple substance may occurring due to the reactivity caused by rarefaction can be inhibited to decline, each
With the generation for forming the particle different from target.
In addition, obtained CoSb3Particle has single-phase skutterudite crystal structure, and CoSb3The crystallite grain size of particle is
100nm or less.In addition, by improving the discharge quantity of compound containing Co and the compound containing Sb, improving [Co2+] and [Sb3+] conjunction
Count concentration, the CoSb that can be further decreased3The crystallite grain size of particle.By by [Co2+] and [Sb3+] total concentration set
For 0.140~0.770mol/l, the CoSb with 75nm crystallite grain sizes below can be obtained3Particle, moreover, by by [Co2 +] and [Sb3+] total concentration be set as 0.350~0.770mol/l, can obtain that there is 50nm crystallite grain sizes below
CoSb3Particle.
In the present invention, by improving the discharge quantity of compound containing Co and the compound containing Sb, R can be increasedCoAnd RSb, improve
Productivity.In addition, by improving discharge quantity, CoSb can be further decreased3The crystallite grain size of particle, therefore can be had
The material of good pyroelecthc properties.
In the present invention, as from the solution comprising compound containing Co and the compound containing Sb by Co2+And Sb3+Point
Co is not reduced to it0And Sb0Reducing agent, as long as can be by Co2+And Sb3+It is reduced to Co respectively in the same solution0And Sb0's
Reducing agent does not just limit, and it can be mentioned, for example the weak reductants of oxalic acid, ascorbic acid, citric acid, their mixture etc..
The amount of reducing agent the compound containing Co used and the redox reaction of reducing agent reaction equation and use
It is molar equivalent or more relative to metal ion, preferably in the reaction equation of compound containing Sb and the redox reaction of reducing agent
For the 2 times or more of molar equivalent.
By adjusting the type and amount of reducing agent as described above, as shown in figure 4, Sb3+It will not be reduced to Sb by crossing3-, energy
Enough it is effectively formed skutterudite compound CoSb3Alloy nano particle (for example, when by cross be reduced to Sb3-In the case of, then with
Proton in conjunction with and gasify, generate composition deviation).
In the present invention, by Co from the solution comprising compound containing Co and the compound containing Sb2+And Sb3+It is reduced to respectively
Co0And Sb0Reaction reaction temperature, usually 250~320 DEG C, preferably 270~320 DEG C, more preferably 280~320 DEG C.
In the present invention, by Co from the solution comprising compound containing Co and the compound containing Sb2+And Sb3+It is reduced to respectively
Co0And Sb0Reaction reaction time, usually 1~10 hour, preferably 1~6 hour.
By adjusting the temperature and time of reaction as described above, can effectively promote Co2+And Sb3+It restores respectively
For Co0And Sb0Reaction.
In the present invention, by Co from the solution comprising compound containing Co and the compound containing Sb2+And Sb3+It is reduced to Co respectively0
And Sb0Reaction solution in dissolved oxygen concentration be preferably regulated as low, for example, 10mg/l is hereinafter, be more preferably adjusted to 5mg/
L or less.
By reducing dissolved oxygen concentration, as-reduced Co can be inhibited0And Sb0Re-oxidation.
In the present invention, will include that the solution and reducing agent of compound containing Co and the compound containing Sb is mixed, reacted
Method in, the order of addition of the solution and reducing agent does not limit, and in solution, is carried out in such a way that reducing agent is mixed in heterogeneity
Mixing.In the present invention, preferably by comprising compound containing Co and the solution of the compound containing Sb and the mixing of reducing agent, implementing to restore
Implement at a temperature of reaction.In the present invention, for example, the solution that will include compound containing Co and the compound containing Sb, is risen with argon gas etc.
Bubble rises to reaction temperature by blender while stirring, and after reaching reaction temperature, slowly adds reducing agent, implements anti-
It answers.
The skutterudite compound CoSb obtained after the reaction3Alloy nano particle, filtered thereafter, pass through water, alcohol etc.
Washer solvent washing, raw material etc. are fully removed.Then, the alloy nano particle by under inert gas air-dry,
Drying or vacuum drying under inert gas atmosphere etc. and dried, according to circumstances crushed.It can be with dry type, wet no matter crushing
Use previous crushing technology, such as mortar, hammer-mill, ball mill, ball mill, jet mill, roller mill etc. likes.
Furthermore for the skutterudite compound CoSb produced in the present invention3Alloy nano particle, the alloy nanoparticle
Son does not use dispersant, such as surfactant during fabrication, therefore contains substantially no Organic impurity, also, in the conjunction
The particle of each constitution element simple substance and the particle that composition is different from target are not generated in gold nanoparticle, or is compared generating yet
Previous few, the composition of each interparticle constitution element is uniform, therefore the Organic that need not be carried out under high temperature, long-time is miscellaneous
Matter removes processing and/or hydro-thermal process.
The present invention can be implemented under batch-type or continous way.
In the present invention, the molar ratio of the discharge quantity of compound containing Co and the compound containing Sb may not become desirable semiconductor
Skutterudite compound CoSb3Co and Sb ratio of components (molar ratio) i.e. 1：3, therefore remaining chemical combination containing Co after the reaction sometimes
Object or compound containing Sb.The compound containing Co or compound containing Sb of remaining can use in lower secondary response.
The skutterudite compound CoSb produced in the present invention3Alloy nano particle be that skutterudite shown in Fig. 1 is brilliant
Body structure is the crystal structure that Co, Z are Sb with M.It is preferred that the alloy nano particle is with X-ray diffraction analysis (XRD
Analysis：When UltimaIV (RIGAKU systems) is measured, only there is CoSb3The peak of skutterudite crystal structure is (that is, in XRD analysis
In, CoSb3Skutterudite crystal structure is with single-phase appearance).
The skutterudite compound CoSb produced in the present invention3Alloy nano particle, seen under the conditions of above-mentioned XRD analysis
Survey 2 θ=31.3 ° (013) peak in, using Scherrer (Scherrer) formula measure crystallite grain size when, have 100nm or less,
The crystallite grain size of preferably 90~75nm, more preferably 80~75nm.In addition, in the present invention, passing through raising [Co2+] and [Sb3 +] the skutterudite compound CoSb that produces of total concentration3Alloy nano particle, 2 observed under the conditions of above-mentioned XRD analysis
In the peak of θ=31.3 ° (013), using Scherrer formula measure crystallite grain size when, have 100nm or less, preferably 90~
The crystallite grain size of 40nm, more preferably 80~40nm, further preferably 75~40nm, particularly 50~40nm.
Here, so-called Scherrer formula, be to acquire the formula that crystallite grain size (D) uses, can be as described below
It indicates：
D=K λ/(β cos θ)
[in formula, K is Scherrer constants, and λ is characteristic X-ray wavelength (CuK α), and β is that half value is wide, and θ is the angle of diffraction].
The cobalt ore compound CoSb produced in the present invention3Alloy nano particle, during fabrication do not use dispersant, example
Such as surfactant, therefore contain substantially no Organic impurity.In addition, the result of the XRD analysis from the alloy nano particle
From the point of view of, do not generate the particle of each constitution element simple substance and the particle that composition is different from target in the alloy nano particle, or
Generating less than in the past, the composition of each interparticle constitution element is uniform, therefore it is miscellaneous to contain substantially no inorganic nature
Matter.Therefore, which can inhibit the decline for the electrical characteristics (output power factor) for coming from impurity, can realize
High output power factor.
In addition, in the present invention, the Organic impurity that do not implement under high temperature, long-time removes processing and/or hydro-thermal process, because
The crystallite grain size of particle in this obtained alloy nano particle is maintained small.Therefore, which can inhibit
The rising for the pyroconductivity that crystallite grain size coarsening is brought, can realize higher output power factor.
Therefore, the skutterudite compound CoSb produced in the present invention3Alloy nano particle have and greatly improved
Conversion efficiency of thermoelectric ZT, thus it is very useful as thermo-electric converting material.
Moreover, the present invention uses the small-sized and easy equipment being made of cheap utensil (such as glass wares), it can
Implement under atmospheric pressure system.Therefore, productivity of the invention, economy, safety are excellent.
The method of the present invention is not only in skutterudite compound CoSb3(contain (Co, Ni) Sb3, (Co, Fe) Sb3) system, it can also
In Bi2Te3(contain (Bi, Sb)2(Te、Se)3) system, PbTe systems, Zn4Sb3It is applied in the manufacture of the thermo-electric converting material of system etc..
Embodiment
Hereinafter, illustrating some embodiments of the present invention, but it is not intended to limit the invention to these embodiment institutes
The range shown.
I. sample preparation
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by comparative example 1：2.0, and by Co2+Also
Originally it was Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed be adjusted to 1：The manufacture of 2.2 powder
(1) tetraethylene glycol (Tetra-EG) 0.017L is added to beaker, is stirred on one side at 30 DEG C, added again on one side as containing
Cobalt acetate (Co (the CH of Co compounds3COO)2) 0.14g, the antimony acetate (Sb (CH as the compound containing Sb3COO)3)0.49g.It holds
Continuous stirring 0.5 hour has modulated mixed solution until each raw material equably dissolve.
(2) in the mixed solution modulated in (1), argon is blistered with the flow of 20 DEG C, 50ml/ points, it will be in mixed liquor
Oxygen degassing.
(3) mixed liquor that the oxygen obtained in (2) has deaerated, is blistered with argon gas on one side, is warming up to 300 DEG C on one side, addition
It will as the oxalic acid of reducing agent ((COOH)2) 0.36g is dissolved in the product in tetraethylene glycol 0.003L.
(4) it will be added to the mixed liquor of reducing agent in (3), blistered on one side with argon, react 360 points at 300 DEG C on one side
Clock forms the particle for promoting the crystallinity of alloying high.
(5) the reactant filtering that will contain the particle formed in (4) after being washed with ethyl alcohol (ethanol), keeps solvent dry
It is dry, obtain powder.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by comparative example 2：3.0, and by Co2+Also
Originally it was Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed be adjusted to 1：The manufacture of 3.8 powder
In (1) of comparative example 1, the discharge quantity of compound containing Co and the compound containing Sb is changed, in addition to this compared with
Example 1 has similarly manufactured powder.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by embodiment 1：2.5, by [Co2+] and
[Sb3+] total concentration be set as 0.140mol/l, and by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0Speed
The ratio between be adjusted to 1：The manufacture of 3.0 powder
In (1) of comparative example 1, change compound containing Co and the compound containing Sb discharge quantity, in addition to this with comparative example 1
Powder is similarly manufactured.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by embodiment 2：2.5, by [Co2+] and
[Sb3+] total concentration be set as 0.210mol/l, and by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0Speed
The ratio between be adjusted to 1：The manufacture of 3.0 powder
In (1) of comparative example 1, change compound containing Co and the compound containing Sb discharge quantity, in addition to this with comparative example 1
Powder is similarly manufactured.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by embodiment 3：2.5, by [Co2+] and
[Sb3+] total concentration be set as 0.350mol/l, and by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0Speed
The ratio between be adjusted to 1：The manufacture of 3.0 powder
In (1) of comparative example 1, change compound containing Co and the compound containing Sb discharge quantity, in addition to this with comparative example 1
Powder is similarly manufactured.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by embodiment 4：2.5, by [Co2+] and
[Sb3+] total concentration be set as 0.490mol/l, and by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0Degree it
Than being adjusted to 1：The manufacture of 3.0 powder
In (1) of comparative example 1, change compound containing Co and the compound containing Sb discharge quantity, in addition to this with comparative example 1
Powder is similarly manufactured.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by embodiment 5：2.5, by [Co2+] and
[Sb3+] total concentration be set as 0.630mol/l, and by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0Speed
The ratio between be adjusted to 1：The manufacture of 3.0 powder
In (1) of comparative example 1, change compound containing Co and the compound containing Sb discharge quantity, in addition to this with comparative example 1
Powder is similarly manufactured.
The molar ratio of the discharge quantity of compound containing Co and the compound containing Sb is set as 1 by embodiment 6：2.5, by [Co2+] and
[Sb3+] total concentration be set as 0.770mol/l, and by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0Speed
The ratio between be adjusted to 1：The manufacture of 3.0 powder
In (1) of comparative example 1, the discharge quantity of compound containing Co and the compound containing Sb is changed, it is same with comparative example 1 in addition to this
Sample powder is manufactured.
II. sample measures
I. in sample preparation comparative example 1 and 2 and Examples 1 to 6 in each powder for modulating, pass through respectively
XRD analysis (device：UltimaIV (RIGAKU systems)) determine crystalline state.Furthermore for what is modulated in Examples 1 to 6
Powder, the peak in 2 θ=31.3 ° (013) determine crystallite grain size using Scherrer formula.
III. result
As a result shown in table 1 and Figures 5 and 6.
Table 1
In Figure 5, (a) is the XRD diffraction patterns of the powder modulated in comparative example 1, (b) is modulated in comparative example 2
The XRD diffraction patterns of powder, (c) be the powder modulated in embodiment 1 XRD diffraction patterns, (d) modulated in embodiment 6
The XRD diffraction patterns of powder.Include not only side in the XRD diffraction patterns of the powder modulated in comparative example 1 from the point of view of table 1 and Fig. 5
Cobalt ore compound CoSb3, also include CoSb2Peak, in the XRD diffraction patterns of the powder modulated in comparative example 2, include not only
Skutterudite compound CoSb3, also include the peak of Sb, in contrast, the XRD diffraction patterns of the powder modulated in Examples 1 to 6
In, only observe skutterudite compound CoSb3Peak.
Fig. 6 is CoSb in the powder modulated in Examples 1 to 6, obtaining3The crystallite grain size of particle is relative to [Co2 +] and [Sb3+] total concentration relationship.
It is 100nm or less by table 1 and Fig. 6 it is found that the crystallite grain size of the powder modulated in embodiment 1 is 75nm.This
Outside, it is known that if [Co2+] and [Sb3+] total concentration become larger, RCoAnd RSbBecome larger, then the CoSb obtained3The crystallite grain size of particle
Become smaller.Specifically, with [Co2+] and [Sb3+] total concentration become 0.350mol/l from 0.140mol/l, obtain
CoSb3The crystallite grain size of particle is tapered into from 75nm, [Co2+] and [Sb3+] add up to a concentration of 0.350~0.770mol/l
When, obtained CoSb3The crystallite grain size constant of particle, crystallite grain size are 50nm or less.It is thought that due in alloy
In the generating process of nano-particle, [Co2+] and [Sb3+] total concentration become larger, the edge that thus a large amount of karyogenesis is promoted
Therefore.
Claims (6)
1. a kind of CoSb3Manufacturing method, be by reducing agent from the solution comprising compound containing Co and the compound containing Sb will
Co2+And Sb3+It is reduced to Co respectively0And Sb0To manufacture CoSb3Method, wherein adjustment compound containing Co and compound containing Sb
Discharge quantity so that by Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed become 1：2.9~1：3.1.
2. CoSb according to claim 13Manufacturing method, adjust compound containing Co and the compound containing Sb discharge quantity, make
It obtains Co2+It is reduced to Co0Speed and by Sb3+It is reduced to Sb0The ratio between speed become 1：3.
3. CoSb according to claim 1 or 23Manufacturing method, as by Co2+And Sb3+It is reduced to Co respectively0And Sb0's
Reducing agent uses at least one kind of weak reductant in oxalic acid, ascorbic acid and citric acid.
4. according to any one of them CoSb of claims 1 to 33Manufacturing method, in 250~320 DEG C of reaction temperatures and 1
Implement under~10 hours reaction time.
5. according to any one of them CoSb of Claims 1 to 43Manufacturing method, [Co2+] and [Sb3+] it is total a concentration of
0.140~0.770mol/l.
6. CoSb according to claim 53Manufacturing method, [Co2+] and [Sb3+] total a concentration of 0.350~
0.770mol/l。
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| JP2017045989A JP6856412B2 (en) | 2017-01-12 | 2017-03-10 | Method for manufacturing alloy nanoparticles |
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| JPH07302259A (en) * | 1994-04-25 | 1995-11-14 | Internatl Business Mach Corp <Ibm> | Method and apparatus for stochastic simulation of process |
| CN101356659A (en) * | 2005-12-07 | 2009-01-28 | 丰田自动车株式会社 | Thermoelectric conversion material and process for producing the same |
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| JP2011184723A (en) * | 2010-03-05 | 2011-09-22 | Tohoku Univ | Method for synthesizing nanocrystalline alloy |
| CN103341641A (en) * | 2013-07-24 | 2013-10-09 | 厦门大学 | Preparing method for CoSb3 thermoelectric nanometer powder materials |
| JP2015045065A (en) * | 2013-08-28 | 2015-03-12 | 住友金属鉱山株式会社 | Silver powder and production method thereof |
| CN105828805A (en) * | 2013-08-07 | 2016-08-03 | 学校法人近畿大学 | Nanoparticles and nanoparticle composition, and method for producing nanoparticles and nonparticle composition |
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2017
- 2017-11-21 CN CN201711163170.1A patent/CN108296492A/en active Pending
- 2017-12-08 US US15/835,599 patent/US20180195153A1/en not_active Abandoned
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| JPH07302259A (en) * | 1994-04-25 | 1995-11-14 | Internatl Business Mach Corp <Ibm> | Method and apparatus for stochastic simulation of process |
| CN101356659A (en) * | 2005-12-07 | 2009-01-28 | 丰田自动车株式会社 | Thermoelectric conversion material and process for producing the same |
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| JP2011184723A (en) * | 2010-03-05 | 2011-09-22 | Tohoku Univ | Method for synthesizing nanocrystalline alloy |
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| CN105828805A (en) * | 2013-08-07 | 2016-08-03 | 学校法人近畿大学 | Nanoparticles and nanoparticle composition, and method for producing nanoparticles and nonparticle composition |
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