CN109371282B - A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite - Google Patents
A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite Download PDFInfo
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- CN109371282B CN109371282B CN201810834784.6A CN201810834784A CN109371282B CN 109371282 B CN109371282 B CN 109371282B CN 201810834784 A CN201810834784 A CN 201810834784A CN 109371282 B CN109371282 B CN 109371282B
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- 238000005551 mechanical alloying Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000010438 heat treatment Methods 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 37
- 229910018985 CoSb3 Inorganic materials 0.000 claims abstract description 35
- 229910018989 CoSb Inorganic materials 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- 230000015572 biosynthetic process Effects 0.000 claims description 28
- 238000003786 synthesis reaction Methods 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- 239000003708 ampul Substances 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010425 asbestos Substances 0.000 claims description 13
- 229910052895 riebeckite Inorganic materials 0.000 claims description 13
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000006096 absorbing agent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000012774 insulation material Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 7
- 230000005619 thermoelectricity Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000007500 overflow downdraw method Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical group 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910018987 CoSb2 Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005616 pyroelectricity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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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
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1054—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by microwave
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention discloses a kind of methods that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite, belong to the preparation technical field of thermoelectric material.A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention, microwave fast heating technology is combined with mechanical alloying, and CoSb first is prepared using microwave heating3, then by CoSb3Powder carries out mechanical alloying processing after being mixed with filling with In powder, is finally sintered the CoSb that high-purity is prepared again3Base filling skutterudite thermoelectric material.The CoSb that common process is difficult to synthesize can be prepared using preparation process of the invention3Base fills alloy, and effectively increases gained CoSb3The thermoelectric figure of merit and purity of base filling thermoelectric material.
Description
Technical field
The invention belongs to the preparation technical fields of thermoelectric material, more specifically more particularly to a kind of microwave fast heating-machine
The method that two step of tool alloying is synthetically prepared high-performance skutterudite.
Background technique
Increasingly depleted with fossil fuel, environment and energy problem become increasingly conspicuous, so as to cause the height of countries in the world
Pay attention to.Thermoelectric material can be realized the direct conversion of thermal energy and electric energy, small, light weight, environmental-friendly, reliability with component ruler
By force, the course of work is noiseless, long service life, being easily integrated and the features such as large-scale production, therefore before being most development
One of new material of scape.Thermoelectric material uses nondimensional thermoelectric figure of merit (ZT) Lai Jinhang performance measure,Its
In, S is Seebeck coefficient, and ρ is resistivity, and κ is thermal conductivity, and T is thermodynamic temperature.Therefore proposing high zt just needs big plug
Seebeck coefficient and low resistivity, thermal conductivity, but since thermoelectricity parameter (ρ, S, κ) is interrelated, be difficult to optimize simultaneously to obtain
Obtain high zt.
Skutterudite compound is one of thermoelectric material most promising at present, and the chemical general formula of compound is MX3,
Wherein M is transition metal Co, Rh or Ir, and X is phosphorus family element P, As or Sb, belongs to body-centered cubic structure, space group Im3,
Each unit cell contains 8 MX3Unit, totally 32 atoms, transition metal M are located at octahedra center, and X atom is located at ligand
Vertex.That most study is CoSb in skutterudite thermoelectric chemical compound3Based square cobalt mineral.Although binary CoSb3Skutterudite has higher
Conductivity, moderate seebeck coefficient, however its lattice thermal conductivity is higher, lower so as to cause its thermoelectric figure of merit, therefore drops
Low CoSb3The lattice thermal conductivity of skutterudite is for CoSb3The popularization and application of skutterudite just have great importance.
Currently, the prior art has Many researchers to begin one's study to binary CoSb3Element filling is carried out in skutterudite to make
It is standby to obtain CoSb3Base ternary skutterudite thermoelectric material, wherein more commonly filling element specifically include that Li, Na, K, Rb, Be,
Mg, Ca, Sr, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Tl and In etc., CoSb3Base ternary side
Cobalt ore thermoelectric material is due to good high-temperature stability and machinability, it is considered to be is most possibly applied to vehicle exhaust
Deng industry more than Waste Heat Recovery thermo-electric generation thermoelectric material.Existing CoSb3The synthetic method of based square cobalt mineral thermoelectric material is mainly wrapped
Include fusion method, solid-phase synthesis, mechanical alloying and vapour deposition process.
Wherein, the preparation of high performance filled skutterudite is usually using high-purity elemental metals as raw material, in vacuum or gas
It melt-synthesizes, quenches in the environment of atmosphere, using long term annealing, final product is obtained, if to obtain available block material
Material will also powder sintering processed.But using melting and long term annealing processing, generated time up to 30 hours (Acta Physica Sinica, 2010,
59 (10): 7219-04), energy consumption is higher, and prolonged high temperature will lead to excessive grain and grow up, and seriously affect its pyroelectricity
Can, and since the fusing point of Co and Sb differs 864K, single-phase CoSb is hardly resulted in this way3Base thermoelectricity material.Such as
The application case that China Patent No. is 201410027252.3 is that synthesis CoSb is prepared using fusion method3Alloy is added simultaneously
Annealing in 2 to 3 days, the efficiency for obtaining monocrystalline is lower, the performance along the direction of growth is unstable.And use the meeting of synthesis in solid state rule
There is Sb and CoSb2Miscellaneous phase uses merely mechanical alloying method, and generated time is also longer, is easy to generate miscellaneous phase
(Thermoelectric Nanomaterials Springer Series in Materials Science,2013,182:
255-285).In addition, preparing synthesis CoSb using the above method3It is generally difficult to be effectively ensured when base ternary skutterudite thermoelectric material
The uniformity for filling Elemental redistribution, to influence its service performance.
Summary of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome existing CoSb3It is above insufficient existing for based square cobalt mineral thermoelectric material preparation process,
Provide a kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite.Using of the invention
The CoSb that common process is difficult to synthesize can be prepared in preparation process3Base fills alloy, and effectively increases gained CoSb3Base
Fill the thermoelectric figure of merit and purity of thermoelectric material.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention are as follows:
A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention, will
Microwave fast heating technology is combined with mechanical alloying, and CoSb first is prepared using microwave heating3, then by CoSb3Powder with
Mechanical alloying processing is carried out after filling In powder mixing, is finally sintered again and CoSb is prepared3Based square cobalt mineral thermoelectricity
Material.
Further, the present invention specifically includes the following steps:
Step 1: raw material preparation, mixing
Using Co, Sb elemental powders as raw material, according to CoSb3Atom mass rate is weighed, and carries out ground and mixed, grinding
Acetone is added in the process；
Step 2: cold moudling
By powder cold moudling, pressure 6-9MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, is placed in micro-wave oven and carries out heating synthesis；
Step 4: second of raw material proportioning
It will be ground after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weigh In powder and
CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, then puts the sample after ball milling
Electric plasma agglomeration to get arrive InxCo4Sb12Skutterudite thermoelectric material.
Further, the power of the microwave heating is 500-1000W, heating time 4-8min.
Further, the revolving speed of ball-milling treatment is 200-230 revs/min in the step 5, Ball-milling Time 6-10h.
Further, sintering temperature is 620-635 DEG C, soaking time 4-6min in the step 5.
Further, the granularity of Co, Sb elemental powders is 400 mesh, purity 99.9% in the step 1；It is described
In step 4 200 mesh or more will be ground to after the sample comminution after synthesis.
Further, guarantee that the vacuum degree in quartz ampoule is 10 in the step 3-3MPa or more.
Further, in the microwave heating synthesis process, the quartz ampoule after sealing is placed in the dry pot of ceramics, dry pot
Place microwave-assisted absorber in inside.
Further, the microwave-assisted absorber uses green silicon carbide.
Further, asbestos are placed around dry pot as thermal insulation material, and asbestos thickness is lower than dry pot height.
3. beneficial effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result:
(1) a kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention,
Microwave fast heating technology is combined with mechanical alloying, by using two step synthesis technologies, on the one hand can synthesize
Common process is difficult to the In synthesized filling CoSb3On the other hand based square cobalt mineral thermoelectric material can effectively improve gained CoSb3Base
The thermoelectric figure of merit of skutterudite thermoelectric material, to guarantee its application effect.
(2) a kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention,
By using microwave heating-mechanical alloying two-step process, and to specific process parameter, such as the power of microwave heating, time, ball
Mill processing time and the technological parameters such as sintering temperature and time optimize, on the one hand can improve to the greatest extent
On the other hand the thermoelectric figure of merit of gained skutterudite can guarantee that In element sufficiently, is uniformly filled into the lattice hole of CoSb3,
Sb, CoSb in synthesis process can also be effectively avoided simultaneously2The generation of equal impurity, advantageously ensures that the purity of gained skutterudite.
(3) a kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention,
CoSb is synthesized using microwave heating method3Alloy, heat temperature raising is more uniform, and speed is fast, can effectively inhibit excessive grain long
Greatly, and apparatus structure is simple, and equipment operation is convenient, and experiment success rate is high, considerably reduces experimentation cost, is easy to scale
Production and popularization.
Detailed description of the invention
Fig. 1 is the XRD diagram that the embodiment of the present invention 1 prepares gained skutterudite block thermoelectric material.
Fig. 2 is the thermoelectric figure of merit that the embodiment of the present invention 1 prepares gained indium filled skutterudite block thermoelectric material.
Specific embodiment
To further appreciate that the contents of the present invention, now in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
For using existing fusion method, solid-phase synthesis, mechanical alloying and vapour deposition process preparation synthesis CoSb3Base side
The thermoelectric figure of merit of existing skutterudite and purity are relatively low when cobalt ore thermoelectric material, so that the deficiency of its using effect is influenced,
The present embodiment combines microwave fast heating technology with mechanical alloying, and CoSb first is prepared using microwave heating3, then
By CoSb3Powder carries out mechanical alloying processing after being mixed with filling with In powder, is finally sintered again, so as to be prepared
In fills CoSb3Based square cobalt mineral thermoelectric material effectively increases gained CoSb3The thermoelectric figure of merit of based square cobalt mineral thermoelectric material.Together
When, by using two step synthesis technology of microwave heating-mechanical alloying, and to specific process parameter, as microwave heating power,
Time, ball-milling treatment time and the technological parameters such as sintering temperature and time optimize, thus on the one hand can be with maximum journey
The thermoelectric figure of merit of skutterudite obtained by the raising of degree may be used also on the other hand on the basis of the thermoelectric figure of merit of the skutterudite obtained by guarantee
To guarantee that In element sufficiently, is uniformly filled into the lattice hole of CoSb3, and it can effectively avoid Sb, CoSb in synthesis process2
The generation of equal impurity, advantageously ensures that the purity of gained skutterudite.
Specifically, a kind of two step of microwave fast heating-mechanical alloying of the present embodiment is synthetically prepared high-performance skutterudite
Method, specifically includes the following steps:
Step 1: raw material preparation, mixing
With granularity for 400 mesh, Co, Sb elemental powders that purity is 99.9% are raw material, according to CoSb3Atom mass rate into
Row weighs, and carries out ground and mixed, and acetone is added in process of lapping；
Step 2: cold moudling
By powder cold moudling, pressure 8MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, controlling the vacuum degree in quartz ampoule is 10-3MPa or more, so
The quartz ampoule after sealing is placed in micro-wave oven by the dry pot of ceramics afterwards and carries out heating synthesis, green silicon carbide is placed inside dry pot
Asbestos are placed as microwave-assisted absorber, while around dry pot as thermal insulation material, and asbestos thickness is lower than dry pot height.This
The power that microwave heating is controlled in embodiment is 1000W, heating time 5min.
Step 4: second of raw material proportioning
200 mesh or more will be ground to after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weighs In
Powder and CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, the revolving speed for controlling ball-milling treatment is 230
Rev/min, then the sample after ball milling is carried out discharge plasma sintering by Ball-milling Time 6h, sintering temperature is 630 DEG C, heat preservation
Time 5min to get arrive InxCo4Sb12Skutterudite thermoelectric material.In conjunction with Fig. 1 it is found that the scheme using the present embodiment prepares gained
The diffraction peak-to-peak value shape of each crystal face of skutterudite is sharp clear, it may be said that bright prepared skutterudite sample purity is higher, system
Preparation Method is feasible.Meanwhile in conjunction with Fig. 2, the present embodiment preparation gained InxCo4Sb12Thermoelectricity of the skutterudite thermoelectric material in 773K
The figure of merit can reach 1.2, effectively increase the thermoelectric figure of merit of skutterudite thermoelectric material, to advantageously ensure that its application performance.Separately
Outside, using the two step synthesis technologies and microwave synthesis process of the present embodiment, additionally it is possible to effectively prevent growing up for crystal grain, and synthesize
It is easy to operate, it is high-efficient, it is easy to promote and utilize.
Embodiment 2
A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention, tool
Body the following steps are included:
Step 1: raw material preparation, mixing
With granularity for 400 mesh, Co, Sb elemental powders that purity is 99.9% are raw material, according to CoSb3Atom mass rate into
Row weighs, and carries out ground and mixed, and acetone is added in process of lapping；
Step 2: cold moudling
By powder cold moudling, pressure 6MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, controlling the vacuum degree in quartz ampoule is 10-3MPa or more, so
The quartz ampoule after sealing is placed in micro-wave oven by the dry pot of ceramics afterwards and carries out heating synthesis, green silicon carbide is placed inside dry pot
Asbestos are placed as microwave-assisted absorber, while around dry pot as thermal insulation material, and asbestos thickness is lower than dry pot height.This
The power that microwave heating is controlled in embodiment is 500W, heating time 8min.
Step 4: second of raw material proportioning
200 mesh or more will be ground to after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weighs In
Powder and CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, the revolving speed for controlling ball-milling treatment is 200
Rev/min, then the sample after ball milling is carried out discharge plasma sintering by Ball-milling Time 10h, sintering temperature is 620 DEG C, heat preservation
Time 6min to get arrive InxCo4Sb12Skutterudite thermoelectric material.
Embodiment 3
A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention, tool
Body the following steps are included:
Step 1: raw material preparation, mixing
With granularity for 400 mesh, Co, Sb elemental powders that purity is 99.9% are raw material, according to CoSb3Atom mass rate into
Row weighs, and carries out ground and mixed, and acetone is added in process of lapping；
Step 2: cold moudling
By powder cold moudling, pressure 9MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, controlling the vacuum degree in quartz ampoule is 10-3MPa or more, so
The quartz ampoule after sealing is placed in micro-wave oven by the dry pot of ceramics afterwards and carries out heating synthesis, green silicon carbide is placed inside dry pot
Asbestos are placed as microwave-assisted absorber, while around dry pot as thermal insulation material, and asbestos thickness is lower than dry pot height.This
The power that microwave heating is controlled in embodiment is 800W, heating time 6min.
Step 4: second of raw material proportioning
200 mesh or more will be ground to after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weighs In
Powder and CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, the revolving speed for controlling ball-milling treatment is 220
Rev/min, then the sample after ball milling is carried out discharge plasma sintering by Ball-milling Time 9h, sintering temperature is 635 DEG C, heat preservation
Time 46min to get arrive InxCo4Sb12Skutterudite thermoelectric material.
Embodiment 4
A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention, tool
Body the following steps are included:
Step 1: raw material preparation, mixing
With granularity for 400 mesh, Co, Sb elemental powders that purity is 99.9% are raw material, according to CoSb3Atom mass rate into
Row weighs, and carries out ground and mixed, and acetone is added in process of lapping；
Step 2: cold moudling
By powder cold moudling, pressure 7MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, controlling the vacuum degree in quartz ampoule is 10-3MPa or more, so
The quartz ampoule after sealing is placed in micro-wave oven by the dry pot of ceramics afterwards and carries out heating synthesis, green silicon carbide is placed inside dry pot
Asbestos are placed as microwave-assisted absorber, while around dry pot as thermal insulation material, and asbestos thickness is lower than dry pot height.This
The power that microwave heating is controlled in embodiment is 900W, heating time 7min.
Step 4: second of raw material proportioning
200 mesh or more will be ground to after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weighs In
Powder and CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, the revolving speed for controlling ball-milling treatment is 209
Rev/min, then the sample after ball milling is carried out discharge plasma sintering by Ball-milling Time 8.5h, sintering temperature is 628 DEG C, is protected
Warm time 5min to get arrive InxCo4Sb12Skutterudite thermoelectric material.
Embodiment 5
A kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite of the invention, tool
Body the following steps are included:
Step 1: raw material preparation, mixing
With granularity for 400 mesh, Co, Sb elemental powders that purity is 99.9% are raw material, according to CoSb3Atom mass rate into
Row weighs, and carries out ground and mixed, and acetone is added in process of lapping；
Step 2: cold moudling
By powder cold moudling, pressure 99MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, controlling the vacuum degree in quartz ampoule is 10-3MPa or more, so
The quartz ampoule after sealing is placed in micro-wave oven by the dry pot of ceramics afterwards and carries out heating synthesis, green silicon carbide is placed inside dry pot
Asbestos are placed as microwave-assisted absorber, while around dry pot as thermal insulation material, and asbestos thickness is lower than dry pot height.This
The power that microwave heating is controlled in embodiment is 1000W, heating time 4min.
Step 4: second of raw material proportioning
200 mesh or more will be ground to after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weighs In
Powder and CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, the revolving speed for controlling ball-milling treatment is 215
Rev/min, then the sample after ball milling is carried out discharge plasma sintering by Ball-milling Time 8h, sintering temperature is 628 DEG C, heat preservation
Time 6min to get arrive InxCo4Sb12Skutterudite thermoelectric material.
Claims (10)
1. a kind of method that two step of microwave fast heating-mechanical alloying is synthetically prepared high-performance skutterudite, it is characterised in that: will
Microwave fast heating technology is combined with mechanical alloying, and CoSb first is prepared using microwave heating3, then by CoSb3Powder with
Mechanical alloying processing is carried out after filling In powder mixing, is finally sintered again and CoSb is prepared3Based square cobalt mineral thermoelectricity
Material.
2. a kind of two step of microwave fast heating-mechanical alloying according to claim 1 is synthetically prepared high-performance skutterudite
Method, which is characterized in that specifically includes the following steps:
Step 1: raw material preparation, mixing
Using Co, Sb elemental powders as raw material, according to CoSb3Atom mass rate is weighed, and carries out ground and mixed, process of lapping
Middle addition acetone；
Step 2: cold moudling
By powder cold moudling, pressure 6-9MPa after acetone volatilizees completely；
Step 3: vacuum sealing, microwave heating
Sample after cold pressing is sealed in vitreosil pipe, is placed in micro-wave oven and carries out heating synthesis；
Step 4: second of raw material proportioning
It will be ground after sample comminution after synthesis, then according to InxCo4Sb12Atom mass rate weighs In powder and CoSb3Powder；
Step 5: mechanical alloying, sintering
Powder after proportion is placed in progress mechanical alloying processing in ball mill, then the sample after ball milling discharges etc.
Ion is sintered to arrive InxCo4Sb12Skutterudite thermoelectric material.
3. a kind of two step of microwave fast heating-mechanical alloying according to claim 2 is synthetically prepared high-performance skutterudite
Method, it is characterised in that: the power of the microwave heating be 500-1000W, heating time 4-8min.
4. a kind of two step of microwave fast heating-mechanical alloying according to claim 2 is synthetically prepared high-performance skutterudite
Method, it is characterised in that: in the step 5 revolving speed of ball-milling treatment be 200-230 revs/min, Ball-milling Time 6-10h, and
The vacuum degree of ball grinder is controlled 10-3MPa or more.
5. a kind of two step of microwave fast heating-mechanical alloying according to claim 2 is synthetically prepared high-performance skutterudite
Method, it is characterised in that: in the step 5 sintering temperature be 620-635 DEG C, soaking time 4-6min.
6. a kind of two step of microwave fast heating-mechanical alloying according to any one of claim 2-5 is synthetically prepared height
The method of performance skutterudite, it is characterised in that: the granularity of Co, Sb elemental powders is 400 mesh in the step 1, and purity is
99.9%；In the step 4 200 mesh or more will be ground to after the sample comminution after synthesis.
7. a kind of two step of microwave fast heating-mechanical alloying according to any one of claim 2-5 is synthetically prepared height
The method of performance skutterudite, it is characterised in that: guarantee that the vacuum degree in quartz ampoule is 10 in the step 3-3MPa or more.
8. a kind of two step of microwave fast heating-mechanical alloying according to claim 7 is synthetically prepared high-performance skutterudite
Method, it is characterised in that: in the microwave heating synthesis process, the quartz ampoule after sealing is placed in ceramic crucible, crucible
Place microwave-assisted absorber in inside.
9. a kind of two step of microwave fast heating-mechanical alloying according to claim 8 is synthetically prepared high-performance skutterudite
Method, it is characterised in that: the microwave-assisted absorber use green silicon carbide.
10. a kind of two step of microwave fast heating-mechanical alloying according to claim 8 is synthetically prepared high-performance skutterudite
Method, it is characterised in that: around crucible place asbestos as thermal insulation material, with a thickness of 50-100mm.
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