CN106191522A - A kind of laser efficiently prepares the method for skutterudite thermoelectric material - Google Patents
A kind of laser efficiently prepares the method for skutterudite thermoelectric material Download PDFInfo
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- CN106191522A CN106191522A CN201610545800.0A CN201610545800A CN106191522A CN 106191522 A CN106191522 A CN 106191522A CN 201610545800 A CN201610545800 A CN 201610545800A CN 106191522 A CN106191522 A CN 106191522A
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- 238000002360 preparation method Methods 0.000 claims abstract description 32
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- 238000005266 casting Methods 0.000 claims abstract description 22
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- 239000007789 gas Substances 0.000 claims description 16
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- 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
- B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
- B22F12/40—Radiation means
- B22F12/41—Radiation means characterised by the type, e.g. laser or electron beam
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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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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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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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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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- 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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Abstract
The present invention relates to a kind of method that laser efficiently prepares skutterudite thermoelectric material, including: 1) according to the chemical formula of skutterudite thermoelectric material, weigh the powder body of elemental metals as material powder, uniformly mixing is placed in graphite matrix；2) graphite matrix that will be equipped with material powder is placed in inert atmosphere, uses lf technology heating material powder, and along with the movement of laser facula, the melted condensation subsequently of material powder obtains ingot casting；3) by step 2) the ingot casting grind into powder prepared, discharge plasma sintering ingot casting powder, obtain described skutterudite thermoelectric material.The present invention utilizes superlaser heating local powder body realize Flashmelt and reduce the loss of Sb phase, and low capacity melt rapid condensation realizes the reduction of segregation size subsequently.Follow-up combination SPS short time Technology for Heating Processing, it is achieved the efficient preparation of skutterudite thermoelectric material.
Description
Technical field
The invention belongs to new energy materials field, relate to a kind of method efficiently preparing skutterudite thermoelectric material.
Background technology
Thermoelectric generation utilizes the Seebeck effect of semi-conducting material directly to convert heat energy into electric energy, has system body
The feature such as long-pending little, compact conformation, no-movable part, non-maintaining, noiselessness, and life-span length high without discharge, reliability, visits at deep space
Survey and obtain important application on power supply and extraordinary Military Power, at solar photoelectric-thermoelectricity compound power-generating, the remaining used heat of industry
Particularly waste heat of automotive exhaust gas recovery thermo-electric generation aspect has broad application prospects and potential economic and social benefits, and having can
The important component part (Science 283:804,1999) of world today's energy crisis solution can be become.
The conversion efficiency of thermoelectric of thermo-electric generation system depends on the performance of thermoelectric semiconductor material, leads to the immeasurable of common used material
Guiding principle performance figure of merit ZT characterizes, ZT=α2σ T/ κ, α are Seebeck coefficients, and σ is electrical conductivity, and T is operating temperature, and κ is thermal conductivity.
Thermoelectric material of good performance should have high power factor (α2σ) and lower thermal conductivity.But, due to thermoelectricity parameter (α, σ, κ)
Interrelated, it is difficult to optimize obtain high zt, so the ZT value of the thermoelectric material of actual application is about 1 simultaneously.CoSb3Base side
Cobalt ore is an apoplexy due to endogenous wind temperature (～600 DEG C) high performance thermoelectric material, and has good high-temperature stability and machinability, is recognized
For being the thermoelectric material being most possibly applied to the remaining Waste Heat Recovery thermo-electric generation of the industry such as vehicle exhaust.
In recent years, for skutterudite preparation means, there is correlational study report.One is direct mechanical alloying,
(CN02147869) disclosing one, to utilize high-energy ball milling (180～350r/min, 8～11h) to combine short time high temperature annealing treatment
The method that reason (650 DEG C～750 DEG C, 1～3h) prepares skutterudite, when shortening high temperature isothermal annealing by pre-mechanical alloying
Between, reduce production cost.From thermodynamic (al) angle, but ma process is CoSb3Formed mutually and decompose the most competing
The process striven, has the existence of impurity peaks all the time, and utilizes the preparation of this method to there is the risk introducing abrasive media.Document recently
(Journal of Materials Chemistry A 2 (2014) 17914) reports and utilizes the method for self-propagating quickly to prepare
Thermoelectric material.This method is in bulk of first being colded pressing by the powder body sample of certain stoichiometric proportion, lights in one end subsequently, utilizes between element
The heat of chemical reaction release maintains the transmission of combustion wave, makes overall specimen reaction, obtains material requested.This method is no doubt simple,
Required energy input is also only initial end and lights, but local response sintering is it is difficult to ensure that the uniformity of overall composition, and side
Adiabatic temperature (the T of cobalt ore reactionad) less than low melting point phase (Tm,L) fusing point, with (the Nature Communication of document before
5 (2014) 4908) maintenance reaction criterion T proposedad/Tm,L＞ 1 is not inconsistent.Additionally since factors such as kinetics of diffusions, utilize simple substance
Co and simple substance Sb is difficult to be directly synthesized and obtains CoSb3Pure phase, and sample needs pre-molding, so initial powder is required ratio
Higher.
Utilizing liquid phase melted is also a kind of traditional preparation method with after-baking to obtain skutterudite mutually.The system of skutterudite
Standby generally with the high-purity elemental metals of certain stoichiometric proportion as raw material, melted in the environment of vacuum or inert atmosphere,
Each element is made uniformly to mix, subsequently rapid quenching condensation, the uniform admixture (Co-Sb of atom when retaining high temperature as far as possible
Phasor, needs to experience two peritectic reaction processes mutually from melt cooling formation skutterudite and there is a certain degree of peritectoid segregation), then
End product is obtained through subsequent heat treatment.Therefore after cooling, the peritectoid segregation yardstick of ingot casting determines the difficulty or ease forming skutterudite
Degree and the uniformity of filling atom distribution, document (Journal of Electronic Materials 44 (2015) 1890-
1895) showing, the Co-Sb peritectoid segregation effect produced in During Quenching will be inherited in preparation process subsequently, becomes
One very important influence factor of microstructure evolution.Comparing little melt volume samples, big melt volume samples segregation degree is relatively
For seriously, segregation yardstick increases, it means that will increase the expansion of component (Yb, Co, and Sb) in the technique of after annealing
Dissipate journey, hinder the formation of single filled skutterudite phase, remaining CoSb2, YbSb2Deng dephasign, cause the reduction of final thermoelectricity capability.
Utilizing increases subsequent heat treatment time and temperature and increases atoms permeating activation energy to eliminate segregation, is power consumption poor efficiency, increases system
The behavior of standby cost.Therefore, in exploitation large-scale production process, how controlling Co-Sb peritectoid segregation will be the key prepared.
Melted rotation is got rid of technique and is achieved the mixing of element even in liquid phase and that Large Copacity melt cooling is changed into continuous line is cold
Solidifying, obtain amorphous and nanocrystal gets rid of band.Later use discharge plasma sintering technique (SPS) synthesis skutterudite phase.Patent
(CN101435029) a kind of method preparing Yb filled skutterudite material is disclosed, 20～30 hours quenching preparation mothers of melted synthesis
Alloy, is then placed in foundry alloy melt rotation and gets rid of in equipment, sensing heating remelting, and melt rotation is got rid of, and obtains amorphous/nanocrystalline and is combined
The strand of product of structure, powder process tabletting, subsequently SPS (550 DEG C, be incubated 5min), it is thus achieved that N-shaped Yb filled skutterudite maximum ZT value reaches
To 1.3.Patent (CN101693962) discloses the preparation method of a kind of p-type filled skutterudite material, weighs simple substance in glove box
Raw material, encapsulates tabletting, is placed in melt rotation and gets rid of in equipment, high-frequency induction heating～5 seconds, repeats to ensure that bath composition is equal for 3～5 times
. even, melt rotation is got rid of, and obtains the strand of product of amorphous/nanocrystalline composite construction, powder process tabletting, subsequently SPS (530 DEG C, insulation
5min), it is thus achieved that pure phase block materials；These two kinds of methods are required to the melt rotation of costliness and get rid of equipment, and foundry alloy reflow process
In be sample to be carried out entirety add heat fusing, there is bigger Sb phase and volatilize, be difficult to accurately control when carrying out scale and preparing
The component content of final block sample, causes material property to fluctuate.
Summary of the invention
For the problems referred to above, the invention provides a kind of composition controlled, preparation cost is low, the efficient preparation side cobalt that the cycle is short
The method of ore deposit thermoelectric material.
To this end, the invention provides a kind of method that laser efficiently prepares skutterudite thermoelectric material, including:
1) according to the chemical formula of skutterudite thermoelectric material, the powder body of weighing elemental metals is as material powder, and uniformly mixing is rearmounted
In graphite matrix；
2) graphite matrix that will be equipped with material powder is placed in inert atmosphere, uses lf technology heating material powder, with
The movement of laser facula, the melted condensation subsequently of material powder obtains ingot casting；
3) by step 2) the ingot casting grind into powder prepared, discharge plasma sintering ingot casting powder, obtain described skutterudite thermoelectric
Material.
The present invention utilizes superlaser heating local powder body realize Flashmelt and reduce the loss of Sb phase；Low capacity subsequently
Melt rapid condensation realizes the reduction of segregation size.Follow-up combination SPS short time Technology for Heating Processing, it is achieved skutterudite thermoelectric material
Efficient preparation.The technique that the preparation of the present invention is sintered by batch mixing, lf and SPS realizes.Wherein lf is sharp
Hot spot bundle size is less, forms molten bath less, it is ensured that composition is controlled.Graphite matrix quick conductive obtains the casting that organizational structure is tiny
Ingot.Low capacity melt process effectively suppresses the volatilization loss of Sb element.Use discharge plasma sintering, utilize powder body to react
Quickly form skutterudite phase, be greatly shortened heat treatment time.
It is preferred that described skutterudite thermoelectric material includes CoSb3, doping CoSb3Based compound and filling CoSb3Base
Compound.
It is preferred that the size of described material powder is 200 mesh.
It is preferred that described graphite matrix has the matrix groove that the degree of depth is 0.5mm～2mm.
It is preferred that described inert atmosphere is at least one in argon, hydrogen, helium.
It is preferred that the technological parameter of described lf technology includes: the output power of heated light sources 150～
200W, hot spot rate travel is 100～150mm/min, and multiple tracks spacing is 3.75～4mm.
Also, it is preferred that described heated light sources is Nd-YAG lasing light emitter, CO2Lasing light emitter or fiber optic laser source.
It is preferred that the technological parameter of described discharge plasma sintering includes: vacuum ＜ 10Pa, heating rate 80～120
DEG C/min, and sintering temperature 580～620 DEG C, temperature retention time 5～10min, sintering pressure 40～50MPa.
The invention has the beneficial effects as follows: lf method can effectively reduce segregation yardstick, eliminate long-time melted, annealing
Operation, sample directly utilizes SPS sintering preparation subsequently, substantially reduces manufacturing cycle, reduces energy consumption, from traditional melted conjunction
More than 10 day of one-tenth-quenching-annealing-sintering preparation method, shortens to (include weighing, lf, powder process and sintering nearly half an hour
Time).Prepare simultaneously and there is not encapsulation link, can effectively reduce the consumption of encapsulating material, reduce preparation cost.Revolve with melt
Get rid of and combine discharge plasma sintering method and prepare filled skutterudite material and compare, inventive process avoids a large amount of Sb phase and volatilize,
It is more easily controlled composition, relatively low to equipment requirements.In sum, the present invention is that the cycle is short, efficiency is high, processability for one
Stable skutterudite material preparation method.
Accompanying drawing explanation
Fig. 1 is the system schematic that in the present invention, laser efficiently prepares skutterudite thermoelectric material；
Fig. 2 is the process chart that in the present invention, laser efficiently prepares skutterudite thermoelectric material；
Fig. 3 is the XRD figure spectrum of the skutterudite block materials of preparation in embodiment of the present invention 1-3；
Fig. 4 is the thermoelectricity capability figure of merit figure in embodiment of the present invention 1-3 under the different temperatures of the skutterudite block materials of preparation.
Detailed description of the invention
The present invention is further illustrated, it should be appreciated that following embodiment is merely to illustrate this below by way of following embodiment
Invention, and the unrestricted present invention.
The present invention utilizes the lasing light emitter of movement as energy input, it is achieved the Flashmelt of powder body and condensation, followed by
SPS sintering technology carries out short time heat treatment and obtains skutterudite phase.During efficiently preparing skutterudite thermoelectric material, key exists
In the segregation phenomena (can effectively shorten subsequent heat treatment skutterudite and be combined to the time) controlled in preparation process, and reduce preparation
During the loss (controlling stablizing of final composition) of element.
Heretofore described skutterudite thermoelectric material includes: CoSb3, doping CoSb3Based compound (such as, tellurium doping side
Cobalt ore CoTe0.15Sb2.85Deng) and fill CoSb3Based compound (such as, indium filled skutterudite In0.1Co4Sb12Deng).The example below
Property the laser method of efficiently preparing skutterudite thermoelectric material that provides of the ground explanation present invention, see Fig. 2.
According to the chemical formula of skutterudite thermoelectric material, the powder body of weighing elemental metals is as material powder, uniformly after mixing
It is placed in graphite matrix.Wherein, the size of described material powder substantially 200 mesh (that is, material powder is crossed the sieve of 200 mesh).
This sized powder is prone to lf and becomes liquid phase, and contributes to the uniformity of reaction.There is the base of different depth in graphite matrix
Body groove, for different melting points material, the depth bounds of matrix groove can be 0.5mm～2mm.Specifically, stoichiometrically claim
Amount skutterudite material simple substance powder stock, utilizes Achates to grind alms bowl and carries out long-time hand lapping, cross the sieve of 200, it is ensured that initial
Powder mix homogeneously.Subsequently by mixed uniformly powder body spreading in the graphite matrix groove with certain depth.Show as one
Example, the present invention, with Co, Sb, Te, In element simple substance powder body as initial feed, measures ratio dispensing according to corresponding chemical, utilizes Achates
Grind alms bowl uniformly to be mixed by powder body, and insert in the graphite matrix that groove depth is 1mm.
The graphite matrix that will be equipped with material powder is placed in inert atmosphere, uses lf technology heating material powder,
Along with the movement of laser facula, the melted condensation subsequently of material powder obtains ingot casting.Wherein, described inert atmosphere can be argon, hydrogen
At least one in gas, helium.Regulation laser technical parameters, utilizes lf powder body, along with laser facula moves, and melted powder
Body solidifies.Due to above-mentioned melt supercooled (104～105K/s), after condensation, ingot casting grain structure is tiny, and segregation size is effectively controlled
System.Various sample segregation adjoining dimensions, about 10 μm, overall shrend condensation sample (that is, ingot casting) much smaller than in traditional handicraft.Institute
The technological parameter stating lf technology includes: the output power of heated light sources is 150～200W.Hot spot rate travel can
It is 100～150mm/min.Multiple tracks spacing can be 3.75～4mm.Preferably, heated light sources can be Nd-YAG lasing light emitter, CO2Swash
Light source or fiber optic laser source etc..As an example, laser processing technology parameter is, mean power: 150W, linear velocity V:
100mm/min, way spacing are 3.75mm.
Seeing Fig. 1, specifically, the graphite matrix that will be equipped with material powder is placed in process chamber, first with indifferent gas
(such as, gas washing atmosphere can be Ar+H to body2Gas, it is also possible to be the noble gases such as Ar gas, He gas) to process chamber gas washing 3 repeatedly
Secondary.Continuous aeration subsequently, it is ensured that inside cavity is in barotropic state (such as 0.12MPa).Lf process is in full inertia
Carry out in the self-built cavity of gas (such as, argon hydrogen protective atmosphere), utilize LASER HEATING to melt powder body.Noble gas can be effective
Ensureing that sample (material powder) is not oxidized when high-temperature fusion, secondly in cavity, barotropic state can ensure that cavity air-tightness,
Outside air cannot affect processing atmosphere.The laser technical parameters of regulation laser instrument, selects proper laser average output power, profit
With reflecting mirror, Laser Processing path is set.On the premise of suitably working process parameter can volatilize reducing Sb phase as far as possible,
Realize the molten homogeneous of a small amount of skutterudite powder body material.Recycling digital control system and monitoring position control coaxially to work head (laser
Speckle) rate travel.Along with laser facula moves, powder body melting rapid condensation subsequently, rapid condensation can effectively control condensation
The peritectoid segregation yardstick of tissue sample.
By above-mentioned condensation sample (ingot casting) grinding flour, suitable SPS technique is used to sinter, the side of being simultaneously achieved in the short time
The synthesis of cobalt ore thermoelectric material and densification process, substantially reduce manufacturing cycle.That is, the solidification sample (casting obtained after melting
Ingot) ground Cheng Fenhou use discharge plasma sintering technique (SPS) prepare compact block material.Wherein said plasma discharging
The technique of sintering includes: vacuum is about 10Pa, and heating rate 80～120 DEG C/min, sintering temperature 580～620 DEG C, during insulation
Between 5～10min, sintering pressure 40～50MPa.As an example, sintering process uses graphite jig to be sintered, sintering temperature
Degree is 600 DEG C, and heating rate is about 100 DEG C/min, and pressure is 40～50Mpa, left at sintering temperature heat-insulation pressure keeping 5～10min
Right.
The method that the laser that the present invention provides efficiently prepares skutterudite thermoelectric material, the method is by lf and electric discharge etc.
Ion sintering (SPS) technique composition, has composition controlled, and preparation cost is low, the feature that the cycle is short.The method can effectively realize
Prepared by binary skutterudite phase and ternary doping and the efficient of filled skutterudite phase, it is thus achieved that single skutterudite phase block thermoelectricity material
Material.Utilize CoTe prepared by the method for the invention0.15Sb2.85The ZT value of material when 800K near can reach more than 1, meet
The requirement of the actual application of thermoelectric material, has fabulous prospects for commercial application.
Enumerate embodiment further below to describe the present invention in detail.It will similarly be understood that following example are served only for this
Invention is further described, it is impossible to being interpreted as limiting the scope of the invention, those skilled in the art is according to this
Some nonessential improvement and adjustment that bright foregoing is made belong to protection scope of the present invention.Following example is concrete
Technological parameters etc. are the most only that an example in OK range, i.e. those skilled in the art can be done properly by explanation herein
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Skutterudite (CoSb3) thermoelectric material lf/SPS fast preparation method, specifically comprise the following steps that
(1) with 200 mesh sieve powders Co, Sb simple substance excessively as raw material, by chemical formula CoSb3Weigh；Raw material will be weighed and grinding alms bowl
Interior uniformly mixing, powder body is laid in the graphite matrix that the degree of depth is 1mm subsequently, is placed in process chamber；
(2) utilizing argon hydrogen gaseous mixture to process chamber gas washing, 3 times repeatedly, final cavity internal gas pressure is 0.12MPa；
(3) regulation laser technical parameters, utilizes lf powder body, along with laser facula moves, and melted powder body solidification；Due to upper
State melt supercooled (104～105K/s), after condensation, ingot casting grain structure is tiny, and segregation size is effectively controlled.Various sample is inclined
Analysis adjoining dimensions, about 10 μm, the overall shrend condensation sample much smaller than in traditional handicraft；Laser processing technology parameter is, averagely
Power: 150W, linear velocity V:100mm/min, way spacing are 3.75mm；
(4) above-mentioned ingot casting powder process, powder body is placed in graphite jig, uses discharge plasma sintering method to sinter in a vacuum, very
Reciprocal of duty cycle is～10Pa, sintering temperature～600 DEG C, sintering pressure 45MPa, sintered heat insulating time～5min, it is thus achieved that fine and close CoSb3Side
Cobalt ore thermoelectric material.
Embodiment 2
Tellurium doping skutterudite (is represented by CoSb2.85Te0.15、Te0.15CoSb2.85Or CoTe0.15Sb2.85) thermoelectric material laser melt
Melt/SPS fast preparation method, specifically comprise the following steps that
(1) with 200 mesh sieve powders Co, Sb, Te simple substance excessively as raw material, by chemical formula CoTe0.15Sb2.85Weigh；To weigh former
Expecting uniformly to mix in grinding alms bowl, powder body is laid in the graphite matrix that the degree of depth is 1mm subsequently, is placed in process chamber；
(2) utilizing argon hydrogen gaseous mixture to process chamber gas washing, 3 times repeatedly, final cavity internal gas pressure is 0.12MPa；
(3) regulation laser technical parameters, utilizes lf powder body, along with laser facula moves, and melted powder body solidification；Due to upper
State melt supercooled (104～105K/s), after condensation, ingot casting grain structure is tiny, and segregation size is effectively controlled.Various sample is inclined
Analysis adjoining dimensions, about 10 μm, the overall shrend condensation sample much smaller than in traditional handicraft；Laser processing technology parameter is, averagely
Power: 150W, linear velocity V:100mm/min, way spacing are 3.75mm；
(4) above-mentioned ingot casting powder process, powder body is placed in graphite jig, uses discharge plasma sintering method to sinter in a vacuum, very
Reciprocal of duty cycle is～10Pa, sintering temperature～600 DEG C, sintering pressure 45MPa, sintered heat insulating time～5min, it is thus achieved that fine and close
CoTe0.15Sb2.85Skutterudite thermoelectric material.
Embodiment 3
Indium filled skutterudite (In0.1Co4Sb12) thermoelectric material lf/SPS fast preparation method, specifically comprise the following steps that
(1) with 200 mesh sieve powders Co, Sb, In simple substance excessively as raw material, by Formula I n0.1Co4Sb12Weigh.Raw material will be weighed
Uniformly mixing in grinding alms bowl, powder body is laid in the graphite matrix that the degree of depth is 1mm subsequently, is placed in process chamber；
(2) utilizing argon hydrogen gaseous mixture to process chamber gas washing, 3 times repeatedly, final cavity internal gas pressure is 0.12MPa；
(3) regulation laser technical parameters, utilizes lf powder body, along with laser facula moves, and melted powder body solidification；Due to upper
State melt supercooled (104～105K/s), after condensation, ingot casting grain structure is tiny, and segregation size is effectively controlled.Various sample is inclined
Analysis adjoining dimensions, about 10 μm, the overall shrend condensation sample much smaller than in traditional handicraft；Laser processing technology parameter is, averagely
Power: 150W, linear velocity V:100mm/min, way spacing are 3.75mm；
(4) above-mentioned ingot casting powder process, powder body is placed in graphite jig, uses discharge plasma sintering method to sinter in a vacuum, very
Reciprocal of duty cycle is～10Pa, sintering temperature～600 DEG C, sintering pressure 45MPa, sintered heat insulating time～5min, it is thus achieved that fine and close
In0.1Co4Sb12Skutterudite thermoelectric material.
The powder x-ray diffraction analysis result of sintered body is as it is shown on figure 3, this result shows either binary skutterudite
CoSb3, or ternary In fill, and Te doping skutterudite all obtain single skutterudite phase.
The present invention records Seebeck coefficient and the conductance of the skutterudite thermoelectric material of preparation in embodiment 1-3 by ZEM-3
Rate.The present invention records the thermal conductivity of the skutterudite thermoelectric material of preparation in embodiment 1-3 by LFA-427.As shown in table 1:
Seebeck coefficient, electrical conductivity and thermal conductivity under skutterudite thermoelectric material room temperature prepared in table 1 embodiment 1-3
The present invention, by the Seebeck coefficient of gained skutterudite thermoelectric material, electrical conductivity and thermal conductivity, utilizes formula ZT=
α2σ T/ κ, calculates the ZT value of skutterudite thermoelectric material, as shown in Figure 4.In fills sample and Te doping sample than pure side's cobalt
Ore deposit phase thermoelectricity capability has had bigger lifting, wherein, CoSb2.85Te0.15Doping sample ZT maximum has reached 1.05@800K, this property
The requirement of the actual application of material can be met.
Claims (8)
1. the method that a laser efficiently prepares skutterudite thermoelectric material, it is characterised in that including:
1) according to the chemical formula of skutterudite thermoelectric material, the powder body of weighing elemental metals is as material powder, and uniformly mixing is rearmounted
In graphite matrix；
2) graphite matrix that will be equipped with material powder is placed in inert atmosphere, uses lf technology heating material powder, with
The movement of laser facula, the melted condensation subsequently of material powder obtains ingot casting；
3) by step 2) the ingot casting grind into powder prepared, discharge plasma sintering ingot casting powder, obtain described skutterudite thermoelectric
Material.
Preparation method the most according to claim 1, it is characterised in that described skutterudite thermoelectric material includes CoSb3, doping
CoSb3Based compound and filling CoSb3Based compound.
Preparation method the most according to claim 1 and 2, it is characterised in that the size of described material powder is 200 mesh.
4. according to the preparation method according to any one of claim 1-3, it is characterised in that described graphite matrix has the degree of depth and is
The matrix groove of 0.5mm～2mm.
5. according to the preparation method according to any one of claim 1-4, it is characterised in that described inert atmosphere is argon, hydrogen
At least one in gas, helium.
6. according to the preparation method described in any one of claim 1-5 1, it is characterised in that the work of described lf technology
Skill parameter includes: the output power of heated light sources is 150～200W, and hot spot rate travel is 100～150mm/min, many
Road spacing is 3.75～4mm.
Preparation method the most according to claim 6, it is characterised in that described heated light sources is Nd-YAG lasing light emitter, CO2Swash
Light source or fiber optic laser source.
8. according to the preparation method according to any one of claim 1-7, it is characterised in that the work of described discharge plasma sintering
Skill parameter includes: vacuum ＜ 10Pa, heating rate 80～120 DEG C/min, sintering temperature 580～620 DEG C, temperature retention time 5～
10min, sintering pressure 40～50MPa.
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