CN108963064B - Hot pressed sintering device, the block thermoelectric material of micro-nano porous structure and its preparation method - Google Patents
Hot pressed sintering device, the block thermoelectric material of micro-nano porous structure and its preparation method Download PDFInfo
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Abstract
The present invention provides a kind of hot pressed sintering devices, it includes top electrode, lower electrode, water-cooled vacuum room and set of molds, wherein set of molds includes die main body, seaming chuck and push-down head, die main body has the through-hole of short transverse, and the sum of seaming chuck and the height of push-down head are less than the height of die main body；When work, set of molds is placed in water-cooled vacuum room, seaming chuck and the through-hole of push-down head press-in die main body until seaming chuck and push-down head are concordant with the upper surface of die main body and lower end surface respectively, are formed the sample room for accommodating sample by top electrode and lower electrode in the through-hole of die main body.It is Mg the invention further relates to the method for preparing thermoelectric material using above-mentioned apparatus and chemical formula3.2‑xMnxSb1.5‑yBi0.5TeyMultiple dimensioned micro-nano porous structure thermoelectric material, wherein 0.0125≤x≤0.1,0.01≤y≤0.05.
Description
Technical field
The invention belongs to thermoelectric material fields.In particular it relates to a kind of hot pressed sintering device, micro-nano porous structure
Block thermoelectric material and micro-nano porous structure block thermoelectric material preparation method.
Background technique
Thermoelectric material is a kind of functional material that can be realized thermal energy and electric energy and directly mutually convert, and has light weight, body
The small, structure of product is simple, noiseless, zero-emission and the advantages that long service life.This is to solution energy crisis and environmental pollution day
The problems such as beneficial severe and the environmentally protective new energy materials of research and development bring hopes, and thermoelectric material is also therefore to receive the world each
The great attention of state.
With the development of the design concept and new process, technology of new material, thermoelectric material is had been achieved with from traditional tool
Have single scale and simple component it is inefficient can (thermoelectric figure of merit ZT≤1) to multiple dimensioned and with complex component and defect type
High performance thermoelectric material transformation, and thermoelectricity capability (thermoelectric figure of merit ZT) gradually rises in recent ten years, certain material systems
ZT peak value has been approached or reaches about 2.5 level.But by most material systems it is flat within the scope of military service warm area
Equal thermoelectric figure of merit ZTavg(or holography ZT value) is still lower, and especially in the ZT value of room temperature generally less than 1, this directly leads material
The low problem of pyrogenicity electrical part transfer efficiency, seriously constrains the promotion and application of thermoelectric energy conversion technology.
Want the conversion efficiency of thermoelectric of raising material, it is necessary to transport and decouple to electroacoustic in thermoelectric figure of merit, realize institute
" electron crystal, phonon glasses " material of meaning, this is also the difficult point and core of thermoelectric material research.Regulation in terms of material electricity
Closely related with the electronic structure near Fermi surface, under small temperature (or energy) disturbance, be excited the load for participating in transporting
It is higher to flow sub- concentration, is more conducive to thermoelectricity and transports.In terms of lattice, by multiple dimensioned crystal structure defects for example point defect, dislocation,
Grain boundary density and superlattices effect, to high frequency and in, low frequency phonon be scattered, reduce material thermal conductivity.The reason is that,
The mean free path (λ e) of carrier transport is less than the mean free path (λ p) of phonon vibration, and multiple dimensioned crystal structure defects utilize
The two difference realizes the decoupling that electroacoustic transports, to effectively improve material entirety thermoelectric figure of merit.
It is analyzed from thermoelectricity transport theory, it is to improve thermoelectric material that preparing, which has the thermoelectric material of the porous structure of micro/nano-scale,
The effective way of performance.The preparation method of existing multiple dimensioned micro-nano porous structure thermoelectric material generallys use following means to produce
Raw hole: (1) by adminiclies such as aggressive agent, pore forming agents material is made to generate hole；(2) by thermoelectric material matrix and nanotube etc.
The compound generation hole of porous material；(3) material internal component volatilization is made to generate hole by long term annealing.However, in this way
Most of method there are universality difference and it is more time-consuming the defects of.
For example, Chinese patent application 200910092656.X discloses a kind of preparation of bismuth-tellurium nano-porous thermoelectric material
Method.However, method disclosed in Chinese patent application 200910092656.X is needed using pore forming agent to form hole, and
This method operating procedure is complicated, can be only applied to bismuth tellurium pyroelectric material system, cannot put into application extensively.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of hot pressing for limitation and defect disadvantage present in the prior art
Sintering equipment, the block thermoelectric material of micro-nano porous structure and a kind of preparation side of the block thermoelectric material of micro-nano porous structure
Method, wherein the block thermoelectric material has multiple dimensioned micro-nano porous structure.
The purpose of the present invention is what is be achieved through the following technical solutions.
On the one hand, the present invention provides a kind of hot pressed sintering device, described device includes that top electrode, lower electrode, water cooling are true
Empty room and set of molds, wherein the set of molds includes die main body, seaming chuck and push-down head, and the die main body has height
The sum of height of the through-hole in direction and the seaming chuck and the push-down head is less than the height of the die main body；
When work, the set of molds is placed in the water-cooled vacuum room, the top electrode and the lower electrode will be described on
Pressure head and the push-down head be pressed into the through-hole of the die main body until the seaming chuck and the push-down head respectively with the mould
The upper surface for having main body is concordant with lower end surface, and the sample room for accommodating sample is formed in the through-hole of the die main body.
Hot pressed sintering device provided by the invention can be used for preparing the block thermoelectric material of multiple dimensioned micro-nano porous structure.
Particularly, present inventor has found unexpectedly, can by be arranged seaming chuck and push-down head height, make seaming chuck and
The sum of height of push-down head is less than the height of die main body, and then in the work of hot pressed sintering device, under heating pressurization, powers on
Pole and lower electrode will form sample room in seaming chuck and the through-hole of push-down head press-in die main body and in through-holes, when top electrode and
Lower electrode directly or indirectly contacts die main body, and (i.e. seaming chuck and push-down head are flat with the upper surface of die main body and lower end surface respectively
When together), upper push-down head can not continue to move into through-hole, so that the thickness (i.e. volume) of sample is effectively controlled, and then
To the sample of desired consistency.
The hot pressed sintering device provided according to the present invention, wherein the hot pressed sintering device is heat isostatic apparatus, direct current
Electric heating pressure device or discharge plasma sintering device.
In preferred embodiments, the hot pressed sintering device be discharge plasma sintering device, it is described electric discharge etc. from
Sub- sintering equipment includes top electrode, lower electrode, water-cooled vacuum room and set of molds, wherein the set of molds include die main body, on
Pressure head, push-down head, upper insulating layer and lower insulating layer, the die main body have the through-hole and the seaming chuck of short transverse
It is less than the sum of the upper insulating layer, the die main body and height of the lower insulating layer with the sum of the height of the push-down head；
When work, the set of molds is placed in the water-cooled vacuum room, the upper insulating layer and the lower insulating layer difference
It is placed in the upper surface and lower end surface of the die main body, the top electrode and the lower electrode are by the seaming chuck and the pushing
Head be pressed into the through-hole of the die main body until the seaming chuck and the push-down head respectively with the upper insulating layer and it is described under
Insulating layer is concordant, and the sample room for accommodating sample is formed in the through-hole of the die main body.
Discharge plasma sintering device provided by the invention is used in particular for preparing the block heat of multiple dimensioned micro-nano porous structure
Electric material.Particularly, present inventor has found unexpectedly, can be made by the height of setting seaming chuck and push-down head
The sum of height of seaming chuck and push-down head is less than the sum of upper insulating layer, die main body and height of lower insulating layer, and then is discharging
When plasma agglomeration device works, under heating pressurization, top electrode and lower electrode are by seaming chuck and push-down head press-in die main body
Through-hole in and form sample room in through-holes, when top electrode and lower electrode directly or indirectly contact upper and lower insulating layer (i.e. upper pressure
Head and push-down head are concordant with upper insulating layer and lower insulating layer respectively) when, upper push-down head can not continue to move into through-hole, so that sample
The thickness (i.e. volume) of product is effectively controlled, and then obtains the sample of desired consistency.Simultaneously as upper and lower insulating layer
Presence, will not change by the current density of sample, ensure that the abundant sintering of sample, better performances can be obtained
Sample.
The device provided according to the present invention, wherein the seaming chuck, the push-down head and the die main body can be by gold
Belong to, alloy or graphite are made.The example of suitable metal includes but is not limited to: iron, aluminium and copper.The example of suitable alloy includes
But it is not limited to aluminium alloy, stainless steel and diamondite.
In some preferred embodiments, the seaming chuck and the push-down head are graphite rod, and the die main body is
Graphite jig main body.
The device provided according to the present invention, wherein the upper insulating layer and the lower insulating layer are silica wool.Present invention choosing
It uses silica wool as insulating layer, the upper and lower end face of upper/lower electrode and die main body can not only be insulated well, but also can play
The effect of heat preservation is conducive to the preferable sample of processability.
The device provided according to the present invention, wherein the apparatus may include 2 graphite plates, the graphite plate is set respectively
It sets between seaming chuck and upper insulating layer between push-down head and lower insulating layer.In this case, the top electrode and it is described under
After the seaming chuck and the push-down head are pressed into the through-hole of the die main body by electrode, the top electrode and upper insulating layer and
The lower electrode contradicts indirectly with the lower insulating layer.
The device provided according to the present invention, wherein described device can also be not provided with graphite plate.In this case, described
After the seaming chuck and the push-down head are pressed into the through-hole of the die main body by top electrode and the lower electrode, the top electrode
It is directly contradicted with upper insulating layer and the lower electrode with the lower insulating layer.
The device provided according to the present invention, wherein described device can also include hot pressed sintering device such as conventional discharge
Other component used in plasma agglomeration.In some embodiments, the other component includes but is not limited to: power supply and
DC current generator or impulse current generator.
On the other hand, the present invention provides a kind of preparation method of the block thermoelectric material of multiple dimensioned micro-nano porous structure,
The described method includes: being carried out using hot pressed sintering device provided by the invention such as discharge plasma sintering device to raw material powder
Sintering, to obtain the block thermoelectric material of multiple dimensioned micro-nano porous structure.
The method provided according to the present invention, wherein by adjusting the amount of raw material powder be added and/or changing seaming chuck
And/or the height of push-down head carrys out the consistency of control block thermoelectric material.
The method provided according to the present invention, wherein the consistency of the thermoelectric material is 60%~100%.In some realities
It applies in scheme, it is in some embodiments 70%~90%, Yi Ji that the consistency of the thermoelectric material, which is 70%~95%,
It is 80%~90% in some embodiments.
The preparation method provided according to the present invention, wherein the thermoelectric material is that N-shaped Mn adulterates Mg3Sb2Material, such as
Half Thomas Hessler (Half-Heusler) alloy thermoelectric material, the Bi of FeNbSb sill2Te3Sill or MgSiSn sill.In
In some embodiments, suitable N-shaped Mn adulterates Mg3Sb2The chemical formula of material is Mg3.2-xMnxSb1.5-yBi0.5Tey, wherein
0.0125≤x≤0.1 and 0.01≤y≤0.05；In some embodiments, suitable half Thomas Hessler (Half-
Heusler) example of alloy thermoelectric material includes but is not limited to Hf0.25Zr0.75NiSn0.99Sb0.01, and in some embodiment party
In case, suitable Bi2Te3The example of sill includes but is not limited to Bi0.5Sb1.5Te3.In some preferred embodiments, institute
Stating thermoelectric material is Mg3.175Mn0.025Sb1.98Bi0.5Te0.02。
The method provided according to the present invention, wherein the particle size range of the raw material powder is 10 nanometers~100 microns, excellent
It is selected as 100 nanometers~10 microns.In some embodiments, the particle size range of the raw material powder is 200 nanometers~10 microns,
In some embodiments it is 200~600 nanometers, and is in some embodiments 100~300 nanometers.
The method provided according to the present invention, wherein the raw material powder can be the respective element comprising thermoelectric material
The mixture of solid elemental powders is also possible to the presintering powder of thermoelectric material.
In some embodiments, the raw material powder is the mixing of the solid elemental powders of the respective element of thermoelectric material
The solid elemental powders of object, respective element are stoichiometrically prepared.
In some embodiments, the raw material powder is the presintering powder of thermoelectric material.The presintering powder can
With by method as known in the art such as conventional discharge plasma agglomeration method and arc melting method be made block and with
Grinding obtains afterwards.
The method provided according to the present invention, wherein the described method includes: assembling die group and simultaneously to die main body
Raw material powder is loaded in through-hole, the set of molds assembled is put into water-cooled vacuum room, and have access to electricity pole and lower electrode clamping mold
Then group is sintered such as discharge plasma sintering.
In some embodiments, sintering such as discharge plasma sintering carries out under vacuum, such as the water cooling
The vacuum degree of vacuum chamber is less than or equal to 5Pa, and in some embodiments, sintering such as discharge plasma sintering is normal
What pressure carried out.
The method provided according to the present invention, wherein it is described sintering such as discharge plasma sintering pressure be 5~
120MPa, such as 40~60MPa.
The method provided according to the present invention, wherein the temperature of the sintering such as discharge plasma sintering is 100~2000
DEG C, such as 450~900 DEG C, it is preferable that the time is 1~120 minute, such as 5~20 minutes.
The method provided according to the present invention, wherein it is described sintering such as discharge plasma sintering heating rate be 5~
100 DEG C/min, preferably 20~60 DEG C/min, more preferably 50~60 DEG C/min.
Another aspect, the present invention also provides a kind of block thermoelectric material of multiple dimensioned micro-nano porous structure, chemical formulas
For Mg3.2-xMnxSb1.5-yBi0.5Tey, wherein 0.0125≤x≤0.1 and 0.01≤y≤0.05.
In some specific embodiments, the chemical formula of the thermoelectric material is Mg3.175Mn0.025Sb1.98Bi0.5Te0.02。
The thermoelectric material provided according to the present invention, wherein the consistency of the thermoelectric material is 60%~100%.One
In a little embodiments, it is in some embodiments 70%~90% that the consistency of the thermoelectric material, which is 70%~95%, with
It and is in some embodiments 80%~90%.
The thermoelectric material provided according to the present invention, wherein the thermoelectric material includes continuous phase (also referred to as " main body object
Phase ") and it is dispersed in dispersed phase (also referred to as " precipitate phase ") in continuous phase.
The thermoelectric material provided according to the present invention, wherein the chemical formula of the continuous phase is Mg3.175Mn0.025Sb1.98- zBizTe0.02, wherein 0≤z≤0.5 and the dispersed phase are β-Mg in the continuous phase3Bi2.In the present invention, " β-is stated
Mg3Bi2" refer to that dispersion phase composition is Mg3Bi2, crystal structure is cubic system, and space group is Ia-3 (206).
Term " multiple dimensioned micro-nano porous structure " is primarily referred to as thermoelectric material with nanoscale and micron meter in the present invention
The pore structure of a variety of scales of degree.
Present invention has the advantage that
1. device provided by the invention is insulated above and below by the height and addition when necessary for adjusting seaming chuck and push-down head
Layer, realizes effective control of thickness of sample (volume), so as to efficiently prepare low density heat electric material.The present invention provides
Device can by improving preparation on the basis of traditional hot pressed sintering device such as discharge plasma sintering device,
It is at low cost, it is easy to accomplish.In addition, device provided by the invention does not have particular/special requirement to the material of set of molds, has and widely answer
Use prospect.
2. method provided by the invention is easy to operate, time-saving and efficiency, adjuvant is not needed to form micro-nano hole, Er Qieke
Accurately to control the consistency of material, the multiple dimensioned micro-nano porous structure thermoelectricity material of high-effect economizing type can be efficiently prepared in batches
Material.In addition, the method for the present invention can be used in preparing a variety of different thermoelectric material systems, there is universality, through the method for the present invention
The thermoelectricity capability of the thermoelectric material of the multiple dimensioned micro-nano porous structure of preparation has a distinct increment, and breaches the property of existing thermoelectric material
Energy bottleneck, development and application to thermoelectric material are of great significance and have important economic benefit, also will effectively promote it
The development of his related fields.
3. the block thermoelectric material for preparing multiple dimensioned micro-nano porous structure has important scientific meaning and application prospect, it is
Realize the most possible approach of current thermoelectricity research great-leap-forward development.Made by introducing micro-nano porous structure and corresponding electricity, sound
With new mechanism, the thermoelectric figure of merit ZT of existing thermoelectric material system can be significantly promoted, widens the application neck of abundant thermoelectric material
Domain.It introduces micro-nano porous structure and has no effect on material mechanical performance, material cost 20% or so can be saved significantly on.
Detailed description of the invention
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:
Fig. 1 is a kind of structural schematic diagram of the device of embodiment according to the present invention；
Fig. 2 is the structural schematic diagram of the device of another embodiment according to the present invention；
Fig. 3 is the SEM figure of 1 sample of the embodiment of the present application；
Fig. 4 is the SEM figure of 1 sample of the embodiment of the present application；
Fig. 5 is the SEM figure of 2 sample of the embodiment of the present application；
Fig. 6 is the SEM figure of 2 sample of the embodiment of the present application；
Fig. 7 is the SEM figure of 3 sample of the embodiment of the present application；
Fig. 8 is the SEM figure of 3 sample of the embodiment of the present application；
Wherein, 1- top electrode, 2- water-cooled vacuum room, the upper insulating layer of 3-, 4- seaming chuck, the sample room 5-, 6- push-down head, under 7-
Electrode, 8- die main body, 9- impulse current generator, insulating layer and 11- graphite plate under 10-.
Specific embodiment
The present invention is further described in detail With reference to embodiment, and the embodiment provided is only for explaining
The bright present invention, the range being not intended to be limiting of the invention.
Thermoelectric figure of merit ZT and conversion efficiency of thermoelectric η calculation method
Thermoelectric figure of merit and engineering thermoelectric figure of merit are the indexs for measuring conducting material thermoelectricity performance, wherein thermoelectric figure of merit ZT calculation formula
Are as follows:
ZT=S2σT/K
Wherein, S is Seebeck coefficient, and σ is conductivity, and T is absolute temperature, and K is thermal conductivity.Thermal conductivity is again by the heat of sample
Diffusion coefficient, density and specific heat capacity are multiplied to obtain, and wherein Seebeck coefficient and resistivity use Germany's LINSEIS LSR-3 instrument
Device is tested, and thermal diffusion coefficient is tested using Germany LINSEIS LFA 1000Laser Flash equipment.
Conversion efficiency of thermoelectric η calculation formula are as follows:
Wherein △ T temperature difference, T between cold end hot endcoldFor cold junction temperature, ThotFor hot-side temperature, ZTavgFor average ZT
Value.
And engineering thermoelectric figure of merit (ZT)engIt can be calculated according to thermoelectric figure of merit, formula are as follows:
Scanning electron microscope (SEM)
It is substantially smooth to surface using the sand paper polishing sample of 2,000 mesh first, then in the work of solvent (water or glycerine)
It is polished in polishing machine using 1 μm of antiscuffing paste with lower, until sample surfaces light and under an optical microscope sample
Then surface carries out observation test using scanning electron microscope substantially without scratch.
Consistency
Consistency is calculated by the ratio of measurement density and theoretical density, wherein theoretical density can be calculated,
It can be consulted and be learnt by the website Springer Materials, network address is http://materials.springer.com/.
Hot pressed sintering device
Referring to Fig.1, which show hot pressed sintering devices according to the present invention.Described device include top electrode 1, lower electrode 7,
Water-cooled vacuum room 2 and set of molds.
Set of molds includes die main body 8, seaming chuck 4 and push-down head 6, and die main body 8 has the through-hole of short transverse, upper pressure
The sum of first 4 and the height of push-down head 6 are less than the height of die main body 8.
When work, set of molds is placed in the water-cooled vacuum room 2, and top electrode 1 and lower electrode 7 are by seaming chuck 4 and push-down head 6
The through-hole of press-in die main body 8 is concordant with the upper surface of die main body 8 and lower end surface respectively up to seaming chuck 4 and push-down head 6, mould
Has the sample room 5 for being formed in the through-hole of main body 8 and accommodating sample.Seaming chuck 4 and push-down head 6 can not continue to move into through-hole simultaneously
It is dynamic, so that sample room 5 (thickness (i.e. volume) of sample) is effectively controlled, and then obtain the sample of expectation consistency.
Seaming chuck 4 and push-down head 6 are graphite rod, and die main body 8 is graphite jig main body.
In use, raw material powder is inserted in the inner cavity of die main body 8 and installs seaming chuck 4 and push-down head 6, will assemble
Set of molds be put into water-cooled vacuum room 2, have access to electricity 7 clamping mold group of pole 1 and lower electrode, sets pressure and temperature program and opens
Begin to be sintered, sample nature furnace cooling is made after sintering.
Discharge plasma sintering device
Referring to Fig. 2, which show discharge plasma sintering devices according to the present invention.Described device include top electrode 1, under
Electrode 7, the graphite plate 11 of water-cooled vacuum room 2,2, set of molds, power supply (not shown) and impulse current generator 9.
Set of molds includes die main body 8, seaming chuck 4, push-down head 6, upper insulating layer 3 and lower insulating layer 10, and die main body 8 has
There is the through-hole of short transverse, the sum of seaming chuck 4 and the height of push-down head 6 are less than upper insulating layer 3, die main body 8 and lower insulating layer
The sum of 10 height.
When work, set of molds is placed in the water-cooled vacuum room 2, and upper insulating layer 3 and lower insulating layer 4 are respectively placed in mold master
The upper surface and lower end surface of body 8, top electrode 1 and lower electrode 7 by the through-hole of 6 press-in die main body 8 of seaming chuck 4 and push-down head until
Seaming chuck 4 and push-down head 6 are concordant with upper insulating layer 3 and lower insulating layer 10 respectively, are formed in the through-hole of die main body 8 and accommodate sample
Sample room 5.Seaming chuck 4 and push-down head 6 can not continue to move into through-hole simultaneously, so that (thickness of sample is (i.e. for sample room 5
Volume)) it is effectively controlled, and then obtain the sample of expectation consistency.
Seaming chuck 4 and push-down head 6 are graphite rod, and die main body 8 is graphite jig main body, upper insulating layer 3 and lower insulation
Layer 10 is silica wool.
In use, raw material powder is inserted in the inner cavity of die main body 8 and installs seaming chuck 4 and push-down head 6, will assemble
Set of molds be put into water-cooled vacuum room 2, have access to electricity 7 clamping mold group of pole 1 and lower electrode, be evacuated to less than or equal to 5Pa, if
Constant-pressure and temperature program, unbalanced pulse electric current device 9 simultaneously start to be sintered, and sample nature furnace cooling is made after sintering.
Embodiment 1
The present embodiment is for illustrating Zintl phase thermoelectric material Mg3.175Mn0.025Sb1.98Bi0.5Te0.02And its preparation.
First, in accordance with stoichiometry by 12 hours of each element simple substance particle ball milling, forming partial size is 200 nanometers~10 micro-
The powder of rice, in the FDS-4000 type discharge plasma sintering that Shenzhen University and thinking spy power-supply device Co., Ltd research and develop jointly
In furnace, use conventional discharge plasma agglomeration method that this is powder sintered at compact block (this process for once sintered), sintering
Condition is as follows: vacuum degree 5Pa, pressure 50MPa, and 50 DEG C/min of heating rate, sintering temperature is 600 DEG C, soaking time 5
Minute.
Then by once sintered 4 hours of block materials ball milling, the raw material powder that partial size is 200 nanometers~10 microns is formed
End will carry out double sintering in this powder device shown in Fig. 2, to obtain the sample with multiple dimensioned micro-nano porous structure
Product.In double sintering, vacuum degree 5Pa, pressure 50MPa, 50 DEG C/min of heating rate, sintering temperature is 800 DEG C, heat preservation
Time 5 minutes, sample nature furnace cooling is made after sintering, obtains the sample with multiple dimensioned micro-nano hole (porous) structure
Product.
Fig. 3 and Fig. 4 shows the representative SEM figure of 1 sample different amplification of embodiment.SEM is the results show that embodiment
1 sample has multiple dimensioned micro-nano hole (porous) structure.The consistency of 1 sample of embodiment is 85%.
Demarcate and compare with ICDD standard database using crystal structure of the transmission electron microscope to sample, finds embodiment
Sample made from 1 includes continuous phase and the dispersed phase that is dispersed in continuous phase, continuous phase Mg3.175Mn0.025Sb1.98- zBizTe0.02, wherein z changes between 0~0.5, and dispersed phase is β-Mg3Bi2。
The heat of the block thermoelectric material (i.e. 1 sample of embodiment) of once sintered block materials and double sintering is measured respectively
Electric figure of merit ZT and engineering thermoelectric figure of merit (ZT)eng.The results show that thermal conductivity is by 1Wm at room temperature-1k-1It is reduced to 0.69Wm-1k-1, and
Thermal conductivity is lower more advantageous to thermoelectricity capability for thermoelectric material, and power factor is by 1149 μ Wm at room temperature-1K-2It is promoted to
2267μWm-1K-2(product square with conductivity that power factor is Seebeck coefficient), thermoelectric figure of merit ZT at room temperature by
0.37 is promoted to 1.06, and the peak value of thermoelectric figure of merit ZT is promoted to 2.14 from 1.6, engineering thermoelectric figure of merit (ZT)engPeak value from 0.82
It is promoted to 1.29.The thermoelectric figure of merit ZT and engineering thermoelectric figure of merit (ZT) of the block thermoelectric material of double sinteringengIt is this current material
Peak in Material system, and the tidemark value of thermoelectric material field block thermoelectric material at present.
Embodiment 2
The present embodiment is for illustrating Half-Heusler alloy thermoelectric material Hf0.25Zr0.75NiSn0.99Sb0.01And its system
It is standby.
Ingot casting is made through electric arc melting in each element simple substance first, in accordance with stoichiometry, 12 hours of ball milling form grain later
The powder that diameter is 200~600 nanometers, will carry out discharge plasma sintering in this powder device shown in Fig. 2, vacuum degree is
5Pa, pressure 60MPa, 40 DEG C/min of heating rate, sintering temperature is 900 DEG C, soaking time 20 minutes, is made after sintering
Sample obtains the sample with multiple dimensioned micro-nano hole (porous) structure with furnace natural cooling.
Fig. 5 and Fig. 6 shows the representative SEM figure of 2 sample different amplification of embodiment.SEM is the results show that embodiment
2 samples have multiple dimensioned micro-nano hole (porous) structure.The consistency of 2 sample of embodiment is 93%.
In addition, FDS-4000 type electric discharge researched and developed jointly using Shenzhen University and thinking spy power-supply device Co., Ltd etc. from
Sub- sintering furnace prepares Hf0.25Zr0.75NiSn0.99Sb0.01 dense material is as reference sample.Specifically, it is counted first, in accordance with chemistry
Ingot casting is made through electric arc melting in each element simple substance by amount, and 12 hours of ball milling form the powder that partial size is 200~600 nanometers later
End, then using conventional discharge plasma agglomeration method that this is powder sintered at compact block, sintering condition is as follows: vacuum degree is
5Pa, pressure 60MPa, 40 DEG C/min of heating rate, sintering temperature is 900 DEG C, soaking time 20 minutes.
The thermoelectric figure of merit ZT and engineering thermoelectric figure of merit (ZT) of reference sample and 2 sample of embodiment are measured respectivelyeng.As a result it shows
Show, the peak value of thermoelectric figure of merit ZT is promoted to 1.13 from 1, engineering thermoelectric figure of merit (ZT)engPeak value be promoted to 0.74 from 0.68.
Embodiment 3
The present embodiment is for illustrating Bi2Te3Sill Bi0.5Sb1.5Te3And its preparation.
First, in accordance with stoichiometry by each element simple substance particle ball milling 9 hours, the powder that partial size is 100~300 nanometers is formed
End will carry out discharge plasma sintering, vacuum degree 5Pa, pressure 50MPa, heating in this powder device shown in Fig. 2
70 DEG C/min of rate, sintering temperature is 450 DEG C, soaking time 5 minutes, makes sample with furnace natural cooling after sintering, obtains
Sample with multiple dimensioned micro-nano hole (porous) structure.
Fig. 7 and Fig. 8 shows the representative SEM figure of 3 sample different amplification of embodiment.SEM is the results show that embodiment
3 samples have multiple dimensioned micro-nano hole (porous) structure.The consistency of 3 sample of embodiment is 81%.
In addition, FDS-4000 type electric discharge researched and developed jointly using Shenzhen University and thinking spy power-supply device Co., Ltd etc. from
Sub- sintering furnace prepares Bi0.5Sb1.5Te3Dense material as reference sample.Specifically, first, in accordance with stoichiometry by each element
Simple substance particle ball milling 9 hours forms the powder that partial size is 100~300 nanometers, then uses conventional discharge plasma agglomeration method
This is powder sintered at compact block, and sintering condition is as follows: vacuum degree 5Pa, pressure 50MPa, and 70 DEG C/minute of heating rate
Clock, sintering temperature are 450 DEG C, soaking time 5 minutes.
Measure the thermoelectric figure of merit and engineering thermoelectric figure of merit (ZT) of reference sample and 3 sample of embodimenteng.The results show that thermoelectricity
The peak value of figure of merit ZT is promoted to 1.34 from 1.22, engineering thermoelectric figure of merit (ZT)engPeak value be promoted to 0.5 from 0.43.
Claims (6)
1. a kind of block thermoelectric material of multiple dimensioned micro-nano porous structure, the thermoelectric material is using hot pressed sintering device to raw material
Powder is sintered acquisition, and described device is discharge plasma sintering device, and described device includes top electrode (1), lower electrode
(7), water-cooled vacuum room (2) and set of molds, the set of molds include die main body (8), seaming chuck (4), push-down head (6), it is upper absolutely
Edge layer (3) and lower insulating layer (10), through-hole and the seaming chuck (4) and institute of the die main body (8) with short transverse
The sum of height of push-down head (6) is stated less than the upper insulating layer (3), the die main body (8) and the lower insulating layer (10)
The sum of height；
Specifically, the set of molds is placed in the water-cooled vacuum room (2), the upper insulating layer (3) and the lower insulating layer
(10) upper surface and lower end surface of the die main body (8) are respectively placed in, the top electrode (1) and the lower electrode (7) are by institute
State seaming chuck (4) and the push-down head (6) be pressed into the die main body (8) through-hole until the seaming chuck (4) and it is described under
Pressure head (6) is concordant with the upper insulating layer (3) and lower insulating layer (10) respectively, shape in the through-hole of the die main body (8)
At the sample room (5) for accommodating sample, raw material powder is put into sample room and is sintered by adjusting raw material powder be added
Amount and/or change the height of the seaming chuck (4) and/or the push-down head (6) and carry out the consistency of control block thermoelectric material,
The block thermoelectric material of the multiple dimensioned micro-nano porous structure is obtained, the chemical formula of the thermoelectric material is
Mg3.175Mn0.025Sb1.98Bi0.5Te0.02Or Mg3.2-xMnxSb1.5-yBi0.5Tey, wherein 0.0125≤x≤0.1 and 0.01
≤ y≤0.05, wherein the thermoelectric material includes continuous phase and the dispersed phase that is dispersed in continuous phase.
2. thermoelectric material according to claim 1, wherein the consistency of the thermoelectric material is 60% ~ 100%.
3. thermoelectric material according to claim 1, wherein the consistency of the thermoelectric material is 70% ~ 95%.
4. thermoelectric material according to claim 1, wherein the consistency of the thermoelectric material is 70% ~ 90%.
5. thermoelectric material according to claim 1, wherein the consistency of the thermoelectric material is 80% ~ 90%.
6. thermoelectric material according to claim 1, wherein the chemical formula of the thermoelectric material is
Mg3.175Mn0.025Sb1.98Bi0.5Te0.02, wherein the chemical formula of the continuous phase is Mg3.175Mn0.025Sb1.98-zBizTe0.02, 0
≤ z≤0.5 and the dispersed phase are β-Mg3Bi2。
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| CN101942581A (en) * | 2010-10-11 | 2011-01-12 | 四川大学 | Preparation method of porous magnesium and porous magnesium alloy |
| CN202571280U (en) * | 2012-04-12 | 2012-12-05 | 北京工业大学 | Mould for discharge plasma sintering equipment |
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