CN108531795A - n-type Mg-Sb based room temperature thermoelectric material and preparation method thereof - Google Patents
n-type Mg-Sb based room temperature thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010935 stainless steel Substances 0.000 claims abstract description 29
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 238000005303 weighing Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 14
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 7
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- 239000007789 gas Substances 0.000 claims description 39
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 239000002305 electric material Substances 0.000 claims description 21
- 210000000270 basal cell Anatomy 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000011324 bead Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 19
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 14
- 230000005619 thermoelectricity Effects 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910000855 zintl phase Inorganic materials 0.000 description 2
- 101150064138 MAP1 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 bismuthino Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C22C23/00—Alloys based on magnesium
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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
- C22C1/0408—Light metal alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—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
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C12/00—Alloys based on antimony or bismuth
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- 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
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- 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
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- 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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- 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
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
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Abstract
The invention provides an n-type Mg-Sb based room temperature thermoelectric material with a chemical general formula of Mg3+MnxSb2‑y‑zBiyAzWherein A is an oxygen element S, Se or Te, and-0.2 is more than or equal to 0.3; x, y and z are atomic ratios, and x is 0.001-0.4; y is 0-1.0; z is 0 to 0.2. The preparation method comprises the following steps: selecting a simple substance material with the purity of more than or equal to 99 percent as a raw material according to a chemical general formula, respectively batching and weighing in an argon atmosphere, then placing in a ball mill, adding a stainless steel ball into the ball mill, and rotating the ball mill at a high speed to obtain powder; and weighing the powder respectively, then loading the powder into a graphite mold, then placing the mold into a high-temperature furnace, vacuumizing, sintering under the condition that the total air pressure is lower than 4Pa, and cooling to room temperature after sintering. The thermoelectric material provided by the invention has the advantages that the thermoelectric figure of merit and the mechanical property at room temperature are obviously superior to the level of the traditional n-type bismuth telluride, the cost is low, the preparation method is simple to operate, the cost is lower, the controllability is strong, and the repeatability is good.
Description
Technical field
The invention belongs to field of thermoelectric material technique more particularly to a kind of basal cells n-type Mg-Sb warm electric material and its systems
Preparation Method.
Background technology
Thermoelectric material is constantly subjected to countries in the world as using waste heat and solar energy as the critical material of the generation technology of heat source
It pays high attention to.The heat conductivility of electric conductivity and difference that excellent thermoelectric material has usually had.Thermoelectric material is commonly divided into
Two kinds of n-type and p-type, multipair p-type and n-type thermoelectric material are integrated can to form thermo-electric device, for being directly realized by electric energy and thermal energy
Between mutual conversion.The energy conversion efficiency of thermo-electric device depends primarily on the thermoelectric figure of merit (ZT) of thermoelectric material.How to carry
The performance for rising thermoelectric material is always the popular research direction of educational circles and industrial quarters, and researchers are in addition to thermoelectric material known to regulation and control
Outside the transmission process of middle electronics and phonon, it is also dedicated to find novel thermoelectric material.Wherein n-type conventional thermoelectric materials are ground
Study carefully the performance in the case where by means such as nanosizing, phonon engineerings optimizing to increase, such as：Bismuth telluride-base thermoelectric material is near room temperature
Most outstanding thermoelectric material (150 DEG C, ZTm≈ 1.06), and warm thermoelectric material such as Skutterudites (450 DEG C, ZTm
≈ 1.08), lead telluride (500 DEG C, ZTm≈ 1.4) and Half-Heuslers (600 DEG C, ZTm≈ 1.0) thermoelectric figure of merit only 400
~600 DEG C of ranges reach peak value, and near room temperature ZT is still less than 0.4.With the micromation of thermo-electric device, to the machinability of material
Certain requirement can be also proposed with mechanical property.Commercial room temperature n-type thermoelectric material is bismuth telluride-base material at present, but its
Poor mechanical property often limits the diversity of thermo-electric device, and fracture toughness is in 0.8~1.3MPa m1/2Between.
Currently, thering are many scholars to be studied regarding to the issue above, such as using Mg-Sb base Zintl compounds as new
Type thermoelectric material, but it is less desirable in room temperature condition thermoelectric figure of merit and mechanical property, limit the service temperature range of the material
And application field.
Therefore, it is necessary to solve above-mentioned technological deficiency.
Invention content
It is an object of the invention to overcome above-mentioned the deficiencies in the prior art, it is excellent to provide firstly a kind of room temperature thermoelectricity capability
N-type Mg-Sb base thermoelectricity materials, room temperature thermoelectric figure of merit and mechanical property are better than the water of traditional n-type bismuth telluride thermoelectric material
It is flat and of low cost.
The basal cells n-type Mg-Sb provided by the invention warm electric material, chemical general formula Mg3+δMnxSb2-y-zBiyAz, wherein
A is oxygen group elements S, Se or Te, -0.2≤δ≤0.3；X, y, z is atom ratio, x=0.001~0.4；Y=0~1.0；Z=0
~0.2.
Above-mentioned room temperature n-type Mg-Sb base thermoelectricity materials provided by the invention, room temperature thermoelectric figure of merit is better than in the prior art
N-type bismuth telluride performance (0.8-1.06), and the oxygen group elements doping that its material selection is cheap and easy to get, these elements are in nature
Middle reserves are relatively large, cheap, can replace existing bismuth telluride as commercial n-type room temperature thermoelectric material completely, can be real
The needs of existing industrialized mass production, use value are high.
The present invention also provides the basal cells n-type Mg-Sb described above to warm electric material preparation method, includes the following steps：
By formula M g3+δMnxSb2-y-zBiyAzSelect the pure metals of purity >=99% for raw material, it is low in oxygen content respectively
The batching weighing in the argon gas atmosphere of 1ppm, is subsequently placed in ball mill, and it is small that a certain amount of stainless steel is added in the ball mill
Ball obtains powder after ball mill high-speed rotation；
Loaded in graphite jig after the powder obtained in above-mentioned steps is weighed respectively, mold is then put into high temperature furnace
In, it vacuumizes, is sintered in the case where total gas pressure is less than 4Pa, is cooled to room temperature after sintering and is to get to density
3.6~4.8g/cm3Block thermoelectric material.
The step optional as preparation method of the present invention, the stainless steel ball are passed through when being rotated in ball mill with raw material
Argon gas is protected.
The step optional as preparation method of the present invention, the stainless steel ball being added in ball mill select at least two differences
The stainless steel ball of diameter.
The step optional as preparation method of the present invention, when selecting two kinds of stainless steel balls, diameter be respectively 6mm and
20mm, quantity ratio are 10:1~5:3.
The step optional as preparation method of the present invention, being placed in stainless steel ball and the weight of raw material in the ball mill is
10：1~20：1.
The step optional as preparation method of the present invention, the stainless steel ball and Ball-milling Time of the raw material in ball mill
For 7~12h.
The running speed of the step optional as preparation method of the present invention, the ball mill is 300~500r/min.
The step optional as preparation method of the present invention, when the mold is put into high temperature furnace sintering, sintering temperature 600
DEG C~900 DEG C, sintering time is 5min~40min.
The step optional as preparation method of the present invention is sintered axial compressive force when the mold is put into high temperature furnace sintering
For 40~120MPa.
The basal cells n-type Mg-Sb provided by the invention warm the preparation method of electric material, small using the stainless steel of different-diameter
Ball to raw material carry out mechanical impact and form alloying powder, then by graphite jig carry out plasma discharging activated sintering at
Type, easy to operate, technical process is short, and cost is relatively low, and the controllability of the thermoelectric material of acquisition is strong, favorable repeatability, in heat
Electric material field has preferable application prospect.
Description of the drawings
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the graphite jig schematic diagram used when prepared by plasma sintering of the present invention；
Fig. 2 is n-type Mg prepared by the present invention3+δMnxSb2-y-zBiyTezThe XRD spectra of room temperature thermoelectric material embodiment 1；
Fig. 3 is n-type Mg prepared by the present invention3+δMnxSb2-y-zBiyTezThe loop test heat of room temperature thermoelectric material embodiment 1
Electrical property figure；
Fig. 4 is n-type Mg prepared by the present invention3+δMnxSb2-y-zBiyTezRoom temperature thermoelectric material embodiment 1 and traditional n-type tellurium
Change the thermoelectric figure of merit comparison diagram of bismuth material；
Fig. 5 is n-type Mg prepared by the present invention3+δMnxSb2-y-zBiyTezRoom temperature thermoelectric material embodiment 1 and traditional n-type heat
The Fracture Toughness comparison of electric material schemes；
Fig. 6 is n-type Mg prepared by the present invention3+δMnxSb2-y-zBiySezThe XRD spectra of room temperature thermoelectric material embodiment 3.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
The present invention provides a kind of basal cells n-type Mg-Sb to warm electric material, and the chemical general formula of the thermoelectric material is Mg3+δ
MnxSb2-y-zBiyAz, wherein A is oxygen group elements S, Se or Te, -0.2≤δ≤0.3；X, y, z is atom ratio, x=0.001~
0.4；Y=0~1.0；Z=0~0.2.
Currently, as a kind of new thermoelectric materials, Mg-Sb base thermoelectricity materials have an excellent thermoelectricity capability, but it is in
Being applied under cryogenic conditions is influenced by the vacancy Mg, and the ZT values of near room temperature still are below 0.4, limit the clothes of the new material
Use as a servant temperature range and application field.Mg3Sb2Belong to a-La2O3The Zintl phase stratified materials of structure usually have larger solid solution
Degree, larger space is provided for doped chemical, is conducive to adjusting Mg vacancy concentrations, will be greatly improved the conductivity of material, Sb
Doping Bi advantageously reduces thermal conductivity.However, different element dopings also can be to Mg in terms of electronic structure3Sb2Energy band generates not
Same influence, to which the temperature for reaching thermoelectric figure of merit peak value can be made to change, it is difficult to reach ideal thermoelectricity capability, still limit
The service temperature range and application field of the material are made.The present invention select the oxygen group elements such as S, Se or Te trace doped in
Mg3Sb2Zintl phase layers in, controllable carrier concentration, reduce lattice thermal conductivity, to improve Mg-Sb base thermoelectricity materials
Thermoelectricity capability, especially its thermoelectric figure of merit at ambient temperature, can reach the level of n-type bismuth telluride performance in the prior art
(0.8-1.06), and in high temperature higher than the level of n-type bismuth telluride performance, and since the material selection of doping is cheap and easy to get
Oxygen group elements, and these elements reserves in nature are relatively large, cheap, and cost is far below bismuth telluride thermoelectricity material
Expect the needs, it can be achieved that industrialized mass production, so existing bismuth telluride can be replaced as commercial n-type room temperature heat completely
Electric material has very high use value.
The present invention also provides the preparation methods that the basal cells above-mentioned n-type Mg-Sb warm electric material, include the following steps：
S1 presses chemical general formula Mg3+δMnxSb2-y-zBiyAzSelect the pure metals of purity >=99% for raw material, respectively in oxygen
Batching weighing in argon gas atmosphere of the content less than 1ppm, is subsequently placed in planetary ball mill, and be added in the ball mill a certain amount of
Stainless steel ball, so that above-mentioned raw materials is crushed and is mixed using the Impact energy of stainless steel ball in ball mill, it is preliminary to synthesize
Powder Mg3+δMnxSb2-y-zBiyAzPhase.
In the step, the stainless steel ball in addition ball mill is passed through argon gas protection when being rotated in ball mill with raw material,
It can prevent powder from aoxidizing.
To further change crystallite dimension, the bead of at least two different-diameters also can be selected in the stainless steel ball of addition,
By the continuous shock of different diameter beads, the grain size smaller of gained powder body material, mixing can be made to be more uniformly distributed.When select two kinds not
Become rusty steel bead, and diameter is chosen as 6mm and 20mm, and the quantity ratio of two kinds of beads is 10:1~5:3.
In the step, it is 10 to be placed in stainless steel ball and the weight ratio of raw material in the ball mill：1~20：1, ball mill
Running speed be 300~500r/min, stainless steel ball and Ball-milling Time of the raw material in ball mill are 7~12h, can be obtained
To ideal powder.
S2 is loaded on after weighing the powder obtained in above-mentioned steps respectively in graphite jig, and mold is then put into high temperature furnace
In, it vacuumizes, is sintered into bulk alloy in the case where total gas pressure is less than 4Pa, is cooled to room temperature after sintering.
Referring to Fig. 1, in the step, graphite jig includes graphite pressure head 1, and graphite pressure chamber 2 and thermocouple 3, powder 4 are placed in stone
In ink pressure chamber 2, bulk is pressed by graphite pressure head 1.When graphite jig is put into sintering in high temperature furnace, sintering temperature is 600 DEG C
~900 DEG C, sintering time is 5min~40min, and sintering axial compressive force is 40~120MPa.
Above-mentioned steps prepare molding block density in 3.6~4.8g/cm3Between, resistivity is 5~70 μ Ω .m, plug
Seebeck coefficient is 140~340 μ V/K, power factor is 0.6~3.0mW/m/K2, thermal conductivity is 0.45~1.25Wm-1K-1, fracture
Toughness is more than 2.1MPa m1/2, thermoelectric figure of merit ZT room temperatures can reach 0.6~0.9, can reach 1.42 at 250 DEG C, hence it is evident that excellent
In bismuth telluride thermoelectric material.
It is tested within the scope of 2 θ=10 °~80 ° using X-ray diffractometer (XRD), five yuan of above-mentioned preparation method preparation
Mg-Sb base thermoelectricity materials Mg3+δMnxSb2-y-zBiyAz, there is Mg3Sb2The corresponding diffraction maximum of phase, and occur without other miscellaneous peaks,
Show that the material of synthesis is Mg3Sb2It is single-phase.
The basal cells n-type Mg-Sb provided by the invention warm the preparation method of electric material, by using the bead of different-diameter
Mechanical impact makes raw material form alloying powder in the ball mill, is then placed in graphite jig and carries out plasma discharging activation burning
Form type, preparation method is easy to operate, and cost is relatively low, and controllability is strong, and favorable repeatability is conducive to industrialized production.
Preparation method of the present invention is further described with reference to embodiment.
Embodiment 1：
It is prepared according to the following steps：
S1 chooses sheet Mg (purity 99.8%), and granular Sb (purity 99.999%), Bi (purity 99.999%), Te is (pure
99.999%), powdery Mn (purity 99.95%) is raw material to degree, is Mg according to general formula3+δMnxSb2-y-zBiyTezStoichiometric ratio
(wherein δ=- 0.1, x=0.1, y=0.5, z=0.01, i.e. chemical general formula are Mg2.9Mn0.1Sb1.49Bi0.5Te0.01), in oxygen
Batching weighing in the vacuum drying chamber of argon gas atmosphere of the content less than 1ppm, and by the stainless steel ball of a diameter of 6mm and 20mm
According to 10:1 quantitative proportion is fitted into planetary ball mill together, and is passed through argon gas protection, prevents powder from aoxidizing, ball material weight ratio
It is 20：1.Wherein the running speed of planetary ball mill is 500r/min, Ball-milling Time 7.5h.
S2 takes the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 0.1ppm
Go out, is packed into graphite jig shown in FIG. 1 after weighing respectively, mould inner wall is lined with the graphite carbon paper of 0.1mm, then puts mold
Enter in high temperature furnace cavity.
It is vacuumized in stove, high temperature sintering is carried out in the case where total gas pressure is less than 4Pa, sintering temperature is 600 DEG C, is controlled
Temperature is burnt within 10 DEG C, and it is 75MPa to apply pressure in sintering process, and sintering time should be controlled in 10min or so.
After the completion of sintering, molding block density is in 4.0g/cm3Left and right.
As shown in Fig. 2, through X-ray diffraction analysis, 1 obtained block materials of the present embodiment are Mg3Sb2It is single-phase, and this five
First Mg-Sb base thermoelectricity materials Mg2.9Mn0.1Sb1.49Bi0.5Te0.01, respectively 22.46 °, 24.61 °, 25.65 °, 33.56 °,
37.29 °, 43.96 ° etc. there is Mg respectively3Sb2(100), (002), (011), (012), (103) diffraction maximum.
The n-type Mg prepared referring to Fig. 3, the present embodiment 12.9Mn0.1Sb1.49Bi0.5Te0.01Material is within the scope of 0 DEG C -500 DEG C
The thermoelectric (al) power factor of loop test is 1.5~2.7mW/m/K2。
As shown in figure 4, five yuan of n-type Mg prepared by the present embodiment 12.9Mn0.1Sb1.49Bi0.5Te0.01The thermoelectric figure of merit of material
ZT, room temperature is up to 0.69,250 DEG C up to 1.42.Suitable with bismuth telluride between 25 DEG C~125 DEG C, ZT values are bright after 125 DEG C
It is aobvious to be better than bismuth telluride material.
As shown in figure 5, five yuan of n-type Mg prepared by the present embodiment 12.9Mn0.1Sb1.49Bi0.5Te0.01The mechanical property of material：
Fracture toughness is 2.95MPa m1/2, Young's modulus 43GPa) wherein modulus and bismuth telluride-base material be suitable, and fracture toughness is tellurium
Change bismuthino material 2.5~3 times；
In addition, five yuan of n-type Mg2.9Mn0.1Sb1.49Bi0.5Te0.01Within the scope of 25-500 DEG C, resistivity is block materials
30~90 μ Ω .m；Seebeck coefficient is -180~-300 μ V/K；Thermal conductivity is 1.1~0.6Wm-1K-1。
Embodiment 2：
It is prepared according to the following steps：
S1 is with sheet Mg (purity 99.8%), granular Sb (purity 99.999%), Bi (purity 99.999%), Te (purity
99.999%), powdery Mn (purity 99.95%) is raw material, according to Mg3+δMnxSb2-y-zBiyTezStoichiometric ratio (δ=0.1x=
0.2, y=0.3, z=0.05, i.e. chemical general formula are Mg3.1Mn0.2Sb1.65Bi0.3Te0.05), it is less than the argon of 1ppm in oxygen content
Batching weighing in gas atmosphere vacuum drying chamber, and by the stainless steel ball of a diameter of 6mm and 20mm according to 10:2 quantitative proportion
It is fitted into ball mill together, and is passed through argon gas protection, prevent powder from aoxidizing, ball material weight ratio is 15：1.The wherein fortune of ball mill
Rotary speed is 400r/min, Ball-milling Time 10h.
S2 takes the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 0.1ppm
Go out, and be fitted into graphite jig shown in FIG. 1 after weighing respectively, mould inner wall is lined with the graphite carbon paper of 0.1mm, then by mold
It is put into high temperature furnace cavity.
It vacuumizes in stove, is sintered in the case where total gas pressure is less than 4Pa, sintering temperature is 700 DEG C, controls burning temperature
It is 80MPa that degree applies pressure within 10 DEG C, in sintering process, and sintering time should be controlled in 20min.It is cooled to after sintering
Room temperature takes out sintered sample.
After the completion of sintering, molding block density is in 4.2g/cm3Left and right.
The five yuan of n-type Mg prepared through X-ray diffraction analysis, the present embodiment 23.1Mn0.2Sb1.65Bi0.3Te0.05Block materials
For Mg3Sb2It is single-phase, and nearby occur respectively in 22.46 °, 24.61 °, 25.65 °, 33.56 °, 37.29 °, 43.96 ° etc. respectively
Mg3Sb2(100), (002), (011), (012), (103) diffraction maximum, no other miscellaneous peaks occur.
In addition, five yuan of n-type Mg3.1Mn0.2Sb1.65Bi0.3Te0.05Within the scope of 25-500 DEG C, resistivity is block materials
10~80 μ Ω .m；Seebeck coefficient is -200~-350 μ V/K；Thermal conductivity is 1.2~0.7Wm-1K-1。
Mechanical property：Fracture toughness is 2.56MPa m1/2, Young's modulus 45GPa.
Thermoelectric figure of merit ZT room temperatures up at 0.74,250 DEG C up to 1.42, hence it is evident that be better than bismuth telluride material.
Embodiment 3：
It is prepared according to the following steps：
S1 is with sheet Mg (purity 99.8%), granular Sb (purity 99.999%), Bi (purity 99.999%), Se (purity
99.999%), powdery Mn (purity 99.95%) is raw material, according to Mg3+δMnxSb2-y-zBiySezStoichiometric ratio (δ=0, x=
0.3, y=0.1, z=0.1, i.e. chemical general formula are Mg3Mn0.3Sb1.8Bi0.1Se0.1) it is less than the argon gas gas of 1ppm in oxygen content
Batching weighing in atmosphere vacuum drying chamber, and by the stainless steel ball of a diameter of 6mm and 20mm according to 5:3 quantitative proportion fills together
Enter in ball mill, and be passed through argon gas protection, prevent powder from aoxidizing, ball material weight ratio is 10：1.The wherein running speed of ball mill
For 500r/min, Ball-milling Time 7.5h.
S2 takes the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 0.1ppm
Go out, and be fitted into graphite jig shown in FIG. 1 after weighing respectively, mould inner wall is lined with the graphite carbon paper of 0.1mm, then by mold
It is put into cavity.
It vacuumizes in stove, is sintered in the case where total gas pressure is less than 4Pa, sintering temperature is 800 DEG C, controls burning temperature
It is 100MPa that degree applies pressure within 10 DEG C, in sintering process, and sintering time should be controlled in 8min.It is cooled to after sintering
Room temperature takes out sintered sample.
After the completion of sintering, molding block density is in 4.5g/cm3Left and right.
As shown in fig. 6, through X-ray diffraction analysis, five yuan of n-type Mg of the preparation of the present embodiment 33Mn0.3Sb1.8Bi0.1Se0.1
Block materials are Mg3Sb2It is single-phase, and respectively near 22.46 °, 24.61 °, 25.65 °, 33.56 °, 37.29 °, 43.96 ° etc.
Occurs Mg respectively3Sb2(100), (002), (011), (012), (103) diffraction maximum, no other miscellaneous peaks occur.
In addition, five yuan of n-type Mg3Mn0.3Sb1.8Bi0.1Se0.1Block materials are within the scope of 25-500 DEG C, resistivity 30
~120 μ Ω .m；Seebeck coefficient is -190~-350 μ V/K；Thermal conductivity is 1.0~0.6Wm-1K-1。
Mechanical property：Fracture toughness is 2.37MPa m1/2, Young's modulus 44GPa.
Thermoelectric figure of merit ZT room temperatures up at 0.65,250 DEG C up to 1.38, hence it is evident that be better than bismuth telluride material.
Embodiment 4：
S1 is with sheet Mg (purity 99.8%), granular Sb (purity 99.999%), Bi (purity 99.999%), powdery Mn
(purity 99.95%), S (purity 99.999%) is raw material, according to Mg3+δMnxSb2-y-zBiySzStoichiometric ratio (δ=- 0.2, x
=0.4, y=0.8, z=0.2, i.e. chemical general formula are Mg2.8Mn0.4Sb1Bi0.8S0.2) it is less than the argon gas gas of 1ppm in oxygen content
Batching weighing in atmosphere vacuum drying chamber, and by the stainless steel ball of a diameter of 6mm and 20mm according to 10:2 quantitative proportion is packed into
In ball mill, and it is passed through argon gas protection, prevents powder from aoxidizing, ball material weight ratio is 20：1.The wherein operating speed of planetary ball mill
Degree is 500r/min, Ball-milling Time 12h.
S2 takes the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 0.1ppm
Go out, and be fitted into graphite jig shown in FIG. 1 after weighing respectively, mould inner wall is lined with the graphite carbon paper of 0.1mm, then by mold
It is put into high temperature furnace cavity.
It vacuumizes in stove, is sintered in the case where total gas pressure is less than 4Pa, sintering temperature is 900 DEG C, in sintering process
Burnt temperature should be controlled within 10 DEG C, application pressure is 120MPa, and sintering time should be controlled in 5min.Sintering finishes postcooling
Sintered sample is taken out to room temperature.
After the completion of sintering, molding block density is in 4.8g/cm3Left and right.
The five yuan of n-type Mg prepared through X-ray diffraction analysis, the present embodiment 42.8Mn0.4Sb1Bi0.8S0.2Block materials are
Mg3Sb2It is single-phase, and nearby occur respectively in 22.46 °, 24.61 °, 25.65 °, 33.56 °, 37.29 °, 43.96 ° etc. respectively
Mg3Sb2(100), (002), (011), (012), (103) diffraction maximum, no other miscellaneous peaks occur.
In addition, five yuan of n-type Mg2.8Mn0.4Sb1Bi0.8S0.2Block materials are within the scope of 25-500 DEG C, resistivity 50
~130 μ Ω .m；Seebeck coefficient is -175~-280 μ V/K；Thermal conductivity is 0.9~0.6Wm-1K-1。
Mechanical property：Fracture toughness is 2.55MPa m1/2, Young's modulus 49.5GPa.
Thermoelectric figure of merit ZT room temperatures up at 0.62,250 DEG C up to 1.29, hence it is evident that be better than bismuth telluride material.
Embodiment 5：
S1 is with sheet Mg (purity 99.8%), and granular Sb (purity 99.999%), powdery Mn (purity 99.95%), S is (pure
99.999%) degree is raw material, according to Mg3+δMnxSb2-y-zBiySz(δ=0.2, x=0.1, y=0, z=0 change stoichiometric ratio
General formula is Mg3.2Mn0.1Sb2) batching weighing in argon gas atmosphere vacuum drying chamber of the oxygen content less than 1ppm, and by diameter
For 6mm and 20mm stainless steel ball according to 10:1 quantitative proportion is fitted into ball mill, and is passed through argon gas protection, prevents powder
Oxidation, ball material weight ratio are 15：1.Wherein the running speed of planetary ball mill is 500r/min, Ball-milling Time 12h.
S2 takes the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 0.1ppm
Go out, and be fitted into graphite jig shown in FIG. 1 after weighing respectively, mould inner wall is lined with the graphite carbon paper of 0.1mm, then by mold
It is put into high temperature furnace cavity.
It vacuumizes in stove, is sintered in the case where total gas pressure is less than 4Pa, sintering temperature is 700 DEG C, in sintering process
Burnt temperature should be controlled within 10 DEG C, application pressure is 120MPa, and sintering time should be controlled in 30min.It is cold after sintering
But sintered sample is taken out to room temperature.
After the completion of sintering, molding block density is in 4.2g/cm3Left and right.
The n-type Mg prepared through X-ray diffraction analysis, embodiment 53.2Mn0.1Sb2Block materials are Mg3Sb2It is single-phase, and point
Nearby do not occur Mg respectively in 22.46 °, 24.61 °, 25.65 °, 33.56 °, 37.29 °, 43.96 ° etc.3Sb2(100),
(002), (011), (012), (103) diffraction maximum, no other miscellaneous peaks occur.
N-type Mg3.2Mn0.1Sb2For block materials within the scope of 25-500 DEG C, resistivity is 110~180 μ Ω .m；Sai Bei
Gram coefficient is -110~-250 μ V/K；Thermal conductivity is 1.3~0.8Wm-1K-1。
Mechanical property：Fracture toughness is 2.15MPa m1/2, Young's modulus 45.5GPa.
Thermoelectric figure of merit ZT room temperatures up at 0.41,250 DEG C up to 0.96, close to bismuth telluride material horizontal.
Comparative example 1：
It is prepared according to the following steps：
S1 is with sheet Mg (purity 99.8%), granular Sb (purity 99.999%), Bi (purity 99.999%), Te (purity
99.999%), powdery Ti (purity 99.99%) is raw material, according to Mg3+δTixSb2-y-zBiyTezStoichiometric ratio (δ=- 0.2~
0.3, x=0~0.4, y=0~0.8, z=0~0.2) match in argon gas atmosphere vacuum drying chamber of the oxygen content less than 1ppm
Material is weighed, and by the stainless steel ball of a diameter of 6mm and 20mm according to 10:1 quantitative proportion is fitted into ball mill, and is passed through argon
Gas shielded prevents powder from aoxidizing, and ball material weight ratio is 20：1.Wherein the running speed of planetary ball mill is 500r/min, ball milling
Time is 7.5h.
S2 takes the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 0.1ppm
Go out, and respectively after weighing in graphite jig shown in load map 1, then mold is put into quartz ampoule.It vacuumizes, it is low in total gas pressure
It is sintered in the case of 10Pa, it is 80MPa to apply pressure in sintering process, and heating rate is controlled at 5~35 DEG C, sintering
Between control in 30~60min.Taking-up sintered sample is cooled to room temperature after sintering.
Through X-ray diffraction analysis, comparative example 1 obtains five yuan of Mg3+δTixSb2-y-zBiyTez(y=0~0.8；Z=0~
0.4；Z=0~0.2) block materials be Mg3Sb2It is single-phase.
Referring to Fig. 6, from this figure, it can be seen that doped chemical selects Ti and hot pressed sintering mode, thermoelectric figure of merit is used to exist
It is 1.24 when being 0.38,250 DEG C when room temperature, is far below 1 thermoelectric figure of merit of the embodiment of the present invention.
Comparative example 2：
S1 is with sheet Mg (purity 99.8%), granular Sb (purity 99.999%), Bi (purity 99.999%), Te (purity
99.999%), powdery Fe (purity 99.99%) is raw material, according to Mg3+δFexSb2-y-zBiyTezStoichiometric ratio (δ=- 0.2~
0.3, x=0~0.4, y=0~0.8, z=0~0.2) match in argon gas atmosphere vacuum drying chamber of the oxygen content less than 1ppm
Material is weighed, and by the stainless steel ball of a diameter of 6mm and 20mm according to 10:1 quantitative proportion is fitted into ball mill, and is passed through argon
Gas shielded prevents powder from aoxidizing, and ball material weight ratio is 20：1.Wherein the running speed of planetary ball mill is 500r/min, ball milling
Time is 7.5h.
S2 takes out the powder obtained in above-mentioned steps in argon gas atmosphere vacuum drying chamber of the oxygen content less than 1ppm,
And be fitted into graphite jig shown in FIG. 1 after weighing respectively, then mold is put into quartz ampoule.It vacuumizes, it is low in total gas pressure
It is sintered in the case of 10Pa, at 5~35 DEG C, sintering time is controlled in 30~60min, sintering process for heating rate control
Middle application pressure is 80MPa.Taking-up sintered sample is cooled to room temperature after sintering.
Through X-ray diffraction analysis, comparative example 2 obtains five yuan of block materials Mg3+δFexSb2-y-zBiyTez(y=0~0.8；
Z=0~0.4；Z=0~0.2) it is Mg3Sb2It is single-phase.
After measured, doped chemical selects transition element Fe and using hot pressed sintering mode, and thermoelectric figure of merit is in room temperature
It is 1.14 at 0.23,250 DEG C, is also far below 1 thermoelectric figure of merit of the embodiment of the present invention.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention made by within principle.
Claims (10)
1. a kind of basal cells n-type Mg-Sb warm electric material, which is characterized in that the chemical general formula of the thermoelectric material is Mg3+δ
MnxSb2-y-zBiyAz, wherein A is oxygen group elements S, Se or Te, -0.2≤δ≤0.3；X, y, z is atom ratio, x=0.001~
0.4；Y=0~1.0；Z=0~0.2.
2. the basal cells n-type Mg-Sb as described in claim 1 warm electric material preparation method, which is characterized in that including following steps
Suddenly：
By formula M g3+δMnxSb2-y-zBiyAzIt selects the pure metals of purity >=99% for raw material, is less than respectively in oxygen content
Batching weighing in the argon gas atmosphere of 1ppm, is subsequently placed in ball mill, and a certain amount of stainless steel ball is added in the ball mill,
Powder is obtained after ball mill high-speed rotation；
Loaded in graphite jig after the powder obtained in above-mentioned steps is weighed respectively, then mold is put into high temperature furnace, is taken out
Vacuum, total gas pressure be less than 4Pa in the case of be sintered, be cooled to room temperature after sintering to get to density be 3.6~
4.8g/cm3Block thermoelectric material.
3. the basal cells n-type Mg-Sb as claimed in claim 2 warm electric material preparation method, which is characterized in that the stainless steel
Bead is passed through argon gas protection when being rotated in ball mill with raw material.
4. the basal cells n-type Mg-Sb as claimed in claim 2 warm electric material preparation method, which is characterized in that ball mill is added
In stainless steel ball select at least two different-diameters stainless steel ball.
5. the basal cells n-type Mg-Sb as claimed in claim 4 warm electric material preparation method, which is characterized in that when two kinds of selection
When stainless steel ball, diameter is respectively 6mm and 20mm, and quantity ratio is 10:1~5:3.
6. as the basal cells claim 2-5 any one of them n-type Mg-Sb warm electric material preparation method, which is characterized in that set
Stainless steel ball and the weight ratio of raw material are 10 in the ball mill：1~20：1.
7. as the basal cells claim 2-5 any one of them n-type Mg-Sb warm electric material preparation method, which is characterized in that institute
It is 7~12h that stainless steel ball, which is stated, with Ball-milling Time of the raw material in ball mill.
8. as the basal cells claim 2-5 any one of them n-type Mg-Sb warm electric material preparation method, which is characterized in that institute
The running speed for stating ball mill is 300~500r/min.
9. as the basal cells claim 2-5 any one of them n-type Mg-Sb warm electric material preparation method, which is characterized in that will
When the mold is put into high temperature furnace sintering, sintering temperature is 600 DEG C~900 DEG C, and sintering time is 5min~40min.
10. as the basal cells claim 2-5 any one of them n-type Mg-Sb warm electric material preparation method, which is characterized in that will
When the mold is put into high temperature furnace sintering, sintering axial compressive force is 40~120MPa.
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| CN110257667A (en) * | 2019-05-30 | 2019-09-20 | 同济大学 | A kind of three magnesiumization of N-type, two antimony alloy thermoelectric material and its preparation |
| CN110635020A (en) * | 2019-08-30 | 2019-12-31 | 中国科学院物理研究所 | Magnesium-antimony-based thermoelectric element and preparation method and application thereof |
| CN110635020B (en) * | 2019-08-30 | 2021-05-25 | 中国科学院物理研究所 | Magnesium-antimony-based thermoelectric element and preparation method and application thereof |
| CN112310269A (en) * | 2020-11-03 | 2021-02-02 | 哈尔滨工业大学（深圳） | Mg with power generation and refrigeration potentials3(Sb,Bi)2Base thermoelectric material and preparation method thereof |
| CN114890791A (en) * | 2022-05-06 | 2022-08-12 | 清华大学 | Magnesium antimonide-based thermoelectric material and preparation method and application thereof |
| CN114890791B (en) * | 2022-05-06 | 2022-12-23 | 清华大学 | Magnesium antimonide-based thermoelectric material and preparation method and application thereof |
| CN115090886A (en) * | 2022-07-30 | 2022-09-23 | 太原理工大学 | Improve Mg 3 Sb 2 Method for power factor of base thermoelectric material |
| CN115090886B (en) * | 2022-07-30 | 2024-06-04 | 太原理工大学 | Improve Mg3Sb2Method for preparing thermoelectric material power factor |
| WO2024060114A1 (en) * | 2022-09-22 | 2024-03-28 | 南方科技大学 | Mg-sb-based thermoelectric device comprising high-entropy thermoelectric interface material, and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108531795B (en) | 2020-09-22 |
| WO2019169970A1 (en) | 2019-09-12 |
| JP2021515411A (en) | 2021-06-17 |
| JP6976012B2 (en) | 2021-12-01 |
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