CN101118946A - Barium zinc antimony based p type thermoelectric material and method for making same - Google Patents
Barium zinc antimony based p type thermoelectric material and method for making same Download PDFInfo
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- CN101118946A CN101118946A CNA2007100438444A CN200710043844A CN101118946A CN 101118946 A CN101118946 A CN 101118946A CN A2007100438444 A CNA2007100438444 A CN A2007100438444A CN 200710043844 A CN200710043844 A CN 200710043844A CN 101118946 A CN101118946 A CN 101118946A
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- thermoelectric material
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- barium zinc
- antimony based
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- 239000000463 material Substances 0.000 title claims abstract description 35
- WLNOETIBHNQWEJ-UHFFFAOYSA-N [Zn].[Ba].[Sb] Chemical compound [Zn].[Ba].[Sb] WLNOETIBHNQWEJ-UHFFFAOYSA-N 0.000 title claims description 8
- 238000000034 method Methods 0.000 title abstract 3
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract 2
- 238000005245 sintering Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 2
- 230000005619 thermoelectricity Effects 0.000 abstract description 5
- 229910052693 Europium Inorganic materials 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 238000005057 refrigeration Methods 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052573 porcelain Inorganic materials 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910016964 MnSb Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910018989 CoSb Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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Abstract
The present invention relates to a barium stibium and zinc based p type thermoelectric material and the preparing method and belongs to the thermoelectric conversion material domain. The chemical general expression of the present invention is Bal-uRuZn2-vTvSb2-zSz, wherein the R element is Ca, Sr, Yb or Eu and X is the R with impurity with an arrange X which is no less than zero and no more than zero point two; the T element is Cu or Ag and y is T with impurity with an arrange y which is no less than zero and no more than zero point two; S is element Ge or Sn and z is S with impurity with an arrange z which is no less than zero and no more than zero point two. The present invention is compounded under the vacuum or inertia gas and the present invention adopts the quick plasma sinter(SPS) or the method of heat pressure sinter porcelain sample. The ZT value of barium stibium and zinc can reach zero point thirty eight and will be enhanced after adding impurity; and the present invention can be applicable to the thermoelectricity conversion generating or the refrigeration.
Description
Technical field
The present invention relates to a kind of barium zinc antimony based p type thermoelectric material and preparation method thereof, belong to the thermo-electric converting material field.
Background technology
The video thermoelectric generation technology is to utilize the Sai Beike of semi-conducting material (Seebeck) effect and Pa Er card (Peltier) effect to carry out heat energy and the directly mutual switch technology of electric energy, comprises thermoelectric power generation and thermoelectric cooling
[1-2]Advantages such as thermoelectric conversion system has that volume is little, reliability is high, pollution-free, noiselessness, Applicable temperature scope are wide have obtained to use widely in high-tech sectors such as space technology, military equipment, IT technology as particular power source and high precision temperature control device.The conversion efficiency of thermoelectric of system depends primarily on the performance of thermoelectric material, i.e. dimensionless performance index the ZT (=α of material
2σ/к, α are the Seebeck coefficients of material, and σ is a conductivity of electrolyte materials, and к is the thermal conductivity of material, and T is an absolute temperature).The ZT value is high more, and the thermoelectric conversion performance of material is good more.According to the difference that transports the charge carrier kind of material, thermoelectric material is divided into n type (electron conduction) and p type (hole conduction).For general thermoelectric material, we can be optimized carrier concentration by the mode of mixing, thereby optimize ZT.Therefore, improve the ZT value of traditional material and seek the main target that novel high ZT value material becomes this area.
In recent years, thermoelectric generation technology is subjected to extensive concern as a kind of novel clean energy technology in the world, especially be applied to industrial surplus used heat and sunlight one hot compound power-generating field, be expected to for improving rate of energy, alleviating the approach that problem of environmental pollution provides a kind of comprehensive coordination.Although thermoelectric generation technology has so many advantage,, its energy conversion efficiency is lower, and the energy conversion efficiency of the thermoelectric conversion system of the application of succeeing in the world at present only is 7-8%, has seriously limited the extensive use of pyroelectric technology.In recent decades, the system of comparative maturity has Bi
2Te
3, Zn
4Sb
3Alloy, PbTe alloy, CoSb
3And the heavy doping system, SiGe alloy etc., they in corresponding temperature range separately the ZT value 0.5～1.3.Recently, Zintl type intermetallic compound more and more attracts much attention.So-called Zintl compound is meant the compound that is made of strong metal of electropositivity and the more intense part of electronegativity, defers to the Zintl rule: electronics is transferred to the part-structure that electronegative element forms from electropositive element and is satisfied the requirement of the full layer of eight electronics.This compounds forms narrow gap semiconductor easily, and has abundant complicated structure, causes the lattice thermal conductance lower, and these all are that good thermoelectric material is needed.But in fact, the exploration of the thermoelectric material of present this type compound also belongs to the starting stage, and the material conversion efficiency of thermoelectric of discovery is all very low, such as Ba
4In
8Sb
16, Yb
5In
2Sb
6, Eu
5In
2Sb
6, BaCu
2Te
2(Ying C.Wang and Francis J.DiSalvo, Journalof Solid State Chemistry 156,44-50 (2001)) or the like.Under the room temperature, their electricity is led greatly about 10
4Sm
-1, Seebeck coefficient 40～100 μ VK
-1, thermal conductance 2Wm
-1K
-1, ZT about 10
-3～10
-4, can not satisfy the requirement of thermoelectric material.[Sun-Jin?Kim?et.al.Chem.Mater.11.3154(1999)；Sung-Jin?Kim?et.al.J.Solid?StateChem.155，55(2000)；Seon-Mi?Park?et.al.J.Mater.Chem，12，1839(2002)；Ying?C.Wang?et.al.J.Solid?StateT?Chem.156，44(2001).]
Recently, also there is the reasonable Zintl section bar of a little performance material to be found, as: Ca
xYb
1-xZn
2Sb
2(ZT
750K～0.5), Yb
14MnSb
11(ZT
1200K~ 1) [Frank Gascoin et.al.Adv.Funct.Mater.2005,15,1860; Shawna R.Brown et.al.Chem.Mater.18,1873 (2006)].Compd B aZn among the present invention
2Sb
2Be a kind of typical Zintl type compound, at present, the thermoelectricity capability of this compound does not appear in the newspapers, BaZn
2Sb
2Show and the suitable good thermoelectricity capability of the two kinds of materials in front: low thermal conductance, electric property preferably.Ca with tripartite P-3ml structure
xYb
1-xZn
2Sb
2Different is BaZn
2Sb
2Belong to a cube Pnma structure, and the former adopts Yb and the solid solution of Ca arbitrary proportion to regulate the thermoelectricity capability of material, and be that suitable Ca is carried out in the Ba position among the present invention, Sr, Yb, Eu mix and further reduce thermal conductance, and Zn position and Sb position are carried out suitable Cu respectively, Ag and Ge, the p type of Sn mixes and further promotes electric property.
Summary of the invention
Originally the purpose of this invention is to provide a kind of novel p type thermoelectric material and preparation method thereof.
This materials chemistry general formula that can be used for thermoelectric conversion that the present invention proposes is Ba
1-uR
uZn
2-vT
vSb
2-zS
z, wherein R is Elements C a, and Sr, Yb or Eu, x are the real composition that R mixes, and scope is in 0≤x≤0.2; T is element Cu or Ag, and y is the real composition that T mixes, and scope is in 0≤y≤0.2; S is element Ge or Sn, and z is the real composition that S mixes, and scope is in 0≤z≤0.2.Compound belongs to a cube Pnma structure among the present invention.
The synthetic method of compound is a solid phase synthesis among the present invention, and preparation process is as follows successively:
Adopt metal Ba or Ba and Ca, Sr, Yb, any binary of Eu or ternary compound are raw material;
Adopt Metal Zn or Zn and Cu, any binary of Ag or ternary compound are raw material;
Adopt metal Sb or Sb and Ge, any binary of Sn or ternary compound are raw material;
At first with raw material by suitable stoichiometric proportion weighing, put into not in the middle of the container with raw material and product reaction, vacuum or following 700 ℃～1000 ℃ following calcinations of inert atmosphere (as nitrogen or argon gas) at least 12 hours, took out the cooling back then.Sample is pulverized and is promptly got pulverous BaZn
2Sb
2The thermoelectric material of base.
The powder body material that previous step is obtained further carries out rapid plasma body sintering (SPS) or hot pressed sintering (500 ℃～600 ℃ of SPS sintering temperatures, pressure 30～50MPa; 400 ℃～700 ℃ of hot pressed sintering temperature, pressure 20～60MPa) can obtain the ceramics sample of density more than 90%.
The preparation technology of material is easy to control among the present invention, can be in room temperature to 400 ℃ stable application, and have thermoelectricity capability preferably.Such as for unadulterated BaZn
2Sb
2, the room temperature thermal conductivity is 1.6Wm
-1K
-1, can with the Bi that is celebrated with low thermal conductance
2Te
3Compare, room-temperature conductivity and Seebeck coefficient are respectively 2 * 10
4Sm
-1With 150 μ VK
-1, the ZT value reaches 0.38 in the time of 400 ℃, can with the similar compound of the better performances of present reported in literature quite (as at 400 ℃, Yb
14MnSb
11ZT be about 0.3 and YbZn
2Sb
2ZT be about 0.35).And for the BaZn that mixes
2Sb
2, electricity is led further raising, and electric property improves, and the ZT value is played optimization function.Such as BaZn
1.99Cu
0.01Sb
2Room-temperature conductivity and Seebeck coefficient are respectively 6 * 10
4Sm
-1With 85 μ VK
-1, the ZT value reaches 0.48 in the time of 430 ℃.Thermoelectric material among the present invention is the p section bar material of hole conduction, and the preparation method is simple, can be used for utilizing in the thermoelectric transfer principle generating or the application of refrigeration.
Description of drawings
Fig. 1,2,3,4 have provided BaZn in the temperature range of 300K to 700K respectively
2Sb
2And BaZn
1.99Cu
0.01Sb
2Thermal conductivity, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).
Fig. 5 has provided BaZn among the present invention
2Sb
2Powder x-ray diffraction (XRD) experiment spectrogram and database in structure be the BaZn of Pnma
2Sb
2XRD calculates spectrogram.
Embodiment
Embodiment 1
In glove box, take by weighing Zn grain (99.999%) 0.392g, Ba metal (＞99%) 0.412g, antimony grain (99.999%) 0.731g, successively raw material is put into the graphite crucible of 25mm * Φ 10mm size that inside is lined with carbon paper from bottom to up, this crucible is put into the quartz ampoule of internal diameter Φ 11mm, rubber stopper takes out from glove box beyond the Great Wall again.With vacuum pump it is vacuumized apace then, treat that vacuum degree reaches 1 * 10
-6With oxyhydrogen flame it is sealed during torr.Put into then in the heating furnace, be warmed up to 800 ℃, be incubated 72 hours, take out with the stove cooling with the heating rate of 1 ℃/min.Product is confirmed as BaZn through powder X-ray RD
2Sb
2Pure phase, the XRD spectra that Fig. 5 has provided experiment and calculated.The powder of the sample that obtains through grinding to form utilizes rapid plasma body sintering (SPS) at 576 ℃ again, 50MPa, and sintering is about 15 minutes in the vacuum atmosphere.Gained ceramics sample density is about 90%.Then to the thermal conductance of sample in the 300K-700K scope, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).Fig. 1,2,3,4 have provided the result respectively.
Embodiment 2
Take by weighing Zn grain (99.999%) 0.651g, Cu sheet (99.999%) 0.003g, Ba metal (＞99%) 0.687g, antimony grain (99.999%) 1.218g, other conditions are with example 1, and the gained powder sample detects through powder X-ray RD and confirms as BaZn
2Sb
2Pure phase, 570 ℃ of SPS sintering temperatures, 50MPa, sintering is about 15 minutes in the vacuum atmosphere.Gained ceramics sample density is about 90%.Then to the thermal conductance of sample in the 300K-700K scope, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).Fig. 1,2,3,4 have provided the result respectively.
Embodiment 3
Take by weighing Zn grain (99.999%) 0.777g, Ag (99.999%) 0.013g, Ba metal (＞99%) 0.824g, antimony grain (99.999%) 1.461g, other conditions are with example 1, and the gained powder sample detects through powder X-ray RD and confirms as BaZn
2Sb
2Pure phase, 590 ℃ of SPS sintering temperatures, 50MPa, sintering is about 15 minutes in the vacuum atmosphere.Gained ceramics sample density is about 90%.Then to the thermal conductance of sample in the 300K-700K scope, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).Fig. 1,2,3,4 have provided the result respectively.
Embodiment 4
Take by weighing Zn grain (99.999%) 0.523g, Ge (99.99%) 0.015g, Ba metal (＞99%) 0.549g, antimony grain (99.999%) 0.950g, other conditions are with example 1, and the gained powder sample detects through powder X-ray RD and confirms as BaZn
2Sb
2Pure phase, 570 ℃ of SPS sintering temperatures, 50MPa, sintering is about 15 minutes in the vacuum atmosphere.Gained ceramics sample density is about 92%.Then to the thermal conductance of sample in the 300K-700K scope, conductivity, Seebeck coefficient and thermoelectric figure of merit (ZT value).Fig. 1,2,3,4 have provided the result respectively.
Claims (5)
1. a barium zinc antimony based p type thermoelectric material is characterized in that the chemical composition of described thermoelectric material is: Ba
1-uR
uZn
2-vT
vSb
2-zS
z, wherein R is Elements C a, Sr, and a kind of among Yb or the Eu or two kinds, x is the real composition that R mixes, 0≤x≤0.2; T is a kind of among element Cu or the Ag or two kinds, and y is the real composition that T mixes, 0≤y≤0.2; S is a kind of among element Ge or the Sn or two kinds, and z is the real composition that S mixes, 0≤z≤0.2.
2. by the preparation method of the described a kind of barium zinc antimony based p type thermoelectric material of claim 1, it is characterized in that:
Adopt metal Ba or Ba and Ca, Sr, Yb, any binary of Eu or ternary compound are raw material;
Adopt Metal Zn or Zn and Cu, any binary of Ag or ternary compound are raw material;
Adopt metal Sb or Sb and Ge, any binary of Sn or ternary compound are raw material;
Put into not in the middle of the container with raw material and product reaction 700 ℃～1000 ℃ following calcinations at least 12 hours under vacuum or inert atmosphere then by the raw material of stoichiometric proportion weighing;
Take out product cooling back after the calcination.
3. by the preparation method of the described a kind of barium zinc antimony based p type thermoelectric material of claim 2, it is characterized in that the product after the calcination carries out rapid plasma body sintering or hot pressed sintering again.
4. by the preparation method of the described a kind of barium zinc antimony based p type thermoelectric material of claim 3, it is characterized in that rapid plasma body sintering condition is 500 ℃～600 ℃ of sintering temperatures, pressure 30～50Mpa.
5. by the preparation method of the described a kind of barium zinc antimony based p type thermoelectric material of claim 3, the condition that it is characterized in that hot pressed sintering is 400 ℃～700 ℃ of hot pressed sintering temperature, pressure 20～60MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100438444A CN101118946B (en) | 2007-07-16 | 2007-07-16 | Barium zinc antimony based p type thermoelectric material and method for making same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100438444A CN101118946B (en) | 2007-07-16 | 2007-07-16 | Barium zinc antimony based p type thermoelectric material and method for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101118946A true CN101118946A (en) | 2008-02-06 |
| CN101118946B CN101118946B (en) | 2011-03-16 |
Family
ID=39054955
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956350A (en) * | 2008-02-14 | 2014-07-30 | 英飞凌科技股份有限公司 | Module including a sintered joint bonding a semiconductor chip to a copper surface |
| CN110265540A (en) * | 2019-05-31 | 2019-09-20 | 上海大学 | Barium copper tellurium based p type thermoelectric material and preparation method thereof |
| CN111081857A (en) * | 2019-12-25 | 2020-04-28 | 哈尔滨工业大学（深圳） | Zintl phase thermoelectric material with hexagonal ZrBeSi structure and preparation method thereof |
-
2007
- 2007-07-16 CN CN2007100438444A patent/CN101118946B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103956350A (en) * | 2008-02-14 | 2014-07-30 | 英飞凌科技股份有限公司 | Module including a sintered joint bonding a semiconductor chip to a copper surface |
| CN110265540A (en) * | 2019-05-31 | 2019-09-20 | 上海大学 | Barium copper tellurium based p type thermoelectric material and preparation method thereof |
| CN110265540B (en) * | 2019-05-31 | 2022-07-08 | 上海大学 | Barium-copper-tellurium-based p-type thermoelectric material and preparation method thereof |
| CN111081857A (en) * | 2019-12-25 | 2020-04-28 | 哈尔滨工业大学（深圳） | Zintl phase thermoelectric material with hexagonal ZrBeSi structure and preparation method thereof |
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