CN100500900C - Alkali-metal atom filled cobalt stibide based skutterudite thermoelectric material and preparation method - Google Patents
Alkali-metal atom filled cobalt stibide based skutterudite thermoelectric material and preparation method Download PDFInfo
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- CN100500900C CN100500900C CNB200610030526XA CN200610030526A CN100500900C CN 100500900 C CN100500900 C CN 100500900C CN B200610030526X A CNB200610030526X A CN B200610030526XA CN 200610030526 A CN200610030526 A CN 200610030526A CN 100500900 C CN100500900 C CN 100500900C
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- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 17
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- 238000002360 preparation method Methods 0.000 title claims description 21
- 229910017052 cobalt Inorganic materials 0.000 title claims description 16
- 239000010941 cobalt Substances 0.000 title claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 16
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000011049 filling Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 11
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- 230000000171 quenching effect Effects 0.000 claims abstract description 9
- 238000007669 thermal treatment Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 238000005516 engineering process Methods 0.000 claims description 16
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- 230000004927 fusion Effects 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 13
- 239000010453 quartz Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- NSRGWYQTFLSLOJ-UHFFFAOYSA-N antimony;cobalt(3+) Chemical compound [Co+3].[Sb] NSRGWYQTFLSLOJ-UHFFFAOYSA-N 0.000 abstract 2
- 238000000227 grinding Methods 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 229910052701 rubidium Inorganic materials 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 15
- 230000005619 thermoelectricity Effects 0.000 description 12
- 239000011734 sodium Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000005538 encapsulation Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 229910018989 CoSb Inorganic materials 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
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- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
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- 239000002918 waste heat Substances 0.000 description 1
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Abstract
This invention relates to a method for preparing alkali-metal-filled cobalt-antimonide-based thermoelectric material having high filling amount and excellent thermoelectric property. The thermoelectric material has a general chemical formula of AyCo4Sb12, wherein y is within 0-1, and A is at least one of Li, Na, K and Rb. The method comprises: (1) preparing metal raw materials with purities higher than 99% according to a stoichiometric ratio of Ay+y'Co4Sb12, wherein y' is within 0-0.5y and y within 0-1; (2) mixing and filling into a carbon-coated quartz tube in vacuum or inert atmosphere; (3) heating to 950-1200 deg.C for melting, and reacting completely; (4) quenching in air or quenching liquid oil (oil or water) to obtain AyCo4Sb12 crystal rod; (5) grinding into powder, mixing uniformly and tableting; (6) performing thermal treatment in inert atmosphere, grinding into powder, placing into a graphite mold, and rapidly sintering by plasma-discharging sintering to obtain compact block. The method has such advantages as simple process and low cost, and the obtained alkali-metal-filled cobalt-antimonide-based thermoelectric material has excellent thermoelectric properties.
Description
Technical field
A kind of alkali metal atom with high filler loading capacity, good thermoelectricity capability is filled cobalt stibide based skutterudite material and preparation method thereof, belongs to the thermoelectric material field.
Technical background
The thermoelectric power generation technology is to utilize the Seebeck effect of semiconductor material directly heat energy to be converted into the technology of electric energy, it has no drive disk assembly, reliability height, long, advantages of environment protection of life-span, plays an important role at numerous areas such as waste-heat power generation, space science, military equipment, household electrical appliance.Its efficiency of conversion depends primarily on the zero dimension thermoelectricity capability performance index ZT (ZT=S of material itself
2σ T/ κ, wherein S is the Seebeck coefficient; σ is a specific conductivity; κ is a thermal conductivity, and T is an absolute temperature).The ZT value of material is high more, and its thermopower generation efficiency is also high more.At present, several sophisticated thermoelectric material systems are as CoSb
3, Bi
2Te
3, GeSi, PbTe etc., the ZT value of its block materials is generally all about 1.0.
Skutterudite compound belongs to body-centered cubic structure, the characteristics of its crystalline structure maximum are that the position, body-centered exists the hollow cage that volume is very big, other atoms metals (as rare earth and alkaline-earth metal) can be filled in the mode that weak bond closes in this cage and produce perturbation action greatly the scattering phonon, reduce the lattice thermal conductivity of material significantly, wherein cage is filled the occupied ratio of atom is become loading level.Simultaneously, provide current carrier to optimize the material electric property in crystalline structure thereby fill atom, the thermoelectricity capability of the skutterudite compound material after the filling increases substantially and makes it to become one of best thermoelectric power generation material of performance, and its ZT value surpasses 1.0.But, rare earth and alkaline-earth metal are as filling the atomic time, because these high valence states of filling atom make optimized electricity and thermal property be difficult to obtain simultaneously and its loading level is also very low (wherein the highest with barium, be 0.44, and loading level is about 0.25 o'clock best performance), the adjustable packing space that obtains good thermoelectricity capability is less.For more active alkali metal atom, because their strong inflammableness, low melting point, high-vapor-pressure and severe corrosive, the skutterudite compound that the alkali metal atom of preparation high purity, high filler loading capacity and good thermoelectricity capability is filled is very difficult.But, because the lower valency of alkali metal atom, it fills the cobalt stibide based skutterudite compound can still can keep higher loading level when obtaining optimized electrical transmission performance, directly cause the further reduction of lattice thermal conductivity, thereby improves the thermoelectricity capability of material.Though alkali metal atom filled skutterudite compound is a kind of very promising high performance thermoelectric material, relevant filling in thermoelectric material of cobalt stibide based skutterudite by alkali-metal atom and preparation method thereof yet there are no report in the past.
Usefulness such as A.Leithe-Jasper two single-step solid phase reaction methods have prepared the skutterudite compound of charge compensation NaFe
4Sb
12And KFe
4Sb
12(Physical Review B, 70,214418,2004), this method is earlier with solid state reaction synthetic mesophase compound N aSb or KSb, because these two kinds of materials are very unstable in air, whole synthesis step will be finished under the atmosphere of protection of inert gas or in the vacuum, make this preparation technology become very complicated and also the cycle long; And the material crystallinity of this method preparation is very poor, and contains a lot of impurity.Intermediate compound (BaSb such as L.Chen
3) synthesized active divalent alkaline-earth metal filling in thermoelectric material of cobalt stibide based skutterudite Ba in conjunction with scorification
yCo
4Sb
12(Journal of Applied Physics, 90,1864,2001), the thermoelectricity capability of material is good, but this method needs repeatedly thermal treatment for a long time, and solid state reaction to prepare the technology of intermediate compound complicated, cause preparation cycle very long.The method that the Nakashima Kenichi youth adopts fusion to add quenching has prepared the thermoelectric material of cobalt stibide based skutterudite (Chinese invention patent that rare earth element is filled, application number: 03823174.3), adopt the bar casting that this melts rapid quenching is formed cured product then the raw metal fusion, the characteristics of this method are that cycle weak point, product are easy to processing, but the degree of purity of production of gained is not high, crystallinity is bad.The double-deck silica tube encapsulation technologies of employing such as Sung-Jin Kim have been synthesized the alloy material Rb that contains active alkali metal
3Yb
7Se
12Deng (Inorganic Chemistry, 35,5283,1996), change technology and can prevent well that the silica tube that is caused by the high pressure of byproduct gas in the reaction process from bursting, obtained very stable preparation technology.
Summary of the invention
The objective of the invention is to utilize stable preparation technology to comprise raw material encapsulation, fusion, quenching and thermal treatment etc., by optimizing processing parameter, it is simple to obtain a kind of technology, and the ripe preparation method of the good basic metal filled skutterudite material of thermoelectricity capability is lacked and can be obtained to preparation cycle.
The present invention is used for the preparation field of skutterudite-base thermoelectrical material with double-deck utter misery silica tube encapsulation technology, and the preparation difficulty that high-vapor-pressure brought that has not only solved alkali metal has also solved its severe corrosive problem simultaneously.
The present invention adopts the method for fusion and quenching to prepare the skutterudite-base high performance thermoelectric material that basic metal is filled, and the materials chemistry general formula is A
yCo
4Sb
12(0＜y≤1), wherein, A is a kind of among Li, Na, K, the Rb at least.Prepare the tin white cobalt material that basic metal is filled by optimizing the technology ginseng.Preparation technology of the present invention is simple, and is with low cost, and industrialization prospect is good.
Key problem in technology of the present invention is to optimize processing parameter to obtain good crystallinity, purity height and the good basic metal filling skutterudite thermoelectric material of thermoelectricity capability, fill atomic species and loading level by control, optimize heat, the electrical transmission performance of material, obtain high performance thermoelectric material.Concrete processing step is:
1, raw material encapsulation
High purity (〉 99%) metal simple-substance raw material is pressed chemical formula A
Y+y, Co
4Sb
12Stoichiometric ratio batching, wherein (0≤y '≤0.5y, 0＜y≤1) is waste in the reaction process, be encapsulated into after mixing in the carbon-coating layer silica tube of vacuum or inert gas atmosphere, the packaged carbon-coating layer silica tube that raw material is housed is Vacuum Package one deck vacuum or inert gas atmosphere carbon-coating layer silica tube more outward, and its structure iron as shown in Figure 1.
2, fusion and quenching
The silica tube that raw metal is housed that step 1 is obtained slowly is heated to 950～1200 ℃, and raw metal carries out quenching in air or hardening liquid (oil, water) behind the abundant chemical reaction under molten state, obtains A
yCo
4Sb
12Crystal bar.The heat-up rate of melting process is less than 5 ℃ of/minute kinds, and the fusion time was less than 30 hours.
3, thermal treatment and sintering
The A that step 2 is obtained
yCo
4Sb
12The crystal bar grind into powder mixes the back compressing tablet, thermal treatment 1～100 hour in inert gas environment then, and heat treated temperature is 400 ℃～800 ℃.A after heat treated
yCo
4Sb
12Sample is grind into powder again, places graphite jig to adopt discharge plasma sintering technology (SPS) that its Fast Sintering is become fine and close block, and sintering temperature is about 450 ℃～800 ℃, and the time is less than 30 minutes, and pressure is 10～100MPa.
The principal feature that the alkali metal atom of the present invention's preparation is filled cobalt stibide based skutterudite material and preparation method is presented as:
At first, loading level alkaline earth, rare earth more in the past has been filled with bigger raising, and the high filler loading capacity of the potassium of the present invention preparation and sodium is respectively 0.45 and 0.65, all is higher than the high filler loading capacity of being reported at present 0.44 (barium atom);
Secondly, because alkali metal atom provides less current carrier during identical loading level in crystalline structure, material has kept high loading level when obtaining optimization electrical transmission performance, thereby has greatly reduced the lattice thermal conductivity of material, and the thermoelectricity capability of final material obtains to increase substantially;
At last, that the application of double-deck utter misery silica tube raw material encapsulation technology has been prepared is high-purity, the thermoelectric material of high filler loading capacity, excellent property, and process stabilizing and cycle are short.
Description of drawings
Fig. 1 is the packaged alloy raw material synoptic diagram of double-deck utter misery silica tube, is vacuum or inert gas environment in internal layer and the outer ampoule chamber, and in the synoptic diagram: 1 is hook; 2 is outer utter misery silica tube; 3 is internal layer utter misery silica tube; 4 is alloy raw material.
Fig. 2 is K
yCo
4Sb
12X ray diffracting spectrum (a.K
0.38Co
4Sb
12, b.CoSb
3The JCPD standard card), resulting product is pure tin white cobalt phase, and crystallinity is good.
Fig. 3 is K
yCo
4Sb
12The lattice thermal conductivity of filled skutterudite material and the relation of temperature during room temperature, are filled the back thermal conductivity and are reduced about 60%.
Fig. 4 is K
yCo
4Sb
12The ZT value of filled skutterudite material and the relation of temperature, maximum ZT value rises to about original 5 times.
Fig. 5 is Na
yCo
4Sb
12X ray diffracting spectrum (a.Na
0.5Co
4Sb
12, b.CoSb
3The JCPD standard card), resulting product is pure tin white cobalt phase, and crystallinity is good.
Fig. 6 is Na
yCo
4Sb
12The thermal conductivity of filled skutterudite material and the relation of temperature during room temperature, are filled the back thermal conductivity and are reduced about 70%.
Fig. 7 is Na
yCo
4Sb
12The ZT value of filled skutterudite material and the relation of temperature, maximum ZT value rises to about original 6 times.
Embodiment
Further illustrate inherent characteristics of the present invention and progressive thereof below by following embodiment.Embodiment 1:K
yCo
4Sb
12Material
Raw metal K, Co, Sb are prepared burden respectively according to 0:4:12 and 0.5:4:12 mol ratio, bilayer is encapsulated in the vacuum utter misery silica tube, raw material after the encapsulation is quenched in air after 30 minutes in 1150 ℃ of following fusions together with quartz ampoule, the crystal bar that obtains is pulverized last in 800 ℃ of thermal treatments 1 hour, and the powder that obtains shows that through X-ray diffraction analysis the synthetic material is pure phase K
yCo
4Sb
12The tin white cobalt material, to loading level be 0.38.The K that the X ray diffracting spectrum explanation is obtained
0.38Co
4Sb
12Good and the very high (see figure 2) of purity of material crystallinity.450 ℃ of following sintering 25 minutes, employing pressure was 100Mpa to the gained powder through SPS.The lattice thermal conductivity of thermal conductivity test shows potassium filled skutterudite material is starkly lower than does not have the body material K that fills atom
0.38Co
4Sb
12(see figure 3); By measuring specific conductivity and Seebeck coefficient, calculate to such an extent that ZT value result shows that monovalent base atoms metal potassium filled skutterudite material has good thermoelectricity capability (maximum ZT value is 1.03, sees Fig. 4).
Embodiment 2:Na
yCo
4Sb
12Material
With raw metal Na, Co, Sb according to 0:4:12 and 0.6:4:12 molar ratio ingredient, bilayer is encapsulated in the utter misery silica tube that is filled with small amounts of inert gas, with the encapsulation after raw material together with quartz ampoule in 950 ℃ of following fusions after 30 hours at quenching-in water, the crystal bar that obtains is pulverized last in 400 ℃ of thermal treatments 100 hours, and the powder that obtains shows that through X-ray diffraction analysis the synthetic material is pure phase NayCo
4Sb
12Tin white cobalt material, resulting loading level are 0.5.The Na of this method preparation
0.5Co
4Sb
12And CoSb
3Good crystallinity, the high (see figure 5) of purity.750 ℃ of following sintering 10 minutes, employing pressure was 30Mpa to the gained powder through SPS.The very low (see figure 6) of lattice thermal conductivity of thermal conductivity test chart natulanar filled skutterudite material; By measuring specific conductivity and Seebeck coefficient, calculate to such an extent that ZT value result shows that monovalent base atoms metal sodium filled skutterudite material has good thermoelectricity capability (maximum ZT value is 1.2, sees Fig. 7).
Claims (3)
1, a kind of filling in thermoelectric material of cobalt stibide based skutterudite by alkali-metal atom is characterized in that its chemical general formula is A
yCo
4Sb
12, 0＜y≤1 wherein, A is a kind of among Li, Na, K, the Rb at least.
2, by the preparation method of the described a kind of filling in thermoelectric material of cobalt stibide based skutterudite by alkali-metal atom of claim 1, comprise the steps:
(1) purity〉99% metal simple-substance raw material presses chemical formula A
Y+y 'Co
4Sb
12Stoichiometric ratio batching, wherein
0＜y≤1 is encapsulated into after mixing in the carbon-coating layer silica tube of vacuum or inert gas atmosphere;
(2) silica tube that raw metal is housed that step 1 is obtained slowly is heated to 950～1200 ℃, the raw metal fusion and under molten state, carry out abundant chemical reaction after quenching in air or hardening liquid (oil, water), obtain A
yCo
4Sb
12Crystal bar, wherein heat temperature raising speed is less than 5 ℃ of/minute kinds, and the fusion time was less than 30 hours;
(3) A that step 2 is obtained
yCo
4Sb
12The crystal bar grind into powder mixes the back compressing tablet, thermal treatment in inert gas environment then, and heat treatment time is 1～100 hour, heat treated temperature is 400 ℃～800 ℃;
(4) A of step 3 after heat treated
yCo
4Sb
12Sample is grind into powder again, places graphite jig to adopt the discharge plasma sintering technology that its Fast Sintering is become fine and close block, and sintering temperature is about 450 ℃～800 ℃, and the time is less than 30 minutes, and pressure is 10～100MPa.
3,, it is characterized in that described carbon-coating layer silica tube is one or more layers by the preparation method of the described a kind of filling in thermoelectric material of cobalt stibide based skutterudite by alkali-metal atom of claim 2.
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| US20100071741A1 (en) * | 2008-03-14 | 2010-03-25 | Gm Global Technology Operations, Inc. | Thermoelectric material including a filled skutterudite crystal structure |
| CN102031416B (en) * | 2009-09-28 | 2012-08-29 | 中国科学院上海硅酸盐研究所 | Composite material of skutterudite filling substrate and preparation method thereof |
| CN103811653B (en) * | 2014-01-21 | 2017-01-25 | 燕山大学 | Multi-cobalt p type skutterudite filled thermoelectric material and preparation method thereof |
| CN104498751B (en) * | 2014-12-25 | 2017-01-18 | 中国科学院上海硅酸盐研究所 | Preparation method of thermoelectric material of skutterudite |
| CN108754230B (en) * | 2018-06-12 | 2020-06-16 | 西北工业大学 | Method for efficiently preparing pure CoSb 3-based medium-temperature thermoelectric material |
| CN109103323A (en) * | 2018-07-16 | 2018-12-28 | 电子科技大学 | A method of Sb is replaced by filling Ga, Te and improves based square cobalt mineral conducting material thermoelectricity performance |
| CN112397635B (en) * | 2020-11-16 | 2023-04-18 | 昆明理工大学 | GeTe doped Co 4 Sb 12 Method for preparing thermoelectric material |
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