CN100445431C - Preparation method of I-type germanium-radical clathrate single-crystal and new single-crystal filled with barium and strontium - Google Patents
Preparation method of I-type germanium-radical clathrate single-crystal and new single-crystal filled with barium and strontium Download PDFInfo
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- CN100445431C CN100445431C CNB2006100246401A CN200610024640A CN100445431C CN 100445431 C CN100445431 C CN 100445431C CN B2006100246401 A CNB2006100246401 A CN B2006100246401A CN 200610024640 A CN200610024640 A CN 200610024640A CN 100445431 C CN100445431 C CN 100445431C
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Abstract
The invention relates to I-type germanium group clathrate monocrystal thermoelectric material and its preparation method. The method for preparing I-type germanium group clathrate monocrystal includes, using fusing assistant method, weighing germanium, gallium and alkali metals (or alkaline earth metals) and placing them in the big corundum crucible, then placing small corundum crucible on the big corundum crucible, airproofing the groove formed between the big corundum crucible and small corundum crucible, at last placing both corundum crucibles together in the inert gas to produce monocrystal. Common stainless steel container can not be used when monocrystal is produced using Ca as fusing assistant, accordingly the method is easier with lower cost. Novel complex monocrystal in which I-type germanium group clathrate containing barium is as the housing of I-type germanium group clathrate containing strontium, having complicated interface of kernel/transition layer/outer layer inside. The interface can scatter the transmission of phonon to reduce heat conductivity, accordingly it has better thermoelectricity property than Sr8Ga16Ge30 and Ba8Ga16Ge30.
Description
Technical field
The present invention relates to I-type germanium-radical clathrate single-crystal thermoelectric material and preparation method thereof technical field.
Background technology
Slack propose desirable thermoelectric material be can resemble conduct electricity the crystal and can resemble the glass heat insulation, i.e. phonon glass electron crystal [phonon glass, electron crystal (PGEC)].I-type germanium-radical clathrate is one of material system that meets the PGEC new ideas [Nolas G.S., Slack G.A., Morelli D.T., Tritt T.M.and Ehrlich A.C., J.Appl.Phys.1996,79:4002.], and its structure expression is M
8Ge
46(M is basic metal or alkaline-earth metal) has cubic structure, and spacer is Pm3n, and the M atom is filled in the structure space by the Ge atomic building.In order to improve thermoelectricity capability, substitute Ge with part Ga usually, expression formula becomes M
8Ga
16Ge
30(M is an alkaline-earth metal) or M
8Ga
8Ge
30(M is a basic metal).
Because I-type germanium-radical clathrate meets the PGEC new ideas, have potential thermoelectric applications value, thereby attracted a lot of people's research interest, but research so far is I-type germanium-radical clathrate polycrystalline material mostly.Because the difference of preparation condition, make that the component, density etc. of polycrystalline material are variant, thereby cause the material property reported uneven.Comparatively speaking, the performance circulation ratio of monocrystal material is better and structural information its reflection is more reliable.Flux method is a kind of fairly simple method for preparing monocrystalline, required device simple.Ga has very low fusing point (29.8 ℃) and very high boiling point (2237 ℃), it is again one of constituent element of required synthetic I-type germanium-radical clathrate, be well suited for doing fusing assistant, and be successfully used to prepare Ge radical clathrate [LatturnerS.E., Bryan J.D., Blake N., Metiu H.and Stuky G.D., Inorganic Chem.2002,41:3956. and BentienA., Palmqvist A.E.C., Bryan J.D., Latturner S., Stucky G., Furenlid L, Iversen B.B.Angew.Chem.Int.Ed.2000,39:3613].And the document from having reported, making fusing assistant with Ga, to prepare the Ge radical clathrate all be that required raw material weighing is placed in the corundum crucible, putting into stove after then corundum crucible being placed a kind of special stainless steel vessel to seal heats again.Because temperature height, the required time of preparation are long, this stainless steel vessel can't repeatedly use, and is therefore uneconomical.
Summary of the invention
Purpose of the present invention is exactly the shortcoming that overcomes existing I-type germanium-radical clathrate single-crystal preparation method, and a kind of method for preparing I-type germanium-radical clathrate single-crystal new, easier economy is provided.
A further object of the invention is to utilize method for preparing to go out the I-type germanium-radical clathrate single-crystal of a kind of filled with barium and strontium, provides more fine monocrystal material for preparing the high efficiency thermoelectric switching device.
For realizing above purpose, the technical scheme that the present invention takes is:
A kind of preparation method of I-type germanium-radical clathrate single-crystal; this method is to adopt flux method; at first weighing germanium, gallium and basic metal (or alkaline-earth metal) are positioned in the big corundum crucible; be upside down on the big corundum crucible with little corundum crucible then; the groove that forms between the big or small corundum crucible is sealed, at last two corundum crucibles are placed together preparation monocrystalline under the protection of inert gas.
The preparation method of described I-type germanium-radical clathrate single-crystal, when weighing germanium, gallium and basic metal (or alkaline-earth metal), the consumption of gallium is its stoichiometric 4-7 times, and carries out in the glove box of argon shield; The groove that forms between the size corundum crucible seals with high vacuum fat.
The I-type germanium-radical clathrate composite single crystal of a kind of filled with barium and strontium, this crystal is divided into kernel, transition layer and skin, and skin contains Sr, Ga and Ge, and transition layer contains Sr, Ba, Ga and Ge, and kernel contains Ba, Ga, Ge.
Beneficial effect of the present invention: we place big corundum crucible with raw material when preparing monocrystalline with Ga as fusing assistant, little corundum crucible is upside down on the big corundum crucible, is sealed with high vacuum fat, has saved stainless steel vessel commonly used, therefore more simple, cost is also lower.The I-type germanium-radical clathrate that has also synthesized a kind of filled with barium with this method is that the I-type germanium-radical clathrate that nuclear is filled strontium is the compound new single-crystal of shell, this new single-crystal includes complicated interface: kernel/transition layer/skin, can reduce thermal conductivity thereby this interface to the transmission of phonon scattering can take place, therefore be expected to have and compare Sr
8Ga
16Ge
30And Ba
8Ga
16Ge
30Better thermoelectricity capability.
Description of drawings
Fig. 1 is the monocrystalline photo of preparing in kind
Fig. 2 be I-type germanium-radical clathrate that the I-type germanium-radical clathrate of embodiment 3 preparation filled with barium is filled strontium for nuclear be shell compound new single-crystal profile scanning Electronic Speculum figure and corresponding to section upper edge white line can spectrogram
Fig. 3 is each atom percentage content distribution plan of the compound new single-crystal of embodiment 3 preparations.
Embodiment
In the glove box of argon shield, press stoichiometric ratio (M: Ga: Ge=8: 8: 30 mol ratios; M is basic metal or M: Ga: Ge=8: 16: 30; mol ratio, M is an alkaline-earth metal) high-purity simple substance M, germanium and the gallium of weighing, but the consumption of gallium is it stoichiometric 4-7 times.Weighing is placed in the corundum crucible that volume is 10ml, is that the corundum crucible of 6ml covers on the corundum crucible of above-mentioned 10ml with volume, moves in the quartz tube type atmosphere furnace after using high vacuum fat (7501) sealing then.Under argon shield with 5 ℃/min be warming up to 1050 ℃ the insulation 2 hours after slowly the cooling (0.03-0.1 ℃/min) to 700 ℃, the speed with 0.5 ℃/min is cooled to room temperature subsequently.Product is removed remaining gallium with the hydrochloric acid of hot water or 1-2M, uses deionized water and dehydrated alcohol ultrasonic cleaning until totally again, obtains required monocrystalline.
Example 1: the I-type germanium-radical clathrate of preparation filled with barium: Ba
8Ga
16Ge
30Monocrystalline
In the glove box of argon shield by stoichiometric ratio (Ba: Ga: Ge=8: 16: 30, mol ratio) high-purity simple substance barium 0.25g, germanium 0.4958g and the gallium 1.27g (consumption of gallium is its stoichiometric 5 times) of weighing.Weighing is placed in the corundum crucible that volume is 10ml, is that the corundum crucible of 6ml covers on the corundum crucible of above-mentioned 10ml with volume, moves in the quartz tube type atmosphere furnace after using high vacuum fat (7501) sealing then.Under argon shield with 5 ℃/min be warming up to 1050 ℃ the insulation 2 hours after slowly the cooling (0.03-0.1 ℃/min) to 700 ℃, the speed with 0.5 ℃/min is cooled to room temperature subsequently.Product is removed remaining gallium with the hydrochloric acid of hot water or 1-2M, uses deionized water and dehydrated alcohol ultrasonic cleaning until totally again, obtains size and is the Ba of 5-8mm
8Ga
16Ge
30Monocrystalline.
Example 2: the I-type germanium-radical clathrate of strontium: Sr is filled in preparation
8Ga
16Ge
30Monocrystalline
In the glove box of argon shield by stoichiometric ratio (Sr: Ga: Ge=8: 16: 30, mol ratio) high-purity simple substance strontium 0.175g, germanium 0.5452g and the gallium 1.396g (wherein the consumption of gallium is its stoichiometric 5 times) of weighing.Weighing is placed in the corundum crucible that volume is 10ml, is that the corundum crucible of 6ml covers on the corundum crucible of above-mentioned 10ml with volume, moves in the quartz tube type atmosphere furnace after using high vacuum fat (7501) sealing then.Under argon shield with 5 ℃/min be warming up to 1050 ℃ the insulation 2 hours after slowly the cooling (0.03-0.1 ℃/min) to 700 ℃, the speed with 0.5 ℃/min is cooled to room temperature subsequently.Product is removed remaining gallium with the hydrochloric acid of hot water or 1-2M, uses deionized water and dehydrated alcohol ultrasonic cleaning until totally again, obtains size and is the Sr of 2-4mm
8Ga
16Ge
30Monocrystalline.
Example 3, the I-type germanium-radical clathrate that the I-type germanium-radical clathrate of filled with barium is filled strontium for nuclear is the compound new single-crystal of shell
In the glove box of argon shield, press stoichiometric ratio (Sr: BaGa: Ge=2: 6: 16: 30; mol ratio; wherein Sr: Ba is also 4: 4; 6: 2) high-purity simple substance strontium 0.04074g, the barium 0.1916g of weighing; germanium 0.5063g and gallium 1.2967g, wherein the consumption of gallium is its stoichiometric 5 times.Weighing is placed in the corundum crucible that volume is 10ml, is that the corundum crucible of 6ml covers on the corundum crucible of above-mentioned 10ml with volume, moves in the quartz tube type atmosphere furnace after using high vacuum fat (7501) sealing then.Under argon shield with 5 ℃/min be warming up to 1050 ℃ the insulation 2 hours after slowly the cooling (0.03-0.1 ℃/min) to 700 ℃, the speed with 0.5 ℃/min is cooled to room temperature subsequently.Product is removed remaining gallium with the hydrochloric acid of hot water or 1-2M, uses deionized water and dehydrated alcohol ultrasonic cleaning until totally again, obtains being of a size of the monocrystalline of 2-4mm.
The section of monocrystalline finds that with scanning electron microscope/energy spectrum analysis (as Fig. 2) the crystalline composition is uneven, and the outside is to contain Sr, Ga, and Ge, inside contains Ba, Ga, Ge, the composition of a transition layer contains Sr, Ba, Ga, Ge at interval.The I-type germanium-radical clathrate that is filled with barium is the compound new single-crystal of shell for examining the I-type germanium-radical clathrate of filling strontium.
Because this kind monocrystalline includes complicated interface: kernel/transition layer/skin, thereby to the transmission of phonon scattering can taking place, this interface can reduce thermal conductivity, therefore have the Sr of ratio
8Ga
16Ge
30And Ba
8Ga
16Ge
30Better thermoelectricity capability.
Claims (4)
1, a kind of preparation method of I-type germanium-radical clathrate single-crystal; this method is to adopt flux method; it is characterized in that: at first a kind of and germanium, the gallium in weighing basic metal or the alkaline-earth metal is positioned in the big corundum crucible; be upside down on the big corundum crucible with little corundum crucible then; the groove that forms between the big or small corundum crucible is sealed, at last two corundum crucibles are placed together preparation monocrystalline under the protection of inert gas.
2, the preparation method of I-type germanium-radical clathrate single-crystal as claimed in claim 1 is characterized in that: when a kind of and germanium in weighing basic metal or alkaline-earth metal, gallium, the consumption of gallium is its stoichiometric 4-7 times, and carries out in the glove box of argon shield.
3, the preparation method of I-type germanium-radical clathrate single-crystal as claimed in claim 1 is characterized in that: the groove that forms between the big or small corundum crucible seals with high vacuum fat.
4, a kind of filled with barium of the described method preparation of the arbitrary claim of claim 1-3 and the I-type germanium-radical clathrate composite single crystal of strontium, this crystal is divided into kernel, transition layer and outer three parts, and skin contains Sr, Ga and Ge, transition layer contains Sr, Ba, Ga and Ge, kernel contains Ba, Ga, Ge.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160910A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院上海硅酸盐研究所 | Method for growing Ba8Ga16Ge30 thermoelectric monocrystal |
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|---|---|---|---|---|
| CN103114215B (en) * | 2013-03-13 | 2015-04-01 | 北京科技大学 | Method for preparing Ga-containing cage-shaped compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6188011B1 (en) * | 1998-01-20 | 2001-02-13 | Marlow Industries, Inc. | Thermoelectric materials fabricated from clathrate compounds and other materials which form an inclusion complex and method for optimizing selected thermoelectric properties |
| US6525260B2 (en) * | 2000-08-18 | 2003-02-25 | Sumitomo Special Metals Co., Ltd. | Thermoelectric conversion material, and method for manufacturing same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6188011B1 (en) * | 1998-01-20 | 2001-02-13 | Marlow Industries, Inc. | Thermoelectric materials fabricated from clathrate compounds and other materials which form an inclusion complex and method for optimizing selected thermoelectric properties |
| US6525260B2 (en) * | 2000-08-18 | 2003-02-25 | Sumitomo Special Metals Co., Ltd. | Thermoelectric conversion material, and method for manufacturing same |
Non-Patent Citations (2)
| Title |
|---|
| 1-型锗基笼形物-极有希望的热电材料. 蔡克峰.功能材料与器件学报，第10卷第2期. 2004 |
| 1-型锗基笼形物-极有希望的热电材料. 蔡克峰.功能材料与器件学报，第10卷第2期. 2004 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160910A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院上海硅酸盐研究所 | Method for growing Ba8Ga16Ge30 thermoelectric monocrystal |
| CN103160910B (en) * | 2011-12-14 | 2015-10-21 | 中国科学院上海硅酸盐研究所 | Ba 8ga 16ge 30the growth method of thermoelectric monocrystal |
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