CN1605417A - Process for preparing N type Co-Sb series skutterudite compound thermoelectric materials - Google Patents
Process for preparing N type Co-Sb series skutterudite compound thermoelectric materials Download PDFInfo
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- CN1605417A CN1605417A CN 200410086894 CN200410086894A CN1605417A CN 1605417 A CN1605417 A CN 1605417A CN 200410086894 CN200410086894 CN 200410086894 CN 200410086894 A CN200410086894 A CN 200410086894A CN 1605417 A CN1605417 A CN 1605417A
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 229910020712 Co—Sb Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000013590 bulk material Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 230000005619 thermoelectricity Effects 0.000 abstract description 12
- 238000001291 vacuum drying Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000010248 power generation Methods 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 1
- 239000007769 metal material Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 229910052787 antimony Inorganic materials 0.000 description 11
- 229910018989 CoSb Inorganic materials 0.000 description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 101100070541 Podospora anserina (strain S / ATCC MYA-4624 / DSM 980 / FGSC 10383) het-S gene Proteins 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The preparation process of pyroelectric material of n-type Co-Sb skutterudite compound includes the following steps: weighing metal material powder based on the expression of RyNixCo4-xSb12, where R is RE element, x is 0-1, y is 0-2 and x and y are not 0 simultaneously; grinding in alcohol medium inside a ball mill for fully mixing; vacuum drying the mixture at 50-75 deg.c inside a vacuum dryer; densifying the mixture inside a mold and vacuum sintering at 500-700 deg.c in a discharging plasma sintering apparatus for 2-10 min to form block material. The present invention has high production efficiency, low cost, capacity of forming n-type material for thermopile without need of further shaping, high thermoelectricity performance and other advantages, and the product may be used in thermoelectric power generation at 400-500 deg.c.
Description
Technical field
The present invention relates to a kind of n-type Co-Sb is the preparation method of skutterudite compound thermoelectric material, belongs to the manufacturing technology field of thermoelectric material.
Background technology
The present invention relates to a kind of Co-Sb pyroelectric material that heat energy is directly changed into electric energy by Seebeck effect and preparation method thereof.
The Co-Sb pyroelectric material is that development in recent years is got up had a kind ofly both had higher thermal photoelectric transformation efficiency, the material that can work again in the operating temperature interval of broad.Typical case's representative of such thermoelectric material is CoSb
3, having skutterudite (skutterudite) type crystal structure, electronics that it is higher or hole mobility make material have high electrical conductivity and Seebeck coefficient; Simultaneously, by rare earth or other metallic atom to the big quality of filling in the lattice hole, and the displacement of carrying out the different metal atom, can reduce the lattice thermal conductivity of material greatly again, thereby increase substantially the thermoelectricity capability of material.Moreover, the displacement of different elements or filling be the conduction type of adjustable thermoelectric material also, obtains the Co-Sb pyroelectric material of p type or n type.Therefore, the Co-Sb pyroelectric material is considered at present one of the most promising thermoelectric material.
The performance of thermoelectric material is characterized by a dimensionless quality factor ZT usually, ZT=S
2σ T/k, wherein S is a Seebeck coefficient, and σ is an electrical conductivity, and k is a thermal conductivity, and T is a temperature.Good thermoelectric material should have high quality factor, promptly has big S, σ and little k, and this just requires material to have higher density and less crystallite dimension.
At present, CoSb
3Fusion-annealing and solid phase reaction method are adopted in the preparation of base thermoelectricity material usually.Because the fusing point of metallic cobalt and antimony differs greatly (about 865 ℃), therefore in preparation process, usually can cause the volatilization of antimony, thereby cause the end product component segregation bigger, dephasign content height in the material, performance descends; In addition, manufacturing cycle is long, and annealing process particularly often requires tens even the annealing of hundreds of hour, causes crystal grain to grow up unusually and the raising of thermal conductivity, and material property has deteriorated significantly.As Japan Patent [open communique 1996 186294A number], about CoSb
3The technology of preparing of base thermoelectricity material sintered body, disclosed Co and Sb fusion, make ingot, then ingot is pulverized, will carry out the method for long-time sintering after its powders compression moulding and behind sintering, make the densified method of sintered body by hot pressing and high temperature insostatic pressing (HIP) technology such as (HIP) again.In this sintering process, obtain fine and close CoSb
3Be sintered body, need long sintering usually, therefore, promptly use attritive powder to carry out sintering,, can not obtain high fine and close and fine crystal grain because the crystal grain of compound can be grown in sintering process.People such as the Yang Jun friend of the Central China University of Science and Technology are [publication number CN 1422969A among the preparation method of skutterudite compound thermoelectric material at patent Co-Sb, open day 2003.6.11], adopt pre-alloyed two sections processing methods in conjunction with the solid phase processing, the material after mechanical alloying is handled prepares single-phase CoSb through the short time annealing in process
3Compound makes the material preparation process shorten 6 hours at least, has significantly reduced energy consumption, but the general reaction time is still longer, can not obtain high fine and close, compact grained product.
Therefore, the invention provides a kind of n type CoSb
3The fast preparation method of pyroelectric material comprises and adopts mechanical ball milling (MG) and discharge plasma sintering process (SPS) with the CoSb that mixes
3The operation of the highdensity sintered body of the powder sintered one-tenth of the forerunner of based compound.Because the discharge plasma sintering process only needs the sintering of short time can obtain highdensity sintered body, therefore, can improve the electrical conductivity of sintered body, improves the performance index of thermo-electric device.
Among the present invention,, adopt extremely short sintering time, for example about 3-10 minute, finish (size that certain sintering time also depends on sintered body) usually, in such time, can stop grain growth basically fully owing to use the discharge plasma sintering process.This means particle diameter, can easily control the grain size of sintered body by compound powder before the control sintering.The size of microcrystal of the sintered body of moulding is preferably below 200 microns, is more preferably below 100 microns, and is best below 10 microns.Crystal grain thinning can reduce the thermal conductivity of sintered body.Therefore, among the present invention, by modulating CoSb in advance
3The particle diameter of based compound forerunner powder and be easy to obtain above-mentioned crystallization particle diameter.Preparation condition is preferably, and the particle diameter of powder is below 10 microns, and the crystal grain of the sintered body behind the sintering is below 10 microns.
In addition, for these materials are used as thermo-electric device, must make p-n junction with p type and two kinds of materials of n type.The CoSb that impurity is less
3Thermoelectric material himself is the p type, and therefore, preparation has the n type CoSb of higher thermal electrical property
3Pyroelectric material also is one of purpose of the present invention.
Summary of the invention
The object of the invention is to overcome the shortcoming of prior art, and the fast preparation method that a kind of preparation time is short, the composition deviation is little is provided, with obtain the density height, single-phase n-type Co-Sb that crystal grain is tiny is a skutterudite compound thermoelectric material.It is characterized in that, comprise and adopt mechanical ball milling (MG) and discharge plasma sintering process (SPS) the powder sintered operation that becomes highdensity sintered body of the forerunner of the Co-Sb based compound that mixes.
The n-type Co-Sb of the present invention's preparation is a skutterudite compound thermoelectric material, and its main component is metallic cobalt, antimony, nickel and rare earth element, and chemical formula is R
yNi
xCo
4-xSb
12, R=rare earth element wherein, x=(0～1), y=(0～1), and x, y are not 0 simultaneously.
N-type Co-Sb is the preparation method of skutterudite compound thermoelectric material, it is characterized in that, is made up of following steps:
(1) presses chemical formula R
yNi
xCo
4-xSb
12Metering is than taking by weighing the raw metal powder, and wherein R is a rare earth element, x=0～1, and y=0～2, and x, y is not 0 simultaneously, places ball mill, grinds under the alcohol medium, fully mixes;
(2) ground mixed-powder is placed in the vacuum drying chamber, under 50～75 ℃, carries out drying;
(3) above-mentioned dried powder is packed in the mould, compacting sinters bulk material into discharging plasma sintering equipment, and sintering condition is 500～700 ℃ of temperature, temperature retention time 2～10min, and atmosphere is vacuum.
Preferably being placed in the vacuum drying chamber when dry, carrying out under 50～75 ℃, is the component segregation that the splash for the oxidation that prevents powder and alcohol medium causes.
The characteristics of the inventive method are:
(1) production efficiency height, cost is low, can directly prepare the required n type of thermoelectric pile block materials as required, need not reprocess shaping.
(2) Zhi Bei thermoelectric material even tissue, the composition deviation is little, the relative density height, grain size can be controlled between 30～100nm.
(3) prepared thermoelectric material single phase property is good, has higher thermoelectricity capability, can be applied to the thermoelectric power generation field near 400～500 ℃.
Table 1: different n type Co-Sb are skutterudite compound thermoelectric material R
yNi
xCo
4-xSb
12, the R=rare earth element, x=(0～1), y=(0～1), relative density and Seebeck coefficient in the time of 500 ℃ and ZT value, wherein Seebeck coefficient all shows as negative value, illustrates successfully to have prepared n type semi-conductor thermoelectric material.
Description of drawings
Fig. 1: Ni
0.2Co
3.8Sb
12The XRD figure spectrum of compound block
Fig. 2: Ni
0.2Co
3.8Sb
12The fracture scanning electron microscopy pattern of compound block.
Fig. 3: Ni
1.0Co
3.0Sb
12The XRD figure spectrum of compound block
Fig. 4: La
1.0Co
4Sb
12The XRD figure spectrum of compound block
Fig. 5: Ce
1.0Co
4Sb
12The XRD figure spectrum of compound block
Fig. 6: Ce
1.0Co
4Sb
12The scanning electron microscopy pattern of compound block
Fig. 7: Nd
0.8Co
3.2Sb
12The XRD figure spectrum of compound block
Fig. 8: Ce
0.3Ni
.02Co
3.8Sb
12The XRD figure spectrum of compound block
The specific embodiment
Example 1: with the powder of nickel, cobalt and antimony mixed in molar ratio, put into the ball grinder that absolute ethyl alcohol is housed and grind 2h, put 70 ℃ of oven dry in the vacuum drying chamber then into by 0.2: 3.8: 12.At last dried powder is packed in the mould, put into the SPS sintering furnace, under 30MPa pressure, sinter to 500 ℃ and be incubated 10min.Can be single-phase skutterudite structure substantially, the alloy block of crystallite dimension about 300nm, its XRD and fracture apperance be respectively as shown in Figure 1, 2, thermoelectricity capability sees Table 1, Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 97.2%.
Example 2:, put into the ball grinder that absolute ethyl alcohol is housed and grind 4h with the powder of nickel, cobalt and antimony mixed in molar ratio by 1.0: 3.0: 12.Put 75 ℃ of oven dry in the vacuum drying chamber then into.At last dried powder is packed in the mould, put into the SPS sintering furnace, under 30MPa pressure, sinter to 600 ℃ and be incubated 10min.The XRD that obtains fast body product is single-phase skutterudite phase structure as shown in Figure 3 substantially.Its thermoelectricity capability sees Table 1, and Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 96.8%.
Example 3: in vacuum glove box,, take by weighing a certain amount ofly, put into the ball grinder that absolute ethyl alcohol is housed and grind 5h with lanthanum, cobalt and antimony powder by 1.0: 4.0: 12 mol ratio.Put 50 ℃ of oven dry in the vacuum drying chamber then into.At last dried powder is packed in the mould, put into the SPS sintering furnace, under 30MPa pressure, sinter to 650 ℃ and be incubated 5min.Can be the alloy block of single-phase skutterudite structure substantially, its XRD as shown in Figure 4.Its thermoelectricity capability sees Table 1, and Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 96.3%.
Example 4: in vacuum glove box, by 1.0: 4.0: 12 mol ratios, take by weighing a certain amount ofly, put into the ball grinder that absolute ethyl alcohol is housed and grind 6h with cerium, cobalt and antimony powder.Put 60 ℃ of oven dry in the vacuum drying chamber then into.At last dried powder is packed in the mould, put into the SPS sintering furnace, under 30MPa pressure, sinter to 700 ℃ and be incubated 2min.Can be single-phase skutterudite phase structure substantially, crystallite dimension be the alloy block of 200～300nm, and its XRD and fracture apperance are respectively shown in Fig. 5,6.Its thermoelectricity capability sees Table 1, and Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 97.0%.
Example 5: in vacuum glove box,, take by weighing a certain amount of neodymium, cobalt and antimony powder, put into the ball grinder that absolute ethyl alcohol is housed and grind 6h by 0.8: 3.2: 12 mol ratio.Put 60 ℃ of oven dry in the vacuum drying chamber then into.At last dried powder is packed in the mould, put into the SPS sintering furnace, under 30MPa pressure, sinter to 650 ℃ and be incubated 6min.Can be the alloy block of single-phase skutterudite structure substantially, its XRD as shown in Figure 7.Its thermoelectricity capability sees Table 1, and Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 95.9%.
Example 6: in vacuum glove box in 0.3: 0.2: 3.8: 12 (mol ratio) ratio, take by weighing a certain amount of cerium, nickel, cobalt and antimony powder, put into the ball grinder that absolute ethyl alcohol is housed and grind 8h.Put 60 ℃ of oven dry in the vacuum drying chamber then into.At last dried powder is packed in the mould, put into the SPS sintering furnace, be warming up to 600 ℃ and be incubated 5min.Can be the alloy block of single-phase skutterudite structure substantially, its XRD as shown in Figure 8.Its thermoelectricity capability sees Table 1, and Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 96.4%.
Example 7: in vacuum glove box in 1.0: 1.0: 3.0: 12 (mol ratio) ratio, take by weighing a certain amount of lanthanum, nickel, cobalt and antimony powder, put into the ball grinder that absolute ethyl alcohol is housed and grind 6h.Put 60 ℃ of oven dry in the vacuum drying chamber then into.At last dried powder is packed in the mould, put into the SPS sintering furnace, be warming up to 600 ℃ and be incubated 5min.Can be the alloy block of single-phase skutterudite structure substantially.Its thermoelectricity capability sees Table 1, and Seebeck coefficient numerical value is negative value, shows as the conduction of n type semiconductor, and relative density reaches 97.6%.
Table 1.Co-Sb is skutterudite compound thermoelectric material R
yNi
xCo
4-xSb
12Density and performance
Dimensionless during Seebeck coefficient 773K when implementing 773K
The composition relative density
Example number (μ V/K) thermoelectric figure of merit ZT
1 Ni
0.2Co
3.8Sb
12 97.2％ -207 0.60
2 Ni
1.0Co
3.0Sb
12 96.8％ -132 0.25
3 La
1.0Co
4Sb
12 96.3％ -133 0.34
4 Ce
1.0Co
4Sb
12 97.0％ -160 0.37
5 Nd
0.8Co
3.2Sb
12 95.9％ -132 0.25
6 Ce
0.3Ni
.02Co
3.8Sb
12 96.4％ -216 0.44
7 Ce
1.0Ni
1.0Co
3.0Sb
12 97.6％ -213 0.32
Claims (1)
1, a kind of n-type Co-Sb is the preparation method of skutterudite compound thermoelectric material, it is characterized in that, is made up of following steps:
1) presses chemical formula R
yNi
xCo
4-xSb
12Metering is than taking by weighing the raw metal powder, and wherein R is a rare earth element, x=0～1, and y=0～2, and x, y is not 0 simultaneously, places ball mill, grinds under the alcohol medium, fully mixes;
2) ground mixed-powder is carried out drying under 50～75 ℃;
3) above-mentioned dried powder is packed in the mould, compacting sinters bulk material into discharging plasma sintering equipment, and sintering condition is 500～700 ℃ of temperature, temperature retention time 2～10min, and atmosphere is vacuum.
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|---|---|---|---|
| CN 200410086894 CN1605417A (en) | 2004-11-05 | 2004-11-05 | Process for preparing N type Co-Sb series skutterudite compound thermoelectric materials |
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|---|---|---|---|
| CN 200410086894 CN1605417A (en) | 2004-11-05 | 2004-11-05 | Process for preparing N type Co-Sb series skutterudite compound thermoelectric materials |
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|---|---|
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100333835C (en) * | 2005-07-29 | 2007-08-29 | 华南理工大学 | High energy ball mill method with plasma aid |
| CN100391021C (en) * | 2005-10-21 | 2008-05-28 | 清华大学 | Ag-Pb-Sb-Te thermoelectric materials and preparation process thereof |
| CN117715497A (en) * | 2024-02-06 | 2024-03-15 | 乌镇实验室 | Antioxidant skutterudite-based thermoelectric composite material and preparation method thereof |
-
2004
- 2004-11-05 CN CN 200410086894 patent/CN1605417A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100333835C (en) * | 2005-07-29 | 2007-08-29 | 华南理工大学 | High energy ball mill method with plasma aid |
| CN100391021C (en) * | 2005-10-21 | 2008-05-28 | 清华大学 | Ag-Pb-Sb-Te thermoelectric materials and preparation process thereof |
| CN117715497A (en) * | 2024-02-06 | 2024-03-15 | 乌镇实验室 | Antioxidant skutterudite-based thermoelectric composite material and preparation method thereof |
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