CN104164580A - Bismuth telluride composite alloy powder, block alloy thereof and manufacturing method thereof - Google Patents
Bismuth telluride composite alloy powder, block alloy thereof and manufacturing method thereof Download PDFInfo
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- CN104164580A CN104164580A CN201310368199.9A CN201310368199A CN104164580A CN 104164580 A CN104164580 A CN 104164580A CN 201310368199 A CN201310368199 A CN 201310368199A CN 104164580 A CN104164580 A CN 104164580A
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- tellurobismuthite
- powder
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- composite
- alloy powder
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 138
- 239000000956 alloy Substances 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 106
- 239000000843 powder Substances 0.000 title claims abstract description 66
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 39
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- 239000005300 metallic glass Substances 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 238000000498 ball milling Methods 0.000 claims description 30
- 239000011812 mixed powder Substances 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 25
- 229910052787 antimony Inorganic materials 0.000 claims description 12
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 10
- 235000012054 meals Nutrition 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 4
- HAGWIPLBDFOLMO-UHFFFAOYSA-N [Ni].[Ti].[Cu].[Sn] Chemical compound [Ni].[Ti].[Cu].[Sn] HAGWIPLBDFOLMO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 abstract description 7
- 230000008018 melting Effects 0.000 abstract description 7
- 238000000713 high-energy ball milling Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000010791 quenching Methods 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 4
- 238000000227 grinding Methods 0.000 abstract description 2
- 229910000808 amorphous metal alloy Inorganic materials 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- MRPWWVMHWSDJEH-UHFFFAOYSA-N antimony telluride Chemical compound [SbH3+3].[SbH3+3].[TeH2-2].[TeH2-2].[TeH2-2] MRPWWVMHWSDJEH-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000010970 precious metal Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000005619 thermoelectricity Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 3
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000000754 repressing effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 229910001215 Te alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
Abstract
The invention relates to bismuth telluride composite alloy powder, a block alloy thereof and a manufacturing method thereof, wherein under the condition of eliminating a pre-melting step, a vacuum melting step, a quenching step and/or a grinding step, bismuth telluride composite alloy powder is prepared by utilizing a plurality of high-energy ball milling steps, and then the bismuth telluride composite block alloy is prepared by molding the bismuth telluride composite alloy powder through a vacuum hot-pressing step. The bismuth telluride composite alloy powder and the bulk alloy thereof have uniformly doped amorphous alloy particles, and the obtained bismuth telluride composite bulk alloy has excellent thermoelectric figure of merit (ZT value) at 500K to 600K.
Description
Technical field
The invention relates to a kind of thermoelectric material and manufacture method thereof, particularly relevant for a kind of Tellurobismuthite composite alloy powder and block alloy thereof with non-crystal structure that utilizes powder metallurgy to prepare.
Background technology
" thermoelectric material " refers to the material of electric energy and the mutual conversion of heat energy.Different according to the use temperature scope of thermoelectric material, can generally be divided into low-temperature thermoelectric material (being applicable to about 100K to the temperature of about 200K), warm thermoelectric material (being applicable to about 300K to the temperature of about 600K) and high temperature thermoelectric material (being applicable to temperature more than about 800K).Wherein, low-temperature thermoelectric material is with Tellurobismuthite (bismuth telluride; Bi
2te
3) base alloy is representative, warm thermoelectric material is with lead telluride (Lead telluride; PbTe) base alloy is representative, and high temperature thermoelectric material is with SiGe (silicone germanium; SiGe) base alloy is representative.
Generally speaking, the conversion efficiency of thermoelectric of thermoelectric material can be according to the thermoelectric figure of merit calculating of following formula (I) (thermoelectric figure of merit; ZT) assess:
ZT=S
2σT/(κ
e＋κ
L) (I)
Wherein S is seat Bake (Seebeck) coefficient, and σ is electric conductivity (electrical conductivity), and T is absolute temperature, κ
efor electronics thermal conductivity (thermal conductivity), κ
lfor phonon thermal conduction rate (relevant with lattice).
From formula (I), as the conversion efficiency of thermoelectric of wish raising thermoelectric material, must improve seat seebeck coefficient and the electric conductivity of material, or reduce its thermal conductivity.Yet when promoting the electric conductivity of material, its thermal conductivity is inevitable to be increased thereupon.Therefore, wish improves seat seebeck coefficient and electric conductivity simultaneously and reduces its thermal conductivity, and reaches the object of the conversion efficiency of thermoelectric that promotes thermoelectric material, very difficult.
In view of the conversion efficiency of thermoelectric of existing thermoelectric material not high, the road of current improvement, mainly from the carrier concentration that increases doping to improve electric conductivity, or reduce the modes such as thermal conductivity and set about from improving the scattering mechanism of phonon.Known polymorphic thermoelectric material is the high-purity raw that mixes suitable proportion, after the steps such as fritting step, vacuum melting method, chilling, makes the block alloy of polymorphic thermoelectric material.Then, block alloy is ground to form after micron order alloy powder again, then development is thermoelectric element.Another kind of mode, after being first synthesis of nano film, single nanotube/line, then makes block alloy.
Yet, the processing procedure of above-mentioned known thermoelectric material, its apparatus expensive, processing procedure are complicated, mixture homogeneity is also not good, are difficult to be applied to industrialization volume production.
In view of this, need badly a kind of thermoelectric material and manufacture method thereof are provided, the variety of problems facing to overcome known processing procedure.
Summary of the invention
Therefore, one aspect of the present invention is to provide a kind of manufacture method of Tellurobismuthite composite alloy powder, it is eliminating use known fritting step, vacuum melting step, quench step and/or grinds in the situation of step, utilize a plurality of high-energy ball milling steps, can make Tellurobismuthite composite alloy powder, wherein the Tellurobismuthite composite alloy powder of gained has the non-crystaline amorphous metal particulate of Uniform Doped but does not contain precious metal.
Secondly, another aspect of the present invention is to provide a kind of manufacture method of Tellurobismuthite composite block alloy, and it is to utilize above-mentioned Tellurobismuthite composite alloy powder, then by it through the moulding of vacuum hotpressing step, can make Tellurobismuthite composite block alloy.The Tellurobismuthite composite block alloy of gained has the non-crystaline amorphous metal particulate of Uniform Doped, and has excellent thermoelectric figure of merit (ZT value) in 500K to 600K.
Moreover also one side of the present invention is to provide a kind of Tellurobismuthite composite alloy powder, it is to utilize aforesaid method obtained.
In addition, another aspect of the present invention is to provide a kind of Tellurobismuthite composite block alloy, and it is to utilize aforesaid method obtained.
According to above-mentioned aspect of the present invention, a kind of manufacture method of Tellurobismuthite composite alloy powder is proposed.In one embodiment, first, carry out the first ball milling step, under the existence of rare gas element and a plurality of abrading-balls, rotating speed with per minute at least 1200 times, make the first metal mixed powder form non-crystaline amorphous metal particulate, wherein the first metal mixed powder is comprised of pure titanium valve body, fine copper powder, pure nickel powder and the pure tin powder of mol ratio 50:28:15:7, and non-crystaline amorphous metal particulate is amorphous titanium copper nickel-tin alloy particulate.Next, carry out one second ball milling step, under the existence of above-mentioned rare gas element and abrading-ball, with above-mentioned rotating speed, make non-crystaline amorphous metal particulate and the second metal mixed powder form Tellurobismuthite composite alloy powder.In an example, the second metal mixed powder is comprised of pure bismuth meal body, star antimony powder and pure tellurium powder.In another example, the usage quantity of non-crystaline amorphous metal particulate can be for example 0.50 weight percent to 1.00 weight percent, and the usage quantity of the second metal mixed powder can be for example 99.00 weight percent to 99.50 weight percents.The Tellurobismuthite composite alloy powder of gained has the non-crystaline amorphous metal particulate of Uniform Doped and does not contain precious metal thus.
According to one embodiment of the invention, the mol ratio of pure bismuth meal body, star antimony powder and the pure tellurium powder of the second above-mentioned metal mixed powder is x:(2-x): 3, and x is 0.3 to 0.5.
According to one embodiment of the invention, the first above-mentioned ball milling step is carried out 6 hours to 8 hours, and the second ball milling step is carried out 1 hour to 2 hours.
A kind of manufacture method of Tellurobismuthite composite block alloy is proposed according to other aspects of the invention.In one embodiment, first, the Tellurobismuthite composite alloy powder that provides aforesaid method to make, wherein non-crystaline amorphous metal particulate is that Uniform Doped is in Tellurobismuthite composite alloy powder but containing precious metal.
Then, carry out vacuum hotpressing step, make above-mentioned Tellurobismuthite composite alloy powder form Tellurobismuthite composite block alloy, wherein non-crystaline amorphous metal particulate is to be uniformly distributed in Tellurobismuthite composite block alloy, and the Tellurobismuthite composite block alloy of gained is at least 1.1 in the thermoelectric figure of merit (ZT value) of 500K to 600K.
According to one embodiment of the invention, above-mentioned Tellurobismuthite composite block alloy is P type thermoelectric material.
According to other aspects of the invention, propose a kind of Tellurobismuthite composite block alloy, it is to utilize aforesaid method to make.
It is to utilize a plurality of ball millings and vacuum hotpressing step to manufacture the compound thermoelectricity bulk of amorphousness (Tellurobismuthite composite block alloy) for the manufacture method of Tellurobismuthite composite alloy powder of the present invention and block alloy thereof, wherein the compound thermoelectricity bulk of the amorphousness of this gained is not containing precious metal, in 500K to 600K, there is excellent thermoelectric figure of merit (ZT value), the present invention not only overcomes the power consumption of known processing procedure, the shortcoming such as consuming time, can independently adjust seat seebeck coefficient, electric conductivity and thermal conductivity values again.
Accompanying drawing explanation
For above and other object of the present invention, feature, advantage and embodiment can be become apparent, being described in detail as follows of appended accompanying drawing:
Fig. 1 illustrates the XRD analysis figure of non-crystaline amorphous metal particulate according to an embodiment of the invention;
Fig. 2 illustrates the XRD analysis figure of pure metal powder, non-crystaline amorphous metal particulate, Tellurobismuthite composite alloy powder and Tellurobismuthite composite block alloy according to an embodiment of the invention;
Fig. 3 shows the SEM photo of antimony telluride bismuth composite block alloy cross section according to an embodiment of the invention;
Fig. 4 illustrates the ZT value variation diagram under differing temps according to the antimony telluride bismuth composite block alloy of one embodiment of the invention and comparative example;
Wherein, nomenclature:
201/203/205/207/209/211/401/403/405: curve;
And curve 201 represents pure bismuth meal body;
Curve 203 represents pure tellurium powder;
Curve 205 represents star antimony powder;
Curve 207 represents Ti
50cu
28ni
15sn
7alloy particle;
Curve 209 represents doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite alloy powder;
Curve 211 represents doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite block alloy;
Curve 401 is for representing the antimony telluride bismuth composite block alloy of embodiment 2;
Curve 403 represents the antimony telluride bismuth block alloy of comparative example 1;
Curve 405 represents the antimony telluride bismuth block alloy of comparative example 2.
Embodiment
Described in brought forward, the invention provides a kind of Tellurobismuthite composite alloy powder, its block alloy and manufacture method thereof, it is in the situation that getting rid of use fritting step, vacuum melting step, quench step and/or grinding step, utilize a plurality of high-energy ball milling steps to make Tellurobismuthite composite alloy powder, again by it through the moulding of vacuum hotpressing step, can make Tellurobismuthite composite block alloy.
Profess it, the present invention is alleged a plurality of high-energy ball milling steps herein, refer to and utilize commercially available high-energy ball mill, for example, under rare gas element exists, the high-energy that rotating speed was provided with per minute at least 1200 times carries out ball milling, makes metal mixed powder and abrading-ball (for example steel ball) carry out alloying.High-energy ball mill has special three-dimensional design, and under high rotating speed, (per minute at least 1200 times) clashes into by abrading-ball and material, mechanical energy can be converted to the required energy of alloying.
In one embodiment, first, carry out the first ball milling step, it is under rare gas element exists, under the existence of blunt gas such as helium, neon, rotating speed with per minute at least 1200 times, utilizes abrading-ball ball milling the first metal mixed powder to reach 6 hours to 8 hours, makes the first metal mixed powder form non-crystaline amorphous metal particulate.In this example, aforementioned the first metal mixed powder can be comprised of pure titanium valve body, fine copper powder, pure nickel powder and pure tin powder, and the non-crystaline amorphous metal particulate of gained is amorphous titanium copper nickel-tin alloy particulate.
At this, it should be noted that, manufacture method of the present invention can change the mol ratio of pure titanium valve body, fine copper powder, pure nickel powder and the pure tin powder of aforementioned the first metal mixed powder, the required electric conductivity of independent lift Tellurobismuthite composite block alloy, or the independent required thermal conductivity of Tellurobismuthite composite block alloy that reduces by this.In an example, aforementioned the first metal mixed powder can be comprised of pure titanium valve body, fine copper powder, pure nickel powder and the pure tin powder of mol ratio 50:28:15:7.
In these supplementary notes, if the first metal mixed powder by above-mentioned form and/or scope beyond pure metal powder formed, the Tellurobismuthite composite block alloy of follow-up gained cannot reach required thermoelectric figure of merit.Secondly, if the rotating speed that the first ball milling step is used is for per minute is lower than 1200 times, or with the rotating speed of per minute at least 1200 times, carry out the first ball milling step but Ball-milling Time less than 6 hours, the non-crystaline amorphous metal particulate of gained cannot be completed into amorphous titanium copper nickel-tin alloy particulate.Moreover, if the first ball milling step carries out the first ball milling step with the rotating speed of per minute at least 1200 times but Ball-milling Time surpasses 8 hours, there are the shortcomings such as consuming time, power consumption.
Next, under rare gas element exists, with above-mentioned rotating speed, carry out the second ball milling step, make above-mentioned non-crystaline amorphous metal particulate and the second metal mixed powder through ball milling 1 hour to 2 hours, to form Tellurobismuthite composite alloy powder, wherein the Tellurobismuthite composite alloy powder of gained has this non-crystaline amorphous metal particulate of Uniform Doped but does not contain precious metal.
In an example, aforesaid the second metal mixed powder is comprised of pure bismuth meal body, star antimony powder and pure tellurium powder, wherein the mol ratio of pure bismuth meal body, star antimony powder and the pure tellurium powder of the second metal mixed powder can be for example x:(2-x): 3, and x can be for example 0.3 to 0.5, so x is better with 0.4.
In an example, the usage quantity of above-mentioned non-crystaline amorphous metal particulate can be for example 0.50 weight percent to 1.00 weight percent, and the usage quantity of the second metal mixed powder can be for example 99.00 weight percent to 99.50 weight percents, however the usage quantity of aforesaid non-crystaline amorphous metal particulate with 0.75 weight percent for better.If the weight percent of above-mentioned non-crystaline amorphous metal particulate and the second metal mixed powder is outside above-mentioned scope, the Tellurobismuthite composite block alloy of follow-up gained cannot reach required thermoelectric figure of merit.
At this, it should be noted that, manufacture method of the present invention also can change the weight percent of above-mentioned non-crystaline amorphous metal particulate and the second metal mixed powder, required seat seebeck coefficient and the electric conductivity of independent lift Tellurobismuthite composite block alloy, also can independently reduce the required thermal conductivity of Tellurobismuthite composite block alloy by this.
In addition, if the rotating speed that the second ball milling step is used is for per minute is lower than 1200 times, or with the rotating speed of per minute at least 1200 times, carry out the second ball milling step but Ball-milling Time less than 1 hour, non-crystaline amorphous metal particulate cannot obtain required Tellurobismuthite composite alloy powder in the second metal mixed powder by Uniform Doped.If the Ball-milling Time of the second ball milling step surpasses 2 hours, there are the shortcomings such as consuming time, power consumption.
Then, carry out vacuum hotpressing step, make above-mentioned Tellurobismuthite composite alloy powder form Tellurobismuthite composite block alloy.Generally speaking, there is no particular restriction for the process parameter of aforesaid vacuum hotpressing step, looks closely used equipment and determine, and can use known process parameter, or carry out at the temperature of the pressure of for example 2GPa to 3GPa and 400 ℃, only the invention is not restricted to this place and lift.
Because the present invention gets rid of, use known fritting step, vacuum melting step, quench step and/or grind step, only utilize two high-energy ball milling steps, can make Tellurobismuthite composite alloy powder, again through vacuum hotpressing step, can make Tellurobismuthite composite block alloy, and formed Tellurobismuthite composite block alloy has again the non-crystaline amorphous metal particulate of Uniform Doped, therefore be conducive to industrialization volume production.
It is worth mentioning that, the non-crystaline amorphous metal particulate that Tellurobismuthite composite block alloy of the present invention adulterates is not particularly limited, and looks closely actual demand and different.In an example, the Tellurobismuthite composite block alloy that the present invention makes can be for example doped Ti
50cu
28ni
15sn
7bi
xsb
2-xte
3composite block alloy, it is P type thermoelectric material.In another example, the Tellurobismuthite composite block alloy of gained is containing the precious metal in the situation that, in the thermoelectric figure of merit (ZT value) of 500K to 600K, can reach at least 1.1.
Below utilize several embodiment so that application of the present invention to be described, so it,, not in order to limit the present invention, has and conventionally knows the knowledgeable in the technology of the present invention field, without departing from the spirit and scope of the present invention, and when being used for a variety of modifications and variations.
Embodiment 1: preparation doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3compound thermoelectricity powder
1. prepare Ti
50cu
28ni
15sn
7non-crystaline amorphous metal particulate
First, by pure titanium valve body, fine copper powder, pure nickel powder and the pure tin powder of mol ratio 50:28:15:7, with the high chromium steel ball of the about 2g of weight, be placed in the high chromium steel tank of diameter 7.9375 millimeters (mm), wherein the weight ratio of above-mentioned pure metal mixed powder and high chromium steel ball is 1:5.In cylinder of steel, still have remnant oxygen when avoiding ball milling, to the ball grinder of pure metal mixed powder and high chromium steel ball be housed, inserting preparation has in the glove box of air purification system after (or under rare gas element exists) sealed cans, utilize subsequently commercially available high-energy ball mill, SPEX 8016 vibration-type ball mills for example, ball milling 8 hours, to form Ti
50cu
28ni
15sn
7(at.%) non-crystaline amorphous metal particulate.Prepared non-crystaline amorphous metal particulate utilizes X-ray diffraction analysis, and its result is as shown in the curve 207 of Fig. 1 and Fig. 2.
Refer to Fig. 1, it is the XRD analysis figure illustrating according to the non-crystaline amorphous metal particulate of the embodiment of the present invention 1.In Fig. 1, the longitudinal axis is relative intensity (arbitrary unit), and transverse axis is scanning angle (2 θ °).From the crest of Fig. 1, prepared Ti
50cu
28ni
15sn
7alloy particle be take amorphous phase really as main.
Similarly result is also found in Fig. 2, and wherein curve 207 is Ti
50cu
28ni
15sn
7the XRD analysis figure of non-crystaline amorphous metal particulate.In Fig. 2, the longitudinal axis is relative intensity (arbitrary unit), and transverse axis is scanning angle (2 θ °).From the curve 207 of Fig. 2, prepared Ti
50cu
28ni
15sn
7alloy particle be take amorphous phase really as main.
2. prepare doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite alloy powder
Then, by the Ti of above-mentioned gained
50cu
28ni
15sn
7non-crystaline amorphous metal particulate, with the pure bismuth meal body of mol ratio 0.4:1.6:3, pure tellurium powder and star antimony powder, with the high chromium steel ball of the about 2g of weight, be placed in the high chromium steel tank of diameter 7.9375 millimeters (mm), wherein the weight ratio of above-mentioned alloy/pure metal mixed powder and high chromium steel ball is 1:5.Afterwards, above-mentioned alloy/pure metal mixed powder and high chromium steel ball are inserted preparation to be had in the glove box of air purification system after (or under rare gas element exists) sealed cans, utilizes immediately high-energy ball mill same as described above, with rotating speed same as described above, ball milling 2 hours, forms doped Ti by this
50cu
28ni
15sn
7bi
0.4sb
1.6te
3(at.%) composite alloy powder, wherein the antimony telluride bismuth composite alloy powder of above-mentioned gained is not containing precious metal.Prepared antimony telluride bismuth composite alloy powder also can utilize X-ray diffraction analysis, and its result is as shown in Fig. 2.
In Fig. 2, curve 201 represents pure bismuth meal body, and curve 203 represents pure tellurium powder, and curve 205 represents star antimony powder, and curve 207 represents Ti
50cu
28ni
15sn
7non-crystaline amorphous metal particulate, and curve 209 represents doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite alloy powder.From the curve 209 of Fig. 2, prepared Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite alloy powder has sharp-pointed Bi really
0.4sb
1.6te
3crystallization phases.
Embodiment 2: preparation doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite block alloy
Then, by embodiment 1 gained doped Ti
50cu
28ni
15sn
7the Bi of non-crystaline amorphous metal particulate
0.4sb
1.6te
3composite alloy powder, inserts in the die cavity in thermocompressor (huge sub-machinery, Taiwan), starts to carry out vacuum hotpressing step after matched moulds.First, composite thermoelectric material powder pressing is formed to green compact body.Then, with the temperature rise rate of approximately 40 ℃ of per minutes, make die cavity and green compact body wherein be heated to 400 ℃ and hold temperature approximately 60 minutes, also vacuumize, to avoid the oxidation of green compact body simultaneously.During holding temperature, apply the pressure of 2.04GPa simultaneously, make raw blank Densification.After holding and finishing during temperature, stop heating, to be cooled to the hot-forming antimony telluride bismuth composite block alloy of taking-up after room temperature (approximately 0 ℃ to approximately 40 ℃).Prepared doped Ti
50cu
28ni
15sn
7the Bi of non-crystaline amorphous metal particulate
0.4sb
1.6te
3composite block alloy can utilize various assessment mode described later to carry out thermoelectric figure of merit (ZT value) analysis, and its result is as shown in table 1.
Table 1
In table 1, the sample number of every group of data is at least 3 (n≤3).As shown in Table 1, the antimony telluride bismuth composite block alloy of embodiment 2 can reach at least 1.1 really in the thermoelectric figure of merit (ZT value) of 573K.
In addition, prepared antimony telluride bismuth composite block alloy also can utilize X-ray diffraction analysis instrument { note: PANalytical X ' PERT PRO type diffractometer, PANalytical B.V., Holland }, sweep electron microscope { note: Hitachi S-4800, Hitachi, Japan } to analyze with thermoelectric figure of merit (ZT value), its result is respectively as shown in Fig. 2, Fig. 3 and Fig. 4.
In Fig. 2, curve 211 represents doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite block alloy.From the curve 211 of Fig. 2, prepared doped Ti
50cu
28ni
15sn
7bi
0.4sb
1.6te
3composite block alloy has more sharp-pointed really ' Bi
0.4sb
1.6te
3crystallization phases.
Refer to Fig. 3, it is to show the SEM photo of antimony telluride bismuth composite block alloy cross section (200 times of enlargement ratios) according to an embodiment of the invention.From the result of Fig. 3, Ti
50cu
28ni
15sn
7the certain Uniform Doped of alloy particle (stain place as shown by arrows) is in Bi
0.4sb
1.6te
3in composite block alloy.
Refer to Fig. 4, it is to illustrate the ZT value variation diagram under differing temps according to the antimony telluride bismuth composite block alloy of one embodiment of the invention and comparative example.In Fig. 4, the longitudinal axis is ZT value, and transverse axis is temperature (K), and curve 401 is the antimony telluride bismuth composite block alloy of embodiment 2.From the result of Fig. 4, the antimony telluride bismuth composite block alloy of embodiment 2 can reach at least 1.1 really in the thermoelectric figure of merit (ZT value) of 500K to 600K.
Comparative example 1:
Comparative example 1 is in science (Science) periodical the 320th volume 634-638 page, title in 2008, to be " the nanometer antimony telluride bismuth block alloy of high thermoelectricity capability (High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys) " civilian disclosed mode according to people such as B.Poudel, by mol ratio, be x:(2-x): 3 antimony telluride bismuth block alloy ingot casting, the ball milling step of take is worn into after the alloy powder that median size is about 20nm, hot repressing becomes (Bi, Sb)
2te
3alloy pig.This alloy pig carries out the thermoelectric figure of merit identical with embodiment 2 (ZT value) analysis, and its result is as shown in table 1 and Fig. 4.Yet difference from Example 2 is, the comparative example 1 non-crystaline amorphous metal particulate that do not adulterate.
Comparative example 2
Comparative example 2 is in nanometer digest (Nano Letters) the 8th volume the 8th phase 2580-2584 page in 2008 according to people such as Y.Ma, title is " promoting the thermoelectric figure of merit (Enhanced Thermoelectric Figure of Merit in p-type Nanostructured Bismuth Antimony Tellurium Alloys Made from Elemental Chunks) of the p-type nanometer antimony telluride bismuth alloy being made by an element blocks body " civilian disclosed mode, by mol ratio, be x:(2-x): 3 pure bismuth block, star antimony block and pure tellurium block, through ball milling step, wear into after alloy powder, hot repressing becomes (Bi, Sb)
2te
3block alloy, and carry out the thermoelectric figure of merit identical with embodiment 2 (ZT value) analysis, its result is as shown in table 1 and Fig. 4.Yet difference from Example 2 is, the comparative example 2 non-crystaline amorphous metal particulate that also do not adulterate.
Refer to Fig. 4.In Fig. 4, curve 403 is the antimony telluride bismuth block alloy of comparative example 1, and curve 405 is the antimony telluride bismuth block alloy of comparative example 2.From the result of Fig. 4, the antimony telluride bismuth composite block alloy of comparative example 1 and comparative example 2 in the thermoelectric figure of merit (ZT value) of 500K to 600K all lower than 1.0.
From the invention described above embodiment, Tellurobismuthite composite alloy powder of the present invention, its block alloy and manufacture method thereof, its advantage is to get rid of use fritting step, vacuum melting step, quench step and/or grinds in the situation of step, utilize a plurality of high-energy ball milling steps to make Tellurobismuthite composite alloy powder, again by it through the moulding of vacuum hotpressing step, can make the Tellurobismuthite composite block alloy of Uniform Doped non-crystaline amorphous metal particulate.The Tellurobismuthite composite block alloy of gained not only can surpass 1 in the thermoelectric figure of merit (ZT value) of 500K to 600K, more solves the apparatus expensive of known processing procedure, the problem such as processing procedure is complicated, mixture homogeneity is not good, industrialization volume production is difficult for.
Although the present invention discloses as above with several embodiment; so it is not in order to limit the present invention; in the technical field of the invention any have conventionally know the knowledgeable; without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, so the scope that protection scope of the present invention ought define depending on accompanying claims is as the criterion.
Claims (11)
1. a manufacture method for Tellurobismuthite composite alloy powder, at least comprises:
Carry out one first ball milling step, it is under the existence of a rare gas element and a plurality of abrading-balls, rotating speed with per minute at least 1200 times, make one first metal mixed powder form a non-crystaline amorphous metal particulate, wherein said the first metal mixed powder is comprised of pure titanium valve body, fine copper powder, pure nickel powder and the pure tin powder of mol ratio 50:28:15:7, and described non-crystaline amorphous metal particulate is an amorphous titanium copper nickel-tin alloy particulate; And
Carry out one second ball milling step, it is under the existence of described rare gas element and described abrading-ball, with described rotating speed, make described non-crystaline amorphous metal particulate and one second metal mixed powder form a Tellurobismuthite composite alloy powder, wherein said the second metal mixed powder is comprised of pure bismuth meal body, star antimony powder and pure tellurium powder, the usage quantity of described non-crystaline amorphous metal particulate is 0.50 weight percent to 1.00 weight percent, the usage quantity of described the second metal mixed powder is 99.00 weight percent to 99.50 weight percents, and
Wherein said Tellurobismuthite composite alloy powder has the described non-crystaline amorphous metal particulate of Uniform Doped.
2. the manufacture method of Tellurobismuthite composite alloy powder according to claim 1, the mol ratio of wherein said pure bismuth meal body, star antimony powder and pure tellurium powder is x:(2-x): 3, and x is 0.3 to 0.5.
3. the manufacture method of Tellurobismuthite composite alloy powder according to claim 2, wherein x is 0.4.
4. the manufacture method of Tellurobismuthite composite alloy powder according to claim 1, the usage quantity of wherein said non-crystaline amorphous metal particulate is 0.75 weight percent.
5. the manufacture method of Tellurobismuthite composite alloy powder according to claim 1, wherein said the first ball milling step is carried out 6 hours to 8 hours.
6. the manufacture method of Tellurobismuthite composite alloy powder according to claim 1, wherein said the second ball milling step is carried out 1 hour to 2 hours.
7. a Tellurobismuthite composite alloy powder, it utilizes the method as described in any one in claim 1 to 6 to make.
8. a manufacture method for Tellurobismuthite composite block alloy, at least comprises:
One Tellurobismuthite composite alloy powder is provided, and wherein said Tellurobismuthite composite alloy powder is to utilize the method as described in any one in claim 1 to 6 to make, and described Tellurobismuthite composite alloy powder has the non-crystaline amorphous metal particulate of Uniform Doped; And
Carry out a vacuum hotpressing step, make described Tellurobismuthite composite alloy powder form Tellurobismuthite composite block alloy, wherein said non-crystaline amorphous metal particulate is to be uniformly distributed in described Tellurobismuthite composite block alloy, and described Tellurobismuthite composite block alloy is at least 1.1 in a thermoelectric figure of merit of 500K to 600K.
9. the manufacture method of Tellurobismuthite composite block alloy according to claim 8, wherein said vacuum hotpressing step is to carry out at the temperature of the pressure of 2GPa to 3GPa and 400 ℃.
10. the manufacture method of Tellurobismuthite composite block alloy according to claim 8, wherein said Tellurobismuthite composite block alloy is a P type thermoelectric material.
11. 1 kinds of Tellurobismuthite composite block alloys, it is to utilize the method as described in any one in claim 8 to 10 to make.
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| TW102117581A TWI507534B (en) | 2013-05-17 | 2013-05-17 | Composite bismuth antimony telluride alloy powder, bulk alloy thereof and method of producing the same |
| TW102117581 | 2013-05-17 |
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| CN110098310A (en) * | 2018-01-30 | 2019-08-06 | 中国科学院宁波材料技术与工程研究所 | A kind of SnSe base thermoelectricity material orientation polycrystalline preparation method |
| CN113800480A (en) * | 2021-09-15 | 2021-12-17 | 先导薄膜材料（广东）有限公司 | N-type bismuth telluride-based thermoelectric material and preparation method and application thereof |
| CN113773083B (en) * | 2021-09-13 | 2022-10-04 | 哈尔滨工业大学 | Bismuth telluride-based material with high strength and high thermoelectric property and preparation method thereof |
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