CN107681043A - A kind of bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application and preparation method thereof - Google Patents
A kind of bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 32
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 58
- 239000011159 matrix material Substances 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000005619 thermoelectricity Effects 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 20
- 239000010439 graphite Substances 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 34
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003708 ampul Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000007578 melt-quenching technique Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000003801 milling Methods 0.000 claims description 7
- 239000010453 quartz Substances 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229940125773 compound 10 Drugs 0.000 claims 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000875 corresponding effect Effects 0.000 description 5
- 125000005909 ethyl alcohol group Chemical group 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- -1 bismuthino Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
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Abstract
The present invention relates to a kind of bismuth telluride-base composite thermoelectric material and preparation method thereof, belongs to heat to electricity conversion new energy materialses field.Material of the present invention is graphite (G) and Bi0.5Sb1.5Te3Composite thermoelectric material, its chemical composition formula is x G/Bi0.5Sb1.5Te3, wherein x is that the second phase graphite accounts for matrix Bi0.5Sb1.5Te3Mass percent, scope is in 0≤x≤0.20%.Method is combined with ultrasonic disperse using powder metallurgic method, the bismuth telluride-base composite thermoelectric material synthesis thermoelectricity capability ZT values prepared significantly improve, can be as the raw material for preparing, assembling high-performance flexible thermo-electric device.Simultaneously as there is the material abundant raw material to be easy to get, preparation method has the characteristics that the simple controllable, short preparation period of technique and energy consumption are low, suitable for industrialized production, is expected to realize in the commercial applications of flexible thermo-electric device and breaks through.
Description
Technical field
The present invention relates to a kind of semiconductor temperature differential generating and refrigerating material, particularly a kind of tellurium of flexible thermo-electric device application
Change bismuthino composite thermoelectric material and preparation method thereof, belong to heat to electricity conversion new energy materialses field.
Background technology
Seebeck (Seebeck) effect and Peltier (Peltier) effect of the thermo-electric device due to thermoelectric material can be utilized
It should realize that heat energy and electric energy directly mutually convert and cause extensive concern.It has pollution-free, noiseless, small volume, reliability
The advantages that high, the field such as utilize to be with a wide range of applications and potentially in thermoelectric power generation, refrigeration and solar energy, industrial exhaust heat
Economic value, it is high-new survey of deep space, military equipment, IT industries etc. are successfully applied to as particular power source and high-precisive temperature controllers
Technical field.The conversion efficiency of thermoelectric of thermo-electric device depends primarily on the thermoelectricity capability figure of merit ZT=α of material2σ T/ κ, wherein α are
Seebeck coefficient, σ are electrical conductivity, and κ is thermal conductivity, and T is absolute temperature.Thermal conductivity κ includes carrier thermal conductivity κEWith lattice heat
Conductance κL, i.e. κ=κE+κL.In theory, thermal conductivity (κ is reducedE+κL) and improve material conductivityσ and Seebeck factor alphas, (carry
High electrical transmission performance α2It σ) can reach the target for putting forward high zt.But due to electron-phonon interatction strong in thermoelectric material, σ, α
It is difficult coordinated regulation with tri- parameters of κ, how optimizes electricity, thermotransport performance obtains the research hardly possible that high zt is thermo-electric device field
Topic.
On the other hand, as electronic equipment is towards miniaturization, integrated direction development, people are to miniature, the efficient, long-life
Flexible thermoelectric power generation and the demand of refrigeration device increasingly increase.Bismuth telluride based alloys are domestic and international research thermoelectricity the most ripe
One of material, while be also the best material of near room temperature thermoelectricity capability.Its preparation method have molecular beam epitaxy, zone-melting process,
Mechanical alloying method, pulsed laser deposition, magnetron sputtering method etc., gained p-type and n-type bismuth telluride-base material maximum thermoelectric figure of merit
ZT is 0.8~1.At present, the performance optimizing research of the bismuth telluride-base thermoelectric material of flexible thermo-electric device application is also prominent in the presence of some
Go wrong, such as thermal conductivity (the 1.11Wm of (1) bismuth telluride-base thermoelectric material in itself-1·K-1) higher, limit its thermoelectricity capability
Improve；(2) bismuth telluride-base film and thick film thermoelectric material electrical conductivity are far below block materials, and its reason is that have in heat treatment process
The volatilization of machine thing causes that membrane structure is loose porous, consistency reduces.In terms of bismuth telluride-base membrane material preparation method for material research, prepare thick
The method of film thermoelectric material mainly has：Silk screen print method, ink-jet printing process, dispensing impact system, electrochemical deposition method and spin-coating method
The problems such as priority is studied reports, these method generally existing equipment costs are higher, complex operation, and because preparation process
Controllability is poor, and the thermoelectricity capability of its membrane material is unstable, therefore large-scale industrial production difficult to realize.In order to improve telluride
The thermoelectricity capability of bismuthino membrane material, there is researcher to propose that adding appropriate sintering aid greatly increases material density, to improve
The electrical conductivity of material.But sintering aid prepares and needs to use substantial amounts of chemical reagent, part organic reagent such as hydrazine hydrate, second sulphur
The problems such as price is high, poisonous, higher to the requirement of operating environment condition also be present in alcohol, tri octyl phosphine etc..Researchers have found will
Small-scale inorganic nano-second-phase (such as SiC) or nano conducting powderses (such as Ag, Cu) and bismuth telluride-base thermoelectric material are compound,
The purpose for improving electrical transmission performance can be reached.It is comprehensive but doping Cu can increase substantially thermal conductivity while electrical conductivity is improved
Closing thermoelectricity capability can even decline sometimes.Nano SiC is typically made using mechanical alloying method (MA), and this method does not only exist energy
High problem is consumed, and product purity is not general high, causes stability difficulty control problem during industrial applications be present.Equally
Ground, nano conducting powderses are generally required in the form of metal compound solution or answered by electrochemical deposition method and matrix material
Close, the shortcomings of preparing cost height, complex process, high appointed condition requirement be present, it is difficult to realize large-scale industrial production.
The content of the invention
The present invention for solve above-mentioned technical problem provide a kind of bismuth telluride-base composite thermoelectric material that flexible device applies and
Its preparation method, the characteristics of there is this method abundant raw material to be easy to get, technique is simple controllable, short preparation period and energy consumption are low, it is suitable to
Industrialized production.Meanwhile composite thermoelectric material obtained by this method has lower thermal conductivity and high thermoelectric figure of merit, system can be used as
Standby, assembling high-performance thick film thermo-electric device raw material, and be expected to realize in the commercial applications of thick film thermo-electric device and break through.
In order to solve the above technical problems, technical scheme is as follows：
A kind of bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application, the composition of the thermoelectric material is x G/
Bi0.5Sb1.5Te3, G is graphite, and wherein x is that the second phase graphite accounts for matrix Bi0.5Sb1.5Te3Mass percent, scope is in 0≤x
≤ 0.20%.
In such scheme, it is characterised in that x 0.05%.
A kind of preparation method of the bismuth telluride-base composite thermoelectric material of described flexible thermo-electric device application, its feature exist
In comprising the following steps：
1) Bi is obtained using melting annealing and quenching legal system0.5Sb1.5Te3Matrix material ingot bar, by Bi0.5Sb1.5Te3Matrix material
Material ingot bar is broken, ball milling, obtains the powder that particle diameter is 1~5 μm；
2) technical grade graphite block body is ground into powder, crosses 400 eye mesh screens, obtain the graphite powder that particle diameter is less than 37 μm, made
For x G/Bi0.5Sb1.5Te3The second phase in composite thermoelectric material；
3) calculated according to chemical composition and weigh matrix powder and corresponding graphite powder, under normal temperature and pressure, in absolute ethyl alcohol
Middle 10~20min of ULTRASONIC COMPLEX, then centrifuge, it is x G/Bi that vacuum drying, which obtains composition,0.5Sb1.5Te3Compound thermoelectricity powder
Body；
4) by x G/Bi0.5Sb1.5Te3Compound thermoelectricity powder pours into stainless steel mould, is suppressed through cold pressing, obtains thickness as 1
~2mm composite body；
5) composite body is inserted into hydrogen atmosphere sintering furnace to be heat-treated, obtains the compound thermoelectricity material of bismuth telluride-base
Material.
In such scheme, the Bi in step 1)0.5Sb1.5Te3The preparation method of matrix material ingot bar is：Formed according to name
For Bi0.5Sb1.5Te3The dosage of high pure metal Bi powder, Sb powder and Te powder is weighed, quartz ampoule is encapsulated under vacuum state,
It is placed in melting furnace, melting annealing 9-11h, by melt quenching, obtains target product Bi at 700-900 DEG C0.5Sb1.5Te3Ingot bar.
In such scheme, the milling parameters in step 2) are：Rotational speed of ball-mill is 200~300r/min, Ball-milling Time
For 3~5h.
In such scheme, the centrifuging process parameter in step 3)：Centrifugal rotational speed is 600~1000r/min, and centrifugation time is
5~10min.
In such scheme, the vacuum drying process parameter in step 3)：Drying temperature is 40~60 DEG C, drying time 1
~2h.
In such scheme, the size of the stainless steel mould in step 4) is internal diameterExternal diameterPressure head
Diameter
In such scheme, the pressing process parameter in step 4)：Pressing pressure is 10~20MPa.
In such scheme, the heat treatment process parameter in step 5)：Heat treatment temperature is 350~450 DEG C, heat treatment time
For 1.5~2.5h, heating rate is 2~10 DEG C/min.
Using technical grade graphite as raw material in the present invention, greatly reduce and prepare cost and equipment requirement, easily realize scale
Metaplasia is produced.Due to introducing the phases of G second, a large amount of crystal boundaries enhance phon scattering mechanism, can effectively reduce the crystalline substance of bismuth telluride-base material
Lattice thermal conductivity κL, the synthesis thermoelectricity capability ZT of prepared composite thermoelectric material, which has been worth to, to be significantly improved.
Beneficial effects of the present invention are：The method provided by the present invention for preparing bismuth telluride-base composite thermoelectric material, has
The features such as technique is simple controllable, short preparation period and energy consumption are low, is easy to large-scale industrial production.Prepared group in the present invention
As x G/Bi0.5Sb1.5Te3The composite thermoelectric material of (x=0,0.05%, 0.10%, 0.15%, 0.20%), there is raw material
It is rich and easy to get, can be in room temperature to 100 DEG C of steady operations the characteristics of focus excellent performance.As the composition obtained by embodiment 1 is
0.05%G/Bi0.5Sb1.5Te3Composite thermoelectric material, thermal conductivity is only 0.40Wm at room temperature-1·K-1, electrical conductivity and Sai Bei
Gram coefficient is respectively 3.04 × 104S·m-1With 228.5 μ VK-1, thermoelectric figure of merit ZT is finally integrated in 320K and reaches 1.05.
Brief description of the drawings
Fig. 1 is that composition is x G/Bi in the present invention0.5Sb1.5Te3(x=0,0.05%, 0.10%, 0.15%, 0.20%)
Composite thermoelectric material XRD spectrum, JCPDS data are Bi0.5Sb1.5Te3Standard diagram data (JCPDS 49-1713).
Fig. 2 is 0.05%G/Bi in the present invention0.5Sb1.5Te3BEI pictures, SEI pictures and the C, Bi of composite thermoelectric material, Sb,
Sweep figure in the wave spectrum face of Te elements.
Fig. 3 is that composition is x G/Bi in the present invention0.5Sb1.5Te3(x=0,0.05%, 0.10%, 0.15%, 0.20%)
Composite thermoelectric material electrical conductivity and temperature between relation curve, 300~480K of temperature range.
Fig. 4 is that composition is x G/Bi in the present invention0.5Sb1.5Te3(x=0,0.05%, 0.10%, 0.15%, 0.20%)
Composite thermoelectric material Seebeck coefficient and temperature between relation curve, 300~480K of temperature range.
Fig. 5 is that composition is x G/Bi in the present invention0.5Sb1.5Te3(x=0,0.05%, 0.10%, 0.15%, 0.20%)
Composite thermoelectric material thermal conductivity and temperature between relation curve, 300~480K of temperature range.
Fig. 6 is that composition is x G/Bi in the present invention0.5Sb1.5Te3(x=0,0.05%, 0.10%, 0.15%, 0.20%)
Composite thermoelectric material ZT values and temperature between relation curve, 300~480K of temperature range.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1：0.05%G/Bi0.5Sb1.5Te3Composite thermoelectric material
Prepare 0.05%G/Bi in the present invention0.5Sb1.5Te3The raw material selection of composite thermoelectric material and concrete operations stream
Journey is as follows：
Bi is obtained using melting annealing+quenching legal system0.5Sb1.5Te3Matrix material ingot bar；Specific preparation method is as follows：According to
Name composition is Bi0.5Sb1.5Te3Weigh high pure metal Bi (99.99%, powder), Sb (99.99%, powder) and Te
The dosage of (99.99%, powder), quartz ampoule is encapsulated under vacuum state, is placed in melting furnace, melting annealing 10h at 800 DEG C,
By melt quenching, target product Bi is obtained0.5Sb1.5Te3Ingot bar is matrix material；
1) ingot bar is crushed, ball milling, obtains the matrix powder that particle diameter is 1~5 μm.Milling parameters：Rotational speed of ball-mill is
200r/min, Ball-milling Time 4h.
2) after technical grade graphite block body is ground, 400 eye mesh screens are crossed, obtain the graphite powder that particle diameter is less than 37 μm, as
0.05%G/Bi0.5Sb1.5Te3Second phase graphite raw material in composite thermoelectric material.
3) according to chemical composition 0.05%G/Bi0.5Sb1.5Te3Calculate and weigh matrix powder 3g and corresponding graphite powder, will
Graphite powder ultrasonic disperse adds matrix powder, ultrasonic disperse 15min, centrifuged under rotating speed 800r/min in 20ml absolute ethyl alcohols
5min, lower slurry is taken, be dried in vacuo 1h at 60 DEG C, obtain 0.05%G/Bi0.5Sb1.5Te3Compound thermoelectricity powder.
4) above-mentioned 0.05%G/Bi is weighed0.5Sb1.5Te31~2g of compound thermoelectricity powder, pours into internal diameterExternal diameterPressure head diameterStainless steel mould in, the cold moudling under 20MPa, obtain thickness be 1~2mm base
Body.
5) by above-mentioned 0.05%G/Bi0.5Sb1.5Te3Composite body is inserted hydrogen atmosphere sintering furnace and is heat-treated.
Heat treatment process parameter：Heat treatment temperature is 400 DEG C, heat treatment time 2h, and heating rate is 2~10 DEG C/min.
The 0.05%G/Bi of gained after above-mentioned heat treatment0.5Sb1.5Te3The XRD spectra of composite is shown in 0.05% in Fig. 1
G/Bi0.5Sb1.5Te3Shown in spectral line：The principal character diffraction maximum of composite sample and standard card JCPDS 49-
1713Bi0.5Sb1.5Te3The characteristic diffraction peak of compound is consistent, and it is Bi to show its phase composition0.5Sb1.5Te3.This is mainly due to
Two-phase G contents 0.05% are far smaller than the minimum value 1% that can detect of XRD measuring instruments, so and being not detected by G phases.BEI
It is as shown in Figure 2 that figure is swept in the wave spectrum face of picture, SEI pictures and C, Bi, Sb, Te element：Analysis contrast SEI and BEI figures are it can be seen that BEI
Phase Bi based on grey colour contrast in figure0.5Sb1.5Te3, black contrast is hole and crystal boundary, and this matches with XRD results.Sweep in wave spectrum face
Image result shows：C element contained by second phase graphite be evenly distributed on bismuth telluride matrix grain shaped into grain boundary sites.300~
In relation curve such as Fig. 3~6 under 480K between the electrical conductivity of material, Seebeck coefficient, thermal conductivity and ZT values and temperature
0.05%G/Bi0.5Sb1.5Te3Shown in curve：In 320K, its power factor has 1.59mWm-1K, thermal conductivity is as little as
0.48W·m-1·K-1, finally, comprehensive thermoelectric figure of merit ZT reaches maximum 1.05.
Embodiment 2：0.10%G/Bi0.5Sb1.5Te3Composite thermoelectric material
Prepare 0.10%G/Bi in the present invention0.5Sb1.5Te3The raw material selection of composite thermoelectric material and concrete operations stream
Journey is as follows：
Bi is obtained using melting annealing+quenching legal system0.5Sb1.5Te3Matrix material ingot bar；Specific preparation method is as follows：According to
Name composition is Bi0.5Sb1.5Te3Weigh high pure metal Bi (99.99%, powder), Sb (99.99%, powder) and Te
The dosage of (99.99%, powder), quartz ampoule is encapsulated under vacuum state, is placed in melting furnace, melting annealing 10h at 800 DEG C,
By melt quenching, target product Bi is obtained0.5Sb1.5Te3Ingot bar is matrix material；
1) ingot bar is crushed, ball milling, obtains the matrix powder that particle diameter is 1~5 μm.Milling parameters：Rotational speed of ball-mill is
200r/min, Ball-milling Time 4h.
2) after technical grade graphite block body is ground, 400 eye mesh screens are crossed, obtain the graphite powder that particle diameter is less than 37 μm, as
0.10%G/Bi0.5Sb1.5Te3Second phase graphite raw material in composite thermoelectric material.
3) according to chemical composition 0.10%G/Bi0.5Sb1.5Te3Calculate and weigh matrix powder 3g and corresponding graphite powder, will
Graphite powder ultrasonic disperse adds matrix powder, ultrasonic disperse 15min, centrifuged under rotating speed 800r/min in 20ml absolute ethyl alcohols
5min, lower slurry is taken, be dried in vacuo 1h at 60 DEG C, obtain 0.10%G/Bi0.5Sb1.5Te3Compound thermoelectricity powder.
4) above-mentioned 0.10%G/Bi is weighed0.5Sb1.5Te31~2g of compound thermoelectricity powder, pours into internal diameterExternal diameterPressure head diameterStainless steel mould in, the cold moudling under 20MPa, obtain thickness be 1~2mm base
Body.
5) by above-mentioned 0.10%G/Bi0.5Sb1.5Te3Composite body is inserted hydrogen atmosphere sintering furnace and is heat-treated.
Heat treatment process parameter：Heat treatment temperature is 400 DEG C, heat treatment time 2h, and heating rate is 2~10 DEG C/min.
The 0.10%G/Bi of gained after above-mentioned heat treatment0.5Sb1.5Te3The XRD spectra of composite is shown in 0.10% in Fig. 1
G/Bi0.5Sb1.5Te3Shown in spectral line, under 300~480K the electrical conductivity of material, Seebeck coefficient, thermal conductivity and ZT values and temperature it
Between relation curve such as Fig. 3~6 in 0.10%G/Bi0.5Sb1.5Te3Shown in curve：In 310K, its power factor is 1.32mW
m-1K, thermal conductivity as little as 0.45Wm-1·K-1, finally, comprehensive thermoelectric figure of merit ZT reaches maximum 0.90.
Embodiment 3：0.15%G/Bi0.5Sb1.5Te3Composite thermoelectric material
Prepare 0.15%G/Bi in the present invention0.5Sb1.5Te3The raw material selection of composite thermoelectric material and concrete operations stream
Journey is as follows：
Bi is obtained using melting annealing+quenching legal system0.5Sb1.5Te3Matrix material ingot bar；Specific preparation method is as follows：According to
Name composition is Bi0.5Sb1.5Te3Weigh high pure metal Bi (99.99%, powder), Sb (99.99%, powder) and Te
The dosage of (99.99%, powder), quartz ampoule is encapsulated under vacuum state, is placed in melting furnace, melting annealing 10h at 800 DEG C,
By melt quenching, target product Bi is obtained0.5Sb1.5Te3Ingot bar is matrix material；
1) ingot bar is crushed, ball milling, obtains the matrix powder that particle diameter is 1~5 μm.Milling parameters：Rotational speed of ball-mill is
200r/min, Ball-milling Time 4h.
2) after technical grade graphite block body is ground, 400 eye mesh screens are crossed, obtain the graphite powder that particle diameter is less than 37 μm, as
0.15%G/Bi0.5Sb1.5Te3Second phase graphite raw material in composite thermoelectric material.
3) according to chemical composition 0.15%G/Bi0.5Sb1.5Te3Calculate and weigh matrix powder 3g and corresponding graphite powder, will
Graphite powder ultrasonic disperse adds matrix powder, ultrasonic disperse 15min, centrifuged under rotating speed 800r/min in 20ml absolute ethyl alcohols
5min, lower slurry is taken, be dried in vacuo 1h at 60 DEG C, obtain 0.15%G/Bi0.5Sb1.5Te3Compound thermoelectricity powder.
4) above-mentioned 0.15%G/Bi is weighed0.5Sb1.5Te31~2g of compound thermoelectricity powder, pours into internal diameterExternal diameterPressure head diameterStainless steel mould in, the cold moudling under 20MPa, obtain thickness be 1~2mm base
Body.
5) by above-mentioned 0.15%G/Bi0.5Sb1.5Te3Composite body is inserted hydrogen atmosphere sintering furnace and is heat-treated.
Heat treatment process parameter：Heat treatment temperature is 400 DEG C, heat treatment time 2h, and heating rate is 2~10 DEG C/min.
The 0.15%G/Bi of gained after above-mentioned heat treatment0.5Sb1.5Te3The XRD spectra of composite is shown in 0.15% in Fig. 1
G/Bi0.5Sb1.5Te3Shown in spectral line, under 300~480K the electrical conductivity of material, Seebeck coefficient, thermal conductivity and ZT values and temperature it
Between relation curve such as Fig. 3~6 in 0.15%G/Bi0.5Sb1.5Te3Shown in curve：In 310K, its power factor is 1.19mW
m-1K, thermal conductivity as little as 0.41Wm-1·K-1, finally, comprehensive thermoelectric figure of merit ZT reaches maximum 0.89.
Embodiment 4：0.20%G/Bi0.5Sb1.5Te3Composite thermoelectric material
Prepare 0.20%G/Bi in the present invention0.5Sb1.5Te3The raw material selection of composite thermoelectric material and concrete operations stream
Journey is as follows：
Bi is obtained using melting annealing+quenching legal system0.5Sb1.5Te3Matrix material ingot bar；Specific preparation method is as follows：According to
Name composition is Bi0.5Sb1.5Te3Weigh high pure metal Bi (99.99%, powder), Sb (99.99%, powder) and Te
The dosage of (99.99%, powder), quartz ampoule is encapsulated under vacuum state, is placed in melting furnace, melting annealing 10h at 800 DEG C,
By melt quenching, target product Bi is obtained0.5Sb1.5Te3Ingot bar is matrix material；
1) ingot bar is crushed, ball milling, obtains the matrix powder that particle diameter is 1~5 μm.Milling parameters：Rotational speed of ball-mill is
200r/min, Ball-milling Time 4h.
2) after technical grade graphite block body is ground, 400 eye mesh screens are crossed, obtain the graphite composite powder that particle diameter is less than 37 μm, as
0.20%G/Bi0.5Sb1.5Te3Second phase graphite raw material in composite thermoelectric material.
3) according to chemical composition 0.20%G/Bi0.5Sb1.5Te3Calculate and weigh matrix powder 3g and corresponding graphite powder,
By graphite powder ultrasonic disperse in 20ml absolute ethyl alcohols, add matrix powder, ultrasonic disperse 15min, under rotating speed 800r/min from
Heart 5min, takes lower slurry, is dried in vacuo 1h at 60 DEG C, obtains 0.20%G/Bi0.5Sb1.5Te3Compound thermoelectricity powder.
4) above-mentioned 0.20%G/Bi is weighed0.5Sb1.5Te31~2g of compound thermoelectricity powder, pours into internal diameterExternal diameterPressure head diameterStainless steel mould in, the cold moudling under 20MPa, obtain thickness be 1~2mm base
Body.
5) by above-mentioned 0.20%G/Bi0.5Sb1.5Te3Composite body is inserted hydrogen atmosphere sintering furnace and is heat-treated.
Heat treatment process parameter：Heat treatment temperature is 400 DEG C, heat treatment time 2h, and heating rate is 2~10 DEG C/min.
The 0.20%G/Bi of gained after above-mentioned heat treatment0.5Sb1.5Te3The XRD spectra of composite is shown in 0.20% in Fig. 1
G/Bi0.5Sb1.5Te3Shown in spectral line, under 300~480K the electrical conductivity of material, Seebeck coefficient, thermal conductivity and ZT values and temperature it
Between relation curve such as Fig. 3~6 in 0.20%G/Bi0.5Sb1.5Te3Shown in curve：In 320K, its power factor is 1.06mW
m-1K, thermal conductivity as little as 0.40Wm-1·K-1, finally, comprehensive thermoelectric figure of merit ZT reaches maximum 0.81.
Reference examples 1：Bi0.5Sb1.5Te3Matrix thermoelectric material
Prepare Bi in the present invention0.5Sb1.5Te3Matrix thermoelectric material concrete operations flow is as follows：
Bi is obtained using melting annealing+quenching legal system0.5Sb1.5Te3Matrix material ingot bar；Specific preparation method is as follows：According to
Name composition is Bi0.5Sb1.5Te3Weigh high pure metal Bi (99.99%, powder), Sb (99.99%, powder) and Te
The dosage of (99.99%, powder), quartz ampoule is encapsulated under vacuum state, is placed in melting furnace, melting annealing 10h at 800 DEG C,
By melt quenching, target product Bi is obtained0.5Sb1.5Te3Ingot bar is matrix material；
1) ingot bar is crushed, ball milling, obtains the matrix powder that particle diameter is 1~5 μm.Milling parameters：Rotational speed of ball-mill is
200r/min, Ball-milling Time 4h.
2) matrix powder 3g is weighed, matrix powder is added in 20ml absolute ethyl alcohols, ultrasonic disperse 15min, in rotating speed 800r/
5min is centrifuged under min, takes lower slurry, 1h is dried in vacuo at 60 DEG C, obtains Bi0.5Sb1.5Te3Thermoelectricity powder.
3) above-mentioned Bi is weighed0.5Sb1.5Te3Thermoelectricity 1~2g of powder, pours into internal diameterExternal diameterPressure head is straight
Footpath Stainless steel mold in, the cold moudling under 20MPa, obtain thickness be 1~2mm base substrate.
4) by above-mentioned Bi0.5Sb1.5Te3Body of material is inserted hydrogen atmosphere sintering furnace and is heat-treated.Technology for Heating Processing is joined
Number：Heat treatment temperature is 400 DEG C, heat treatment time 2h, and heating rate is 2~10 DEG C/min.
The Bi of gained after above-mentioned heat treatment0.5Sb1.5Te3The XRD spectra of thermoelectric material is shown in Bi in Fig. 10.5Sb1.5Te3Spectral line
It is shown, relation curve such as Fig. 3 under 300~480K between the electrical conductivity of material, Seebeck coefficient, thermal conductivity and ZT values and temperature
Bi in~60.5Sb1.5Te3Shown in curve：In 320K, its power factor is 1.40mWm-1K, thermal conductivity 0.60Wm-1·
K-1, finally, comprehensive thermoelectric figure of merit ZT reaches maximum 0.74.Result in comparative example 1~4 is found：Composite ZT values
Compared with the height of matrix material, illustrate that the micro second phase G of addition can be with the thermoelectricity capability of Effective Regulation material, and then lift material
Thermoelectricity capability.And with optimal ZT values be G addition for 0.05% sample, its maximum ZT value 1.05 in 320K compared with
Matrix material improves 42%.
Reference examples 2：Bi0.5Sb1.5Te3Matrix and graphene composite thermoelectric material
Using graphene as the second phase, with paper " the compound bismuth telluride-base heat of graphene that Donghua University author is Liang Beibei
It is by Bi compared with the preparation of electric material and performance study ", in the paper0.5Sb1.5Te3By SPS, (plasma discharging burns
Knot) composite thermoelectric material made from technique.Although graphite G thermoelectricity capability can not show a candle to graphene, G/Bi0.5Sb1.5Te3Heat
Electrical property is but better than graphene/Bi0.5Sb1.5Te3Composite thermoelectric material, correlated performance contrast are as shown in table 1 below.The compound thermoelectricity
Material can be as preparation, the raw material of assembling high-performance flexible thermo-electric device, and are expected to answer in the commercialization of flexible thermo-electric device
Broken through with middle realize.
The G/Bi of table 10.5Sb1.5Te3With graphene/Bi0.5Sb1.5Te3Composite thermoelectric material thermoelectricity capability contrasts
Claims (10)
- A kind of 1. bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application, it is characterised in that the group of the thermoelectric material As xG/Bi0.5Sb1.5Te3, G is graphite, and wherein x is that the second phase graphite accounts for matrix Bi0.5Sb1.5Te3Mass percent, scope In 0≤x≤0.20%.
- 2. a kind of bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 1, its feature exist In x 0.05%.
- A kind of 3. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 1 Method, it is characterised in that comprise the following steps：1) Bi is obtained using melting annealing and quenching legal system0.5Sb1.5Te3Matrix material ingot bar, by Bi0.5Sb1.5Te3Matrix material is cast Block is broken, ball milling, obtains the powder that particle diameter is 1~5 μm；2) technical grade graphite block body is ground into powder, crosses 400 eye mesh screens, the graphite powder that particle diameter is less than 37 μm is obtained, as xG/ Bi0.5Sb1.5Te3The second phase in composite thermoelectric material；3) calculated according to chemical composition and weigh matrix powder and corresponding graphite powder, under normal temperature and pressure, surpassed in absolute ethyl alcohol Compound 10~the 20min of sound, then centrifuge, it is x G/Bi that vacuum drying, which obtains composition,0.5Sb1.5Te3Compound thermoelectricity powder；4) by x G/Bi0.5Sb1.5Te3Compound thermoelectricity powder pours into stainless steel mould, is suppressed through cold pressing, it is 1~2mm to obtain thickness Composite body；5) composite body is inserted into hydrogen atmosphere sintering furnace to be heat-treated, obtains bismuth telluride-base composite thermoelectric material.
- A kind of 4. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the Bi in step 1)0.5Sb1.5Te3The preparation method of matrix material ingot bar is：It is according to name composition Bi0.5Sb1.5Te3The dosage of high pure metal Bi powder, Sb powder and Te powder is weighed, quartz ampoule is encapsulated under vacuum state, puts In melting furnace, melting annealing 9-11h, by melt quenching, obtains target product Bi at 700-900 DEG C0.5Sb1.5Te3Ingot bar.
- A kind of 5. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the milling parameters in step 2) are：Rotational speed of ball-mill is 200~300r/min, Ball-milling Time is 3~ 5h。
- A kind of 6. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the centrifuging process parameter in step 3)：Centrifugal rotational speed is 600~1000r/min, centrifugation time is 5~ 10min。
- A kind of 7. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the vacuum drying process parameter in step 3)：Drying temperature is 40~60 DEG C, and drying time is 1~2h.
- A kind of 8. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the size of the stainless steel mould in step 4) is internal diameterExternal diameterPressure head diameter
- A kind of 9. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the pressing process parameter in step 4)：Pressing pressure is 10~20MPa.
- A kind of 10. preparation side of the bismuth telluride-base composite thermoelectric material of flexible thermo-electric device application according to claim 3 Method, it is characterised in that the heat treatment process parameter in step 5)：Heat treatment temperature is 350~450 DEG C, heat treatment time 1.5 ~2.5h, heating rate are 2~10 DEG C/min.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649147A (en) * | 2019-09-11 | 2020-01-03 | 大连理工大学 | Second-phase doped TiNiSn-based Half-Heusler thermoelectric material and preparation method thereof |
| CN110767796A (en) * | 2019-10-14 | 2020-02-07 | 东华大学 | Two-dimensional transition metal carbide/bismuth telluride or derivative thereof based thermoelectric composite material and preparation thereof |
| CN110828664A (en) * | 2019-11-19 | 2020-02-21 | 中国科学院上海微系统与信息技术研究所 | Phase change material, preparation method of phase change material and phase change memory |
| CN112234137A (en) * | 2020-10-30 | 2021-01-15 | 武汉理工大学 | Large-area flexible thermoelectric refrigeration thin film cascade device and preparation method thereof |
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| CN114210978A (en) * | 2021-12-22 | 2022-03-22 | 中国电子科技集团公司第十八研究所 | Hot extrusion molding method of bismuth telluride thermoelectric material |
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| CN116813347A (en) * | 2023-05-22 | 2023-09-29 | 合肥睿力工业科技有限公司 | Bismuth telluride composite and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102694116A (en) * | 2012-05-30 | 2012-09-26 | 天津大学 | Method for preparing thermoelectric material with P-type nano-structure and bismuth telluride matrix |
| CN102760827A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Bi2Te3 thin-piece/graphene composite material, preparation method and applications thereof |
| CN103165808A (en) * | 2011-12-19 | 2013-06-19 | 财团法人工业技术研究院 | Thermoelectric composite material |
| CN103332679A (en) * | 2013-05-31 | 2013-10-02 | 天津安品有机硅材料有限公司 | Superconductive graphite synthesized slice, preparation method therefor and applications thereof |
| KR20140103765A (en) * | 2013-02-19 | 2014-08-27 | 삼성전자주식회사 | Heterogeneous laminate comprising graphene, preparing method thereof, thermoelectric material, thermoelectric module and thermoelectric apparatus comprising same |
| CN105895796A (en) * | 2016-05-11 | 2016-08-24 | 深圳市芯华芯动力技术有限公司 | Preparation method of CuGaX2/ multilayer nano graphene sheet composite material |
| EP3381069B1 (en) * | 2015-11-24 | 2019-10-30 | Consejo Superior De Investigaciones Científicas (CSIC) | A process of obtainment of an n-type or a p-type organic semiconductor by uv-vis irradiation |
-
2017
- 2017-09-15 CN CN201710832548.6A patent/CN107681043B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165808A (en) * | 2011-12-19 | 2013-06-19 | 财团法人工业技术研究院 | Thermoelectric composite material |
| CN102694116A (en) * | 2012-05-30 | 2012-09-26 | 天津大学 | Method for preparing thermoelectric material with P-type nano-structure and bismuth telluride matrix |
| CN102760827A (en) * | 2012-07-23 | 2012-10-31 | 浙江大学 | Bi2Te3 thin-piece/graphene composite material, preparation method and applications thereof |
| KR20140103765A (en) * | 2013-02-19 | 2014-08-27 | 삼성전자주식회사 | Heterogeneous laminate comprising graphene, preparing method thereof, thermoelectric material, thermoelectric module and thermoelectric apparatus comprising same |
| CN103332679A (en) * | 2013-05-31 | 2013-10-02 | 天津安品有机硅材料有限公司 | Superconductive graphite synthesized slice, preparation method therefor and applications thereof |
| EP3381069B1 (en) * | 2015-11-24 | 2019-10-30 | Consejo Superior De Investigaciones Científicas (CSIC) | A process of obtainment of an n-type or a p-type organic semiconductor by uv-vis irradiation |
| CN105895796A (en) * | 2016-05-11 | 2016-08-24 | 深圳市芯华芯动力技术有限公司 | Preparation method of CuGaX2/ multilayer nano graphene sheet composite material |
Non-Patent Citations (3)
| Title |
|---|
| DAEWOO SUH, ET AL: "Enhanced thermoelectric performance of Bi0.5Sb1.5Te3-expanded graphene composites by simultaneous modulation of electronic and thermal carrier transport", 《NANO ENERGY》 * |
| KHUSHBOO AGARWAL，ET AL: "Nanoscale thermoelectric properties of Bi2Te3 e Graphene nanocomposites: Conducting atomic force, scanning thermal and kelvin probe microscopy studies", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| MARIO CULEBRAS,ET AL: "Thermoelectric measurements of PEDOT:PSS/expanded graphite composites", 《J MATER SCI》 * |
Cited By (14)
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|---|---|---|---|---|
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| CN112582527A (en) * | 2020-12-13 | 2021-03-30 | 安徽大学 | Preparation method of graphite-doped GeS2 thermoelectric material |
| CN113206185B (en) * | 2021-05-18 | 2022-06-17 | 四川大学 | Preparation method of p-type bismuth telluride-based composite thermoelectric material |
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| CN116283295B (en) * | 2023-03-15 | 2023-12-05 | 佛山(华南)新材料研究院 | Bismuth telluride-based composite thermoelectric material and preparation method thereof |
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