CN108103336B - Bi1-xSbxThermoelectric material and preparation method thereof - Google Patents

Bi1-xSbxThermoelectric material and preparation method thereof Download PDF

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Publication number
CN108103336B
CN108103336B CN201611053017.9A CN201611053017A CN108103336B CN 108103336 B CN108103336 B CN 108103336B CN 201611053017 A CN201611053017 A CN 201611053017A CN 108103336 B CN108103336 B CN 108103336B
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thermoelectric material
preparation
thermoelectric
powder body
orientation
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CN108103336A (en
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苏箐
李山鹰
刘向云
陈湘
李银峰
李辉
张艳花
丁明洁
赵海鹏
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Henan University of Urban Construction
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Henan University of Urban Construction
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/007—Preparing arsenides or antimonides, especially of the III-VI-compound type, e.g. aluminium or gallium arsenide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C12/00—Alloys based on antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention relates to a kind of Bi1‑xSbxThermoelectric material and preparation method thereof belongs to thermoelectric material preparation technical field.1) preparation method of the invention includes the following steps: Bi1‑xSbxPowder body material is orientated in magnetic field, and orientation is 0.5 ~ 1 h；The value range of the x is 0.05≤x≤0.35；2) by the Bi after orientation1‑xSbxPowder body material carries out vacuum hotpressing；The hot pressing temperature be 260-280 DEG C, hot pressing time be 120-300s to get.Bi can be improved by orientation field orientation in this method1‑xSbxThe oriented of powder body material, and then weaken and the electron scattering in migration is acted on, the thermoelectricity capability of thermoelectric material is improved, thermal conductivity is 250 ~ 360W/(cmK), thermoelectric figure of merit ZT is 0.1 ~ 0.13, and being widely applied has good economic benefit.

Description

Bi1-xSbxThermoelectric material and preparation method thereof
Technical field
The present invention relates to a kind of Bi1-xSbxThermoelectric material and preparation method thereof belongs to thermoelectric material preparation technical field.
Background technique
For thermoelectric material under the potential difference effect at both ends, the directional migration of carrier can produce the temperature difference, realize electric energy with Mutual conversion between thermal energy is a kind of new green energy material.There is body using the thermo-electric device that the electric temperature difference is freezed Product it is small, without machine driving, low-power consumption, it is noiseless, pollution-free, non-maintaining, do not need moving component and cycle fluid at work, The advantages of arbitrary size and shape can be made, is suitable for various energy resources occasion.Currently, electric temperature difference device high-tech, military affairs, The fields such as agricultural, medical treatment and daily life have a wide range of applications.As a kind of novel energy utilization type, research and preparation New thermoelectric materials promote sustainable economic development to be of great significance for improving efficiency of energy utilization.
1843667 A(applying date 2006.5.16 of patent CN) disclose a kind of preparation side of Bi-Sb-Te pyroelectric material Method, this method mainly include that raw material high-energy ball milling handles to obtain alloy powder, and alloy powder is shaped with plasma activated sintering, Sintering process carries out under vacuum or inert gas shielding, and sintering temperature is 300 DEG C ~ 500 DEG C, and pressure is 40Mpa ~ 60Mpa, protects Warm 10 ~ 30 min of time, but 0.811 ~ 1.321W/(m of its thermal conductivity K) and thermoelectric figure of merit Z be 1.53 × 10-3/K~5.26× 10-3/ K effect is bad, and in order to obtain better thermoelectric material, scientist has also developed Bi1-xSbxBase thermoelectricity material.
In order to improve Bi1-xSbxThe performance of base thermoelectricity material, researcher it has been carried out synthetic method, doping vario-property, Pattern improves and the research of low-dimensional etc., and current many preparation processes are used to prepare Bi1-xSbxMaterial: melting quenching, length Time diffusion annealing, mechanical alloying, discharge plasma sintering (SPS), electrochemical deposition, solvent-thermal method etc..Melting quenching and Diffusion annealing combination can promote alloying elements distribution uniform, but energy consumption is high for synthesis, and the time is long, at high cost.Plasma discharging Sintering technology (SPS) reaction time is short, it is desirable that temperature is lower, but product component is difficult to control.Metal electrodeposition is easier Component, the pattern of product are controlled, but process route is complex, yield is lower.The product of solvent structure can achieve Nano grade, but be easy to be mixed into organic impurities, it can not home position observation.In recent years, not with nano material and nanotechnology Disconnected development carries out structure regulating on nanoscale, and then improves conducting material thermoelectricity performance, becomes an important research direction, grinds Studying carefully personnel to attempt new moulding process includes that hot-forming, hot extrusion molding, plasma activated sintering molding and channel turn Angle extruding etc., but it is limited to pyroelectric material performance raising, it not can be carried out extensive use.
Summary of the invention
Bi is prepared the purpose of the present invention is to provide a kind of1-xSbxThe method of thermoelectric material, this method pass through to Bi1-xSbx Powder body material is orientated in magnetic field, can be dramatically increased the thermal conductivity and thermoelectric figure of merit ZT of thermoelectric material, be improved thermoelectric material Thermoelectricity capability.
Another object of the present invention, which also resides in, provides a kind of thermoelectric material prepared according to the above method.
It is a kind of to prepare Bi1-xSbxThe method of thermoelectric material, includes the following steps:
1) by Bi1-xSbxPowder body material is orientated in magnetic field, and orientation is 0.5 ~ 1 h；The value range of the x is 0.05≤x≤0.35；
2) by the Bi after orientation1-xSbxPowder body material carries out vacuum hotpressing；The hot pressing temperature is 260-280 DEG C, hot pressing Time be 120-300s to get.
In order to obtain preferable orientation effect, the alignment magnetic field in magnetic field described in step 2 of the present invention is 1800 ~ 2200kA/m。
Bi used in step 1) of the present invention1-xSbxPowder body material is from a wealth of sources, can pass through method comprising the following steps It is made: Bi and Sb is subjected to mechanical alloying under inert gas protection, dehydrated alcohol is added as dispersing agent, then vacuum is dry It is dry to get.It can also be achieved other ways, such as directly purchase obtains.
In order to obtain preferable grinding effect and higher comprehensive benefit, the mechanical alloying turns to ball milling, this hair It is bright that the condition of ball milling is optimized in R&D process, the condition of the ball milling after optimization are as follows: ratio of grinding media to material is 10:1 ~ 20: 1, Revolving speed is 300 ~ 500r/min, and the time is 80 ~ 120 h.
Mechanical alloying is carried out in order to make Bi and Sb be sufficiently mixed dispersion, the dehydrated alcohol amount of addition is preferably every mole Bi1-xSbxThermoelectric material needs 50 ~ 150mL dehydrated alcohol.
The inert gas is nitrogen or argon gas.
The vacuum pressure of vacuum hotpressing described in step 2 is not more than -0.1MPa.
The pressure of hot pressing described in step 2 is 30 ~ 60MPa.
The present invention also provides using Bi made from the right above method1-xSbxThermoelectric material.
In view of practical application place and cost, Bi of the invention1-xSbxDisc-shaped is made in thermoelectric material, the disk Diameter is 10mm, with a thickness of 2 mm, it is of course also possible to other shapes be made in hot forming, such as according to other actual needs Ellipsoid, cuboid etc..
Preparation Bi provided by the invention1-xSbxThe method of thermoelectric material, this method using mechanical alloying, magnetic field orientating and Hot press forming technology improves Bi1-xSbxThe oriented of powder body material, and then reduce the work of the scattering to the electronics in migration With reducing lattice thermal conductivity, significantly increase the thermal conductivity and thermoelectric figure of merit ZT of thermoelectric material, improve the heat of thermoelectric material Electrical property；It secondly, first using magnetic field orientating, then can be improved the consistency of material using vacuum hot-pressing process, improve sample block Density reduces porosity, also improves the thermoelectricity capability of thermoelectric material；Here, the preparation method is simple, and it is easy to operate, it is big Sizable application has preferable extensive prospect.
The thermoelectric material of preparation of the invention, thermal conductivity be 250 ~ 360W/(cmK), thermoelectric figure of merit ZT be 0.1 ~ 0.13。
Detailed description of the invention
Fig. 1 is the XRD diagram of thermoelectric material prepared by embodiment 1,2,3,4；
Fig. 2 is the figure of thermoelectric material DSC prepared by embodiment 1,2,3,4；
Fig. 3 is the molar fraction relational graph of thermoelectric material resistivity and Bi prepared by embodiment 1,2,3,4；
Fig. 4 is the molar fraction relational graph of thermoelectric material thermal conductivity and Bi prepared by embodiment 1,2,3,4；
Fig. 5 is the molar fraction relational graph of thermoelectric material Seebeck coefficient and Bi prepared by embodiment 1,2,3,4；
Fig. 6 is the molar fraction relational graph of thermoelectric material thermoelectric figure of merit ZT and Bi prepared by embodiment 1,2,3,4.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, embodiment of the present invention will be made into one below Step ground detailed description.
Embodiment 1
The present embodiment prepares Bi1-xSbxThe method of thermoelectric material includes the following steps:
1) 0.65mol raw material Bi and 0.35mol raw material Sb is weighed respectively；It is put into agate jar, in high energy ball mill Middle carry out mechanical alloying is added 50ml dehydrated alcohol and is used as dispersing agent, using nitrogen protection when ball milling, ratio of grinding media to material 10: 1, Speed of agitator is 300r/min, milling time 100h；Drying material in vacuum after grinding is obtained into Bi0.65Sb0.35Powder material Material；
2) Bi obtained in step 1)0.65Sb0.35Powder body material is fitted into mold, is put into magnetic field and is orientated, magnetic field strength For 1800KA/m, mold carries out slight vibration, orientation 0.5h in orientation process；
3) mold after orientation operation will be carried out in step 2 and is put into vacuum hotpressing machine, be evacuated to -0.1MPa, then plus Pressure heating is sintered, and sintering temperature is 260 DEG C, pressure 60MPa；Soaking time is 180s；Wafer sample is made, diameter is 10mm, with a thickness of 2 mm to get.
The Bi of the present embodiment1-xSbxThermoelectric material is the Bi directly obtained according to the above method1-xSbxThermoelectric material.
Embodiment 2
The present embodiment prepares Bi1-xSbxThe method of thermoelectric material includes the following steps:
1) by Bi0.75Sb0.25Powder body material is fitted into mold, is put into magnetic field and is orientated, and magnetic field strength 2100KA/m takes Slight vibration, 0.6 h of orientation are carried out to mold in the process；
2) mold is put into vacuum hotpressing machine, is evacuated to -0.1MPa, then pressurized, heated is sintered, sintering temperature 280 DEG C, 50 MPa of pressure；150 s of soaking time；Be made wafer sample, diameter 10mm, 2 mm of thickness to get.
The Bi of the present embodiment1-xSbxThermoelectric material is the Bi directly obtained according to the above method1-xSbxThermoelectric material.
Embodiment 3
The present embodiment prepares Bi1-xSbxThe method of thermoelectric material includes the following steps:
1) 0.85mol raw material Bi and 0.15mol raw material Sb is weighed respectively；It is put into agate jar, in high energy ball mill Middle carry out mechanical alloying is added 100ml dehydrated alcohol and is used as dispersing agent, using argon gas protection when ball milling, ratio of grinding media to material 15: 1, speed of agitator 500r/min, 120 h of milling time；Then vacuum drying obtains Bi0.85Sb0.15Powder body material；
2) Bi0.85Sb0.15Powder body material is fitted into mold, is put into magnetic field and is orientated, and magnetic field strength 2000KA/m takes Slight vibration, 1.0 h of orientation are carried out to mold in the process；
3) mold is put into vacuum hotpressing machine, is evacuated to -0.1MPa, then pressurized, heated is sintered, sintering temperature 270 DEG C, 60 MPa of pressure；240 s of soaking time；Be made wafer sample, diameter 10mm, 2 mm of thickness to get.
The Bi of the present embodiment1-xSbxThermoelectric material is the Bi directly obtained according to the above method1-xSbxThermoelectric material.
Embodiment 4
The present embodiment prepares Bi1-xSbxThe method of thermoelectric material includes the following steps:
1) 0.95mol raw material Bi and 0.05mol raw material Sb is weighed respectively；It is put into agate jar, in high energy ball mill Middle carry out mechanical alloying is added 100ml dehydrated alcohol and is used as dispersing agent, using argon gas protection when ball milling, ratio of grinding media to material 20: 1, Speed of agitator is 450r/min, 100 h of milling time；Then vacuum drying obtains Bi0.95Sb0.05Powder body material；
2) Bi0.95Sb0.05Powder body material is fitted into mold, is put into magnetic field and is orientated, and magnetic field strength 2200KA/m takes Slight vibration, orientation 0.5h are carried out to mold in the process；
3) mold is put into vacuum hotpressing machine, is evacuated to -0.1MPa, then pressurized, heated is sintered, sintering temperature 260 DEG C, 50 MPa of pressure；300 s of soaking time；Be made wafer sample, diameter 10mm, 2 mm of thickness to get.
The Bi of the present embodiment1-xSbxThermoelectric material is the Bi directly obtained according to the above method1-xSbxThermoelectric material.
Experimental example
1) XRD is tested
XRD test is carried out to thermoelectric material prepared by embodiment 1-4, test results are shown in figure 1, can be with from Fig. 1 Find out thermoelectric material structure uniformity prepared by embodiment 1 ~ 4.
2) DSC is tested
Differential scanning heat analysis DSC test, test result such as Fig. 2 institute are carried out to thermoelectric material prepared by embodiment 1-4 Show there is an apparent absorption peak between 290 ~ 300 DEG C, illustrates to have obtained structure by mechanical alloying uniform Bi1-xSbxThermoelectric material.
3) relationship of thermoelectric material resistivity and the molar fraction of Bi
The resistivity of thermoelectric material prepared by embodiment 1-4 is tested under room temperature, normal pressure, test result is as schemed Shown in 3, it can be seen from the figure that the resistivity 1.52 × 10 of embodiment 1-45~1.52×105Between Ω cm.
4) relationship of thermoelectric material thermal conductivity and the molar fraction of Bi
The thermal conductivity of thermoelectric material prepared by embodiment 1-4 is tested under room temperature, normal pressure, test result is as schemed Shown in 4, it can be seen from the figure that the thermal conductivity of embodiment 1-4 is in 250 ~ 360W/(cmK) between.
5) relationship of the molar fraction of thermoelectric material Seebeck coefficient and Bi
The Seebeck coefficient of thermoelectric material prepared by embodiment 1-4 is tested under room temperature, normal pressure, test knot Fruit is as shown in figure 5, it can be seen from the figure that the Seebeck coefficient of embodiment 1-4 is between 75 ~ 110 μ V/K.
6) relationship of the molar fraction of thermoelectric material thermoelectric figure of merit ZT and Bi
The thermoelectric figure of merit ZT of thermoelectric material prepared by embodiment 1-4 is tested under room temperature, normal pressure, test result As shown in fig. 6, it can be seen from the figure that the thermoelectric figure of merit ZT of embodiment 1-4 is between 0.1 ~ 0.13.

Claims (9)

1. a kind of prepare Bi1-xSbxThe method of thermoelectric material, which comprises the steps of:
1) by Bi1-xSbxPowder body material is orientated in magnetic field, and orientation is 0.5 ~ 1h；The value range of the x is 0.05≤x ≤0.35；The magnetic field strength in the magnetic field is 1800 ~ 2200kA/m；
2) by the Bi after orientation1-xSbxPowder body material carry out vacuum hotpressing to get；The hot pressing temperature is 260-280 DEG C, hot pressing Time is 120-300s.
2. preparation Bi according to claim 11-xSbxThe method of thermoelectric material, it is characterised in that: Bi described in step 1)1- xSbxPowder body material is made by method comprising the following steps: Bi and Sb being carried out mechanical alloying under inert gas protection, added Enter dehydrated alcohol as dispersing agent, be then dried in vacuo to get.
3. preparation Bi according to claim 21-xSbxThe method of thermoelectric material, it is characterised in that: the mechanical alloying For ball milling, the condition of the ball milling are as follows: ratio of grinding media to material 10: 1 ~ 20: 1, revolving speed are 300 ~ 500r/min, and the time is 80 ~ 120h.
4. preparation Bi according to claim 21-xSbxThe method of thermoelectric material, it is characterised in that: the inert gas is Nitrogen or argon gas.
5. preparation Bi according to claim 21-xSbxThe method of thermoelectric material, it is characterised in that: the dehydrated alcohol Dosage is every mole of Bi1-xSbx50 ~ 150ml ethyl alcohol need to be added in thermoelectric material.
6. preparation Bi according to claim 11-xSbxThe method of thermoelectric material, it is characterised in that: vacuum described in step 2 The vacuum degree of hot pressing is not more than ﹣ 0.1MPa.
7. preparation Bi according to claim 11-xSbxThe method of thermoelectric material, it is characterised in that: hot pressing described in step 2 Pressure is 30 ~ 60MPa.
8. a kind of using Bi made from method described in claim 11-xSbxThermoelectric material.
9. Bi according to claim 81-xSbxThermoelectric material, it is characterised in that: the Bi1-xSbxThermoelectric material is circle Sheet, diameter 10mm, with a thickness of 2mm.
CN201611053017.9A 2016-11-25 2016-11-25 Bi1-xSbxThermoelectric material and preparation method thereof Expired - Fee Related CN108103336B (en)

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CN114807890B (en) * 2022-05-06 2024-05-28 东南大学 Preparation method of two-dimensional bismuth antimonide with large thermoelectric potential

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1426120A (en) * 2001-12-13 2003-06-25 雅马哈株式会社 Thermoelectric material and its preparing method
CN101803050A (en) * 2006-12-01 2010-08-11 麻省理工学院 Methods for high figure-of-merit in nanostructured thermoelectric materials
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
CN102808212A (en) * 2012-08-31 2012-12-05 哈尔滨师范大学 Method for preparing n type pseudo ternary Er-doped thermoelectric material by using mechanical alloying hot pressing method

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1426120A (en) * 2001-12-13 2003-06-25 雅马哈株式会社 Thermoelectric material and its preparing method
CN101803050A (en) * 2006-12-01 2010-08-11 麻省理工学院 Methods for high figure-of-merit in nanostructured thermoelectric materials
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
CN102808212A (en) * 2012-08-31 2012-12-05 哈尔滨师范大学 Method for preparing n type pseudo ternary Er-doped thermoelectric material by using mechanical alloying hot pressing method

Non-Patent Citations (1)

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Title
Fabrication and thermoelectric properties of c-axis-aligned Bi0.5Sb1.5Te3 with a high magnetic field;Dong Hwan Kim等;《Acta Materialia》;20110518;第4958页右栏第2章、第4963页第4章

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