CN102339946B - High-performance thermoelectric composite material and preparation method thereof - Google Patents
High-performance thermoelectric composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 48
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 28
- 238000005245 sintering Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 38
- 230000005619 thermoelectricity Effects 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 150000004706 metal oxides Chemical group 0.000 claims description 21
- 239000011858 nanopowder Substances 0.000 claims description 19
- 239000012071 phase Substances 0.000 claims description 17
- 238000004857 zone melting Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 230000004224 protection Effects 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229920000193 polymethacrylate Polymers 0.000 claims 1
- 229910017629 Sb2Te3 Inorganic materials 0.000 abstract 2
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000010298 pulverizing process Methods 0.000 description 14
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- 238000002490 spark plasma sintering Methods 0.000 description 10
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- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
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- 229910018989 CoSb Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
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- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention relates to a high-performance thermoelectric composite material and a preparation method thereof, belonging to the field of thermoelectric materials. The composite material consists of two phases. A first phase is n-type Bi2Te3-Bi2Se3 or p-type Bi2Te3-Sb2Te3, and a second phase is nanometer powder of a metallic oxide. The nanometer powder of the metallic oxide accounts for 0.05-10% in terms of the total weight of the thermoelectric composite material. According to the preparation method provided by the invention, the n-type Bi2Te3-Bi2Se3 or p-type Bi2Te3-Sb2Te3 powder is ultrasonically mixed with the nanometer oxide, and discharge plasma sintering is carried out on the mixture to obtain a dense block material. Compared with the bismuth-telluride-based thermoelectric base material, under the condition that the electric conductivity of the thermoelectric base material is maintained to be unchanged basically in the invention, the high-performance thermoelectric composite material, provided by the invention, achieves the advantages of obviously reduced lattice heat conductivity and increased Seeback coefficient, and therefore the thermoelectric performance of the material can be greatly improved.
Description
Technical field
The present invention relates to a kind of high-performance thermoelectric composite material and preparation method thereof, belong to thermoelectric material field.
Background technology
Thermoelectric generation technology is a kind of technology of utilizing Seebeck (Seebeck) effect of material heat energy to be directly changed into electric energy or to utilize Pa Er note (Peltier) effect of material to freeze, there is movement-less part, the feature such as reliability is high, the life-span is long, environmental friendliness, can be widely used in the fields such as waste-heat power generation, Aero-Space, military equipment, household electrical appliances.Conversion efficiency of thermoelectric depends primarily on the dimensionless thermoelectricity capability factor Z T (ZT=S of material
2σ T/ κ, wherein S is Seebeck coefficient, and σ is conductivity, and κ is thermal conductivity, T is absolute temperature).The ZT value of material is higher, and conversion efficiency of thermoelectric is higher.So far, Bi
2te
3base alloy is still the material near room temperature with best thermoelectricity conversion performance, and its ZT value can reach 1 left and right, has broad application prospects in various refrigeration temperature occasion low, that cooling load is less.Along with constantly widening and the raising of level of modern technology application, all kinds of thermoelectric devices that reach its maturity be subject to extensive concern.
The maximum restraining factors that affect thermo-electric converting material are that its conversion efficiency of thermoelectric is low, improve the conversion efficiency of thermoelectric of material, first will improve the thermoelectricity capability of material.With regard to the traditional preparation technology of thermoelectric material, general all to eliminate dephasign, to regulate carrier concentration to reach the object of optimizing material electrical transmission performance.And for reducing material hot property, to improve the report of conducting material thermoelectricity performance relatively less.Phonon as heat transmission has wider frequency distribution scope, in traditional thermoelectric material, introducing crystal boundary or point defect can only the relatively high phonon of scattering frequency, the phonon lower to frequency can not play effective scattering process, and the nano level particle low frequency phonon that these wavelength of energy scattering are grown just.Mean free path while it is generally acknowledged electronics (hole) transmission is less than phonon.In the time that various charge carriers transport with the form of ripple, meeting is less than by yardstick or the particle suitable with wavelength own carries out strong scattering.For further reduce material lattice thermal conductivity, improve the ZT value of various thermoelectric materials, particle diameter is often introduced in matrix between the nanometer second phase particles of electronics (hole) mean free path and mean free path of phonons.Expect, by the selectivity scattering of nano particle, is not affecting under the prerequisite of electrical transmission performance as far as possible, reduces the lattice thermal conductivity of material.Generally introduce by the following method nanometer second-phase: (1) mechanical mixture is introduced nanometer powder (Zeming He, Dieter Platzek, Gabriele Karpinski, Eckhard M ü ller, Shanghua Li, Muhammet Toprak and Mamoun Muhammed, Nanotechnology 18,235602,2007; Chen Lidong, Shi Xun, Bai Shengqiang, antimony cobalt-based thermoelectric composite material and preparation method, CN Patent 200410025544.X, 2004; Lidong Zhao et al.Thermoelectric and mechanicalproperties of nano-SiC-dispersed Bi
2te
3fabricated by mechanical and SPS, Journal of alloys andcompounds.455,259,2008).The method technique is fairly simple.Nanometer powder is owing to having very high surface activity, very easily reunites, and this reunion is difficult to break completely by ball milling, realizes dispersed in matrix of nano particle.General ball grinding method is easy to introduce impurity in addition, as the Fe in stainless steel can adulterate to cobalt, N-shaped material property is sharply worsened.Al
2o
3, can mix with bulky grain form because thering is larger fragility Deng oxide, affect the electrical property of material.High-energy ball milling is because having great mechanical energy, and the extremely difficult oxidation of controlling powder, can make the conductivity of material occur declining to a great extent equally.(2) original position is separated out a certain constituent element, as Sb, Pb (Y Imanishi, M Miyoshi, K Shinohara, M Kobayashi, Thermoelectricconversion material and a process for producing the same, US Pat.5,965,841; P H Joseph, M.T.Christopher, et al. (2005). " Thermopower enhancement in PbTe with Pb precipitates. " Journal ofApplied Physics 98 (6): 063703).The method can ensure that second-phase is dispersed in matrix.But it is single that nanophase constituent element is selected, as at CoSb
3the excessive of middle Co can generate conductive phase CoSb
2.The fusing point lower (～323 DEG C) of Pb, can increase the unsteadiness of materials'use.The size of second-phase, form are difficult to control in technique in addition, and repeatability is lower.(3) oxidation thermoelectricity matrix or wherein a certain constituent atoms (H Kusakabe, H Gyoten, M Takigawa, Co-Sb based thermoelectricmaterial and a method of producing the same, US Patent 5,929,351; Chen Lidong, Zhao Xueying, Bai Shengqiang, Shi Xun, a kind of filled skutterudite-base thermoelectrical composite material and preparation method thereof, CN Patent 200610027340.9,2006.6.7).By regulating the technological parameters such as temperature, partial pressure of oxygen accurately to control the oxidation of thermoelectricity matrix, in practical operation, there is larger difficulty.Optionally scattering phonon schematic diagram is as shown in Figure 1 for nano particle.
Summary of the invention
The object of the invention is to adopt crystal for business bismuth telluride-based thermoelectric device is thermoelectric element more, exist the low and lower problem of temperature end thermoelectricity capability of mechanical strength, thermoelectric composite material that a kind of mechanical strength is higher and thermoelectricity capability is higher and preparation method thereof is provided.
The present invention adopts the method for ultrasonic mixing to introduce nano combined, and in conjunction with method (the SparkPlasma Sintering of plasma discharging pressure sintering, be called for short SPS), the thermoelectricity that obtains excellent performance is changed composite material, the new method that has formed research and produced.This composite material is made up of a kind of thermoelectricity matrix and nanometer second-phase, and nanometer second-phase is evenly dispersed in thermoelectricity matrix.
Technical scheme of the present invention is: a kind of high-performance thermoelectric composite material, it is characterized in that, and described composite material is by two phase compositions, the Bi that first-phase is N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3, second-phase is metal oxide nano powder end; In the total weight of described thermoelectric composite material, described metal oxide nano powder end accounts for 0.05%～10%.
Preferably, in the total weight of described thermoelectric composite material, described metal oxide nano powder end accounts for 0.05～1%.
Preferably, described Bi
2te
3-Bi
2se
3in, Bi
2te
3with Bi
2se
3mol ratio be 9: 1; Described Bi
2te
3-Sb
2te
3in, Bi
2te
3with Sb
2te
3mol ratio be 1: 3.
Preferably, described metal oxide is TiO
2, ZnO, ZrO
2, VO
2, NiO, Al
2o
3, CeO
2, Yb
2o
3, Eu
2o
3or one or more in MgO.
Nanometer second-phase is metal oxide nano powder end, in thermoelectricity matrix, has chemical inertness, and its crystallite dimension is 20～100nm, is evenly dispersed in crystal boundary or the crystal grain inside of thermoelectricity basis material, and effectively scattering low frequency phonon reduces lattice thermal conductivity.This kind of nano particle can also effectively filter the low energy electrons of electricity being led to the less contribution of do, and a crystal boundary potential barrier is provided, and improves the Seebeck coefficient of material.Because nanometer second-phase content is less, and size is greater than the mean free path of carrier transport, so less on the impact of conductivity.Contrast is introduced before nanometer second-phase, and the thermoelectric figure of merit of material is greatly improved, and increase rate has reached more than 20%.
The present invention also provides a kind of preparation method of above-mentioned high-performance thermoelectric composite material, adopts the Bi of N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3powder, metal oxide nano powder end are raw material, make nano-oxide be dispersed in matrix obtain nano composite powder, then obtain thermoelectric composite material by the method for plasma discharging pressure sintering by the method for ultrasonic dispersion in liquid phase environment.Specifically comprise the following steps:
1) by the Bi of described N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3material disintegrating sieves and obtains thermoelectricity matrix powder, by described proportioning, described thermoelectricity matrix powder is carried out ultrasonic mixing under the existence of liquid phase dispersion medium and dispersant with metal oxide nano powder end;
2) material after ultrasonic dispersion is heat-treated under vacuum condition, obtain the homodisperse composite powder of nano-metal-oxide, heat treatment temperature is 80～280 DEG C, is preferably 100～200 DEG C; Time is 1～24h, is preferably 2～10h;
3) by step 2) composite powder that obtains carries out discharge plasma sintering under vacuum condition, obtains fine and close block materials; Sintering temperature is 360～460 DEG C, preferably 400～440 DEG C; Time is 5～10min; Pressure is 10～100MPa, preferably 50～70MPa.
The Bi of described N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3material is the crystal bar preparing by zone-melting process, and described zone-melting process is the conventional method in this area, and crystal growth condition is: melt temperature is 500～800 DEG C, preferably 650～800 DEG C; Temperature gradient is 10～30 DEG C/mm, is preferably 20～28 DEG C/mm; The speed of growth is 2.5～5mm/h, is preferably 2.5～4mm/h.
Preferably, described step 1) in, crushing process carries out under inert atmosphere protection, and selection standard nylon mesh is sieved, and the particle diameter that obtains thermoelectricity matrix powder is 1～100 μ m; The standard nylon sieve of selecting is 500 order nylon mesh.
Preferably, described step 2) in, ultrasonic jitter time is 0.5～24h, is preferably 0.5～2h; Liquid phase dispersion medium is acetone or alcohol, and dispersant is polyethylene glycol, and the molecular weight of polyethylene glycol is 2000～10000.
Preferably, the particle diameter at described metal oxide nano powder end is 20～100nm, is preferably 20～50nm.
The present invention adopts said method by the Bi of nano-oxide powder and N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3powder carries out compound, can guarantee not produce in matrix impurity in preparation process.The prepared thermoelectric composite material of the present invention has the Seeback coefficient increasing substantially, lower total heat conductance, and then has the ZT value significantly improving within the scope of whole warm area, and increase rate can reach 20%.
Compared with bismuth telluride-based thermoelectric basis material, the present invention in the case of maintain the conductivity of matrix thermoelectric material substantially constant, can significantly reduce the lattice thermal conductivity of material, improve the Seeback coefficient of material, can improve greatly thus the thermoelectricity capability of material.In addition, also can increase material utilance, improve technique machinability, reduce production costs and improve the dependability of final products, thereby there is good industrialization prospect.
Brief description of the drawings
Fig. 1: nano particle is scattering phonon schematic diagram optionally.
Fig. 2: the process chart of thermoelectric composite material and preparation method thereof.
The Bi making in Fig. 3: embodiment 1 and 2
2se
0.3te
2.7/ 0.4wt%Al
2o
3the XRD spectra of composite powder.Al
2o
3after compound, do not make Bi
2se
0.3te
2.7matrix thing changes mutually.
Gained Bi in Fig. 4: embodiment 1 and 2
2se
0.3te
2.7/ 0.4wt%Al
2o
3the conductivity of thermoelectric composite material and the relation of temperature, the nanometer Al that mass fraction is 0.4%
2o
3conductivity impact on matrix is very micro-.
Gained Bi in Fig. 5: embodiment 1 and 2
2se
0.3te
2.7/ 0.4wt%Al
2o
3the Seebeck of thermoelectric composite material and the relation of temperature, the nanometer Al of disperse in matrix
2o
3a crystal boundary potential barrier is provided, has improved Seebeck coefficient.
Gained Bi in Fig. 6: embodiment 1 and 2
2se
0.3te
2.7/ 0.4wt%Al
2o
3the thermal conductivity of thermoelectric composite material and the relation of temperature, nanometer Al
2o
3particle is scattering low frequency phonon effectively, can significantly reduce lattice thermal conductivity.
Fig. 7: embodiment 1 and 2 gained Bi
2se
0.3te
2.7/ 0.4wt%Al
2o
3the ZT value of thermoelectric composite material and the relation of temperature, nanometer Al
2o
3introducing can significantly improve the ZT value of material.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment are only for limiting the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, for example, is the condition in workshop manual, or the condition of advising according to manufacturer.Ratio and percentage are based on molar ratio and mass fraction, unless specified otherwise.
The present invention, by introducing the method for nano-complex particle, obtains the thermo-electric converting material that mechanical strength and thermoelectricity capability are higher.Below taking second-phase as nanometer Al
2o
3for example describes in detail to various aspects of the present invention, described nanometer Al
2o
3average grain diameter between 20～50nm.Content disclosed according to the present invention and general principle, adopting disclosed other nano-metal-oxides in specification (is TiO
2, ZnO, ZrO
2, VO
2, NiO, Al
2o
3, CeO
2, Yb
2o
3, Eu
2o
3or one or more in MgO) substitute nanometer Al
2o
3, can reach equally technique effect of the present invention, this is apparent to those skilled in the art.
Embodiment 1: component is Bi
2se
0.3te
2.7n-shaped matrix powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 700 DEG C of melt temperatures, and temperature gradient is 25 DEG C/mm, and the speed of growth is 2.5mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100 μ m.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 440 DEG C, and programming rate is 100 DEG C/min, and temperature retention time is 10min, the plus-pressure 60MP of institute.The sintered body bending strength obtaining approaches 80Mpa, and the thermoelectricity capability figure of merit is up to 0.88 at 450K.
Embodiment 2: component is Bi
2se
0.3te
2.7n-shaped matrix powder+0.4wt.%Al
2o
3nanometer powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 700 DEG C of melt temperatures, and temperature gradient is 25 DEG C/mm, and the speed of growth is 2.5mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100um.
The matrix powder of above-mentioned gained is carried out to ultrasonic mixing with metal oxide nano powder end, ultrasonic mixing liquid medium used is ethanolic solution, do dispersant with polyethylene glycol, ultrasonic mixing 0.5h, obtains nano-oxide and in matrix, pulverizes thermoelectricity composite powder comparatively uniformly.Then gained composite powder is above heat-treated to 2h under vacuum condition, heat treatment temperature is 180 DEG C.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 440 DEG C, and programming rate is 100 DEG C/min, and temperature retention time is 10min, the plus-pressure 60MP of institute.In the sintered body obtaining, contain mass fraction and be 0.4% Al
2o
3, its bending strength reaches 80Mpa, and the thermoelectricity capability figure of merit has been up to 1.09 at 450K.
Embodiment 3: component is Bi
2se
0.3te
2.7n-shaped matrix powder+0.2wt.%Al
2o
3nanometer powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 650 DEG C of melt temperatures, and temperature gradient is 20 DEG C/mm, and the speed of growth is 3mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100um.
The matrix powder of above-mentioned gained is carried out to ultrasonic mixing with metal oxide nano powder end, ultrasonic mixing liquid medium used is ethanol, do dispersant with polyethylene glycol, ultrasonic mixing 2h, obtains nano-oxide and in matrix, pulverizes thermoelectricity composite powder comparatively uniformly.Then gained composite powder is above heat-treated to 5h under vacuum condition, heat treatment temperature is 200 DEG C.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 420 DEG C, and programming rate is 100 DEG C/min, temperature retention time 5min, the plus-pressure 70MP of institute.In the sintered body obtaining, contain mass fraction and be 0.2% Al
2o
3, after testing, its bending strength reaches 80Mpa, and the thermoelectricity capability figure of merit has been up to 1.0 at 450K.
Embodiment 4: component is Bi
2se
0.3te
2.7n-shaped matrix powder+0.8wt.%Al
2o
3nanometer powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 750 DEG C of melt temperatures, and temperature gradient is 28 DEG C/mm, and the speed of growth is 4mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100um.
The matrix powder of above-mentioned gained is carried out to ultrasonic mixing with metal oxide nano powder end, ultrasonic mixing liquid medium used is ethanol, do dispersant with polyethylene glycol, ultrasonic mixing 1h, obtains nano-oxide and in matrix, pulverizes thermoelectricity composite powder comparatively uniformly.Then gained composite powder is above heat-treated to 10h under vacuum condition, heat treatment temperature is 100 DEG C.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 400 DEG C, and programming rate is 100 DEG C/min, and temperature retention time is 8min, the plus-pressure 50MP of institute.In the sintered body obtaining, contain mass fraction and be 0.8% Al
2o
3, after testing, its bending strength reaches 75Mpa, and the thermoelectricity capability figure of merit has been up to 0.9 at 400K.
Embodiment 5: component is Bi
2se
0.3te
2.7n-shaped matrix powder+5wt.%Al
2o
3nanometer powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 700 DEG C of melt temperatures, and temperature gradient is 25 DEG C/mm, and the speed of growth is 2.5mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100um.
The matrix powder of above-mentioned gained is carried out to ultrasonic mixing with metal oxide nano powder end, ultrasonic mixing liquid medium used is ethanol, do dispersant with polyethylene glycol, ultrasonic mixing 0.5h, obtains nano-oxide and in matrix, pulverizes thermoelectricity composite powder comparatively uniformly.Then gained composite powder is above heat-treated to 2h under vacuum condition, heat treatment temperature is 180 DEG C.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 440 DEG C, and programming rate is 100 DEG C/min, and temperature retention time is 10min, the plus-pressure 60MP of institute.In the sintered body obtaining, contain mass fraction and be 5% Al
2o
3, after testing, its bending strength reaches 50Mpa, and the thermoelectricity capability figure of merit has been up to 0.85 at 400K.
Embodiment 6: component is Bi
2se
0.3te
2.7n-shaped matrix powder+0.5wt.%VO
2nanometer powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 700 DEG C of melt temperatures, and temperature gradient is 25 DEG C/mm, and the speed of growth is 2.5mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100um.
The matrix powder of above-mentioned gained is carried out to ultrasonic mixing with metal oxide nano powder end, ultrasonic mixing liquid medium used is ethanol, do dispersant with polyethylene glycol, ultrasonic mixing 0.5h, obtains nano-oxide and in matrix, pulverizes thermoelectricity composite powder comparatively uniformly.Then gained composite powder is above heat-treated to 2h under vacuum condition, heat treatment temperature is 180 DEG C.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 440 DEG C, and programming rate is 100 DEG C/min, and temperature retention time is 10min, the plus-pressure 60MP of institute.In the sintered body obtaining, contain mass fraction and be 0.5% VO
2, after testing, its bending strength reaches 80Mpa, and the thermoelectricity capability figure of merit has been up to 1.0 at 400K.
Embodiment 7: component is Bi
0.5sb
1.5te
3p-type matrix powder+0.5wt.%Al
2o
3nanometer powder
First obtain the directed polycrystalline rod of said components by the method for growing by zone melting, the condition of growing by zone melting is 800 DEG C of melt temperatures, and temperature gradient is 25 DEG C/mm, and the speed of growth is 2.5mm/h.Remove after the part of polycrystalline rod surface, pulverize and sieve, adopt steel vessel as pulverizing tool, crushing process utilizes the inert atmosphere protections such as argon gas.After pulverizing, utilize the nylon mesh of standard to sieve to powder, the initial powder distributing to obtain desired particle size, chooses the powder that particle diameter is 1～100um.
The matrix powder of above-mentioned gained is carried out to ultrasonic mixing with metal oxide nano powder end, ultrasonic mixing liquid medium used is ethanol, do dispersant with polyethylene glycol, ultrasonic mixing 0.5h, obtains nano-oxide and in matrix, pulverizes thermoelectricity composite powder comparatively uniformly.Then gained composite powder is above heat-treated to 2h under vacuum condition, heat treatment temperature is 180 DEG C.
Utilize graphite jig, under vacuum condition, carry out SPS sintering.Adopting sintering temperature is 420 DEG C, and programming rate is 100 DEG C/min, and temperature retention time is 10min, the plus-pressure 60MP of institute.In the sintered body obtaining, contain mass fraction and be 0.5% Al
2o
3, after testing, its bending strength reaches 80Mpa, and the thermoelectricity capability figure of merit has been up to 1.10 at 350K.
Adopt nano-metal-oxide TiO
2, ZnO, ZrO
2, NiO, CeO
2, Yb
2o
3, Eu
2o
3with the nanometer Al in MgO difference alternate embodiment 2
2o
3with the nanometer VO in embodiment 6
2, after testing, the mechanical strength of gained composite material and thermoelectricity capability and embodiment 2 and embodiment 6 are basic identical.
The prepared thermoelectric composite material of the above embodiment of the present invention has the Seeback coefficient increasing substantially, lower total heat conductance, and then has the ZT value significantly improving within the scope of whole warm area, and increase rate can reach 20%.
The mentioned all documents of the present invention are all quoted as a reference in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or amendment to the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (7)
1. a thermoelectric composite material, is characterized in that, described composite material is by two phase compositions, the Bi that first-phase is N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3, second-phase is metal oxide nano powder end; In the total weight of described thermoelectric composite material, described metal oxide nano powder end accounts for 0.05%～10%; Described metal oxide is TiO
2, ZnO, ZrO
2, VO
2, NiO, Al
2o
3, CeO
2, Yb
2o
3or Eu
2o
3in one or more; Described thermoelectric composite material adopts following steps to prepare:
1) by the Bi of described N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3material disintegrating sieves and obtains thermoelectricity matrix powder, by proportioning, described thermoelectricity matrix powder is carried out ultrasonic mixing under the existence of liquid phase dispersion medium and dispersant with metal oxide nano powder end;
2) ultrasonic mixed material is heat-treated under vacuum condition, obtain the homodisperse composite powder of nano-metal-oxide, heat treatment temperature is 80～280 DEG C, and the time is 1～24h;
3) by step 2) composite powder that obtains carries out discharge plasma sintering under vacuum condition, obtains fine and close block materials; Sintering temperature is 360～460 DEG C, and the time is 5～10min, and pressure is 10～100MPa.
2. thermoelectric composite material as claimed in claim 1, is characterized in that, described metal oxide nano powder end is evenly dispersed in the Bi of N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3crystal boundary or crystal grain inside.
3. the preparation method of the thermoelectric composite material as described in arbitrary claim in claim 1-2, comprises the following steps:
1) by the Bi of described N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3material disintegrating sieves and obtains thermoelectricity matrix powder, by proportioning, described thermoelectricity matrix powder is carried out ultrasonic mixing under the existence of liquid phase dispersion medium and dispersant with metal oxide nano powder end;
2) ultrasonic mixed material is heat-treated under vacuum condition, obtain the homodisperse composite powder of nano-metal-oxide, heat treatment temperature is 80～280 DEG C, and the time is 1～24h;
3) by step 2) composite powder that obtains carries out discharge plasma sintering under vacuum condition, obtains fine and close block materials; Sintering temperature is 360～460 DEG C, and the time is 5～10min, and pressure is 10～100MPa.
4. preparation method as claimed in claim 3, is characterized in that, the Bi of described N-shaped
2te
3-Bi
2se
3or the Bi of p-type
2te
3-Sb
2te
3material is the crystal bar preparing by zone-melting process, and crystal growth condition is: melt temperature is 500～800 DEG C, and temperature gradient is 10～30 DEG C/mm, and the speed of growth is 2.5～5mm/h.
5. preparation method as claimed in claim 3, is characterized in that, in described step 1), crushing process carries out under inert atmosphere protection, and the particle diameter of described thermoelectricity matrix powder is 1～100 μ m.
6. preparation method as claimed in claim 3, is characterized in that, described step 2) in, liquid phase dispersion medium is acetone or alcohol, dispersant is polyethylene glycol or ammonium polymethacrylate.
7. preparation method as claimed in claim 3, is characterized in that, the particle diameter at described metal oxide nano powder end is 20～100nm.
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| CN102807195B (en) * | 2012-07-27 | 2014-02-19 | 西南交通大学 | Method for preparing semi-arc Bi2Se3ultrathin nanosheets |
| CN106145062B (en) * | 2015-03-30 | 2018-05-01 | 武汉理工大学 | A kind of quick method for preparing antimony telluride thermoelectric material |
| CN105226180B (en) * | 2015-10-29 | 2018-02-23 | 南京工业大学 | TiS2Composite nano MoS2Method for preparing thermoelectric material |
| CN105702847B (en) * | 2016-01-29 | 2017-12-15 | 合肥工业大学 | A kind of method of raising BiTeSe base N-type semiconductor pyroelectric material performances |
| CN106533265A (en) * | 2017-01-12 | 2017-03-22 | 王赞 | Energy-saving device and method for thermoelectric power generation based on heat distribution pipeline |
| KR102395296B1 (en) * | 2017-09-26 | 2022-05-09 | 현대자동차주식회사 | Thermoelectric material and method for manufacturing the same |
| CN107814571B (en) * | 2017-11-01 | 2021-03-02 | 上海海关工业品与原材料检测技术中心 | SnTe nano composite material and preparation method and application thereof |
| CN110767796B (en) * | 2019-10-14 | 2021-06-01 | 东华大学 | Two-dimensional transition metal carbide/bismuth telluride or derivative thereof based thermoelectric composite material and preparation thereof |
| CN111341902B (en) * | 2020-04-02 | 2021-07-06 | 台州智奥通信设备有限公司 | Preparation method of high-strength high-performance composite thermoelectric material |
| CN113540332A (en) * | 2020-04-17 | 2021-10-22 | 中国科学院大连化学物理研究所 | P-type ZnO/Bi0.5Sb1.5Te3Composite material and preparation method and application thereof |
| CN111430532A (en) * | 2020-05-14 | 2020-07-17 | 上海应用技术大学 | Preparation method of antimony telluride block thermoelectric material |
| CN114639770B (en) * | 2022-02-21 | 2024-10-25 | 哈尔滨工业大学（深圳） | Room temperature-based thermoelectric material containing metal organic polymer and preparation method thereof |
| 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 |
| 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 |
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