CN110391327A - A kind of composite thermoelectric material and its preparation method and application - Google Patents
A kind of composite thermoelectric material and its preparation method and application Download PDFInfo
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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
- H10N10/01—Manufacture or treatment
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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
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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
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Abstract
This application discloses a kind of composite thermoelectric materials and its preparation method and application.The composite thermoelectric material of the application is coated at least one layer of inorganic semiconductor compound interface layer by the surface of thermoelectric material particle and is formed, wherein inorganic semiconductor compound interface layer is by ZnO, Al2O3、TiO2, at least one of ZnS, ZnSe and ZnTe formed.The composite thermoelectric material of the application, in the surface coated inorganic semiconducting compound boundary layer of conventional thermoelectric material, change interface performance by inorganic semiconductor compound interface layer, to the Seebeek coefficient for reducing thermal conductivity, increasing material, so that composite thermoelectric material has higher thermoelectric figure of merit, the transfer efficiency of thermal energy and electric energy is effectively raised.
Description
Technical field
This application involves thermoelectric material fields, more particularly to a kind of composite thermoelectric material and its preparation method and application.
Background technique
Thermoelectric material is primarily referred to as converting thermal energy into the material of electric energy, is one of very promising new energy materials, In
The fields such as refrigeration and thermo-electric generation have broad application prospects.And the maximum technical bottleneck for limiting pyroelectric technology development is it
Energy conversion efficiency is relatively low, is unable to reach the requirement of industrial application.
The index for characterizing the conversion efficiency of thermoelectric of thermoelectric material is the thermoelectric figure of merit (abbreviation ZT) of material, and thermoelectric figure of merit can be with
Pass through formula: ZT=σ2S T/ κ, is calculated, and wherein σ is Seebeck coefficient (i.e. seebeck coefficient), T is absolute temperature, ρ
It is thermal conductivity for conductivity, κ.ZT value is higher, shows that the transfer efficiency between the thermal energy of material and electric energy is higher.
But the type of thermoelectric material is fewer at present, the thermoelectric material of especially high thermoelectric figure of merit is extremely limited；Cause
This, the thermoelectric material for researching and developing a kind of new high thermoelectric figure of merit is the art critical issue urgently to be resolved.
Summary of the invention
The purpose of the application is to provide a kind of new composite thermoelectric material and its preparation method and application.
The application uses following technical scheme:
The one side of the application discloses a kind of composite thermoelectric material, the composite thermoelectric material by thermoelectric material particle table
Bread covers at least one layer of inorganic semiconductor compound interface layer and is formed, and inorganic semiconductor compound interface layer is by ZnO, Al2O3、
TiO2, at least one of ZnS, ZnSe and ZnTe formed.
Wherein, inorganic semiconductor compound interface layer can be multilayer or single layer；Wherein, single layer can be a kind of material shape
At single layer, be also possible to the single layer that multiple material is mixed to form；Multilayer can be a kind of material and carry out what multiple cladding was formed
Multilayered structure is also possible to multiple material and successively coats form multilayered structure, for example, one layer be ZnO, one layer be TiO2, one layer be
ZnS is successively coated in this way；It is not specifically limited herein.
It should be noted that the composite thermoelectric material of the application, thermoelectric material particle refers to conventional thermoelectric material, this Shen
Key please is in conventional thermoelectric material surface cladding at least one layer by ZnO, Al2O3、TiO2, in ZnS, ZnSe and ZnTe
At least one formation inorganic semiconductor compound interface layer；The inorganic semiconductor compound interface layer, on the one hand, can dissipate
Penetrating phonon reduces thermal conductivity κ, on the other hand, can increase the carrier mobility and load of material by quantum scale heterojunction structure
Sub- effective mass is flowed, to increase the Seebeek factor sigma of material；Therefore, the composite thermoelectric material of the application and general routine
Thermoelectric material is compared, and with higher thermoelectric figure of merit, the transfer efficiency of thermal energy and electric energy is higher.
Preferably, in the composite thermoelectric material of the application, inorganic semiconductor compound interface layer with a thickness of 0.1nm-
10nm。
Preferably, in the composite thermoelectric material of the application, thermoelectric material particle is Bi2Te3, N-shaped Bi2Te2.7Se0.3, p-type
Bi2Te2.7Se0.3, at least one of PbTe and SnSe.
Preferably, in the composite thermoelectric material of the application, inorganic semiconductor compound interface layer is by being based on atomic layer deposition
The growth in situ method of principle is formed.
It is furthermore preferred that inorganic semiconductor compound interface layer is by liquid phase coating, atom in the composite thermoelectric material of the application
At least one of layer deposition and vapor deposition are prepared.
The another side of the application discloses a kind of block thermoelectric material, the block thermoelectric material by the application compound thermoelectricity
Material is sintered.
Preferably, in the block thermoelectric material of the application, it is sintered using plasma hot pressed sintering.It is furthermore preferred that wait from
The condition of daughter hot pressed sintering is that vacuum degree is not less than 8 × 10-3Pa, pressure 30-60MPa, heating rate be 5-200 DEG C/
Min, sintering temperature are 100-400 DEG C, soaking time 2-100min.
The composite thermoelectric material for disclosing the application on one side again of the application or the block thermoelectric material of the application are freezing
Application in equipment or thermo-electric generation equipment.
It should be noted that the composite thermoelectric material or block thermoelectric material of the application be compared with conventional thermoelectric material,
It is therefore, general to need that answering for the application is used using thermoelectric material equipment or field with higher thermoelectric figure of merit
Thermoelectric material or block thermoelectric material are closed, and better conversion efficiency of thermoelectric can be obtained.
The preparation method of the composite thermoelectric material for disclosing the application on one side again of the application, including by thermoelectric material alloy
Ball milling is at nanometer powder under anaerobic for block, then using at least one in liquid phase coating, atomic layer deposition and vapor deposition
Kind, on the nanometer powder surface of thermoelectric material, cladding at least one layer is by ZnO, Al2O3、TiO2, in ZnS, ZnSe and ZnTe at least
A kind of inorganic semiconductor compound interface layer of formation obtains the composite thermoelectric material of the application.
Preferably, ball milling is high-energy ball milling, three-dimensional vibration at least one of ball milling and common planetary ball milling.More preferably
, ball milling carries out in glove box, and water content is less than 0.1ppm in glove box, and oxygen content is less than 0.1ppm.
It should be noted that carrying out ball milling in glove box or under oxygen free condition, its purpose is to avoid that oxygen occurs
Change, avoids causing thermoelectricity capability to decline because of oxidation.
The preparation method of the block thermoelectric material for disclosing the application on one side again of the application, including in the compound of the application
On the basis of thermoelectric material preparation method, further, prepared composite thermoelectric material is sintered to form block thermoelectricity
Material.
Preferably, it is sintered to plasma hot pressing sintering.It is furthermore preferred that the condition of plasma hot pressing sintering is vacuum degree
For not less than 8 × 10-3Pa, pressure 30-60MPa, heating rate are 5-200 DEG C/min, sintering temperature is 100-400 DEG C, are protected
The warm time is 2-100min.
The beneficial effects of the present application are as follows:
The composite thermoelectric material of the application, in the surface coated inorganic semiconducting compound boundary layer of conventional thermoelectric material,
Change interface performance by inorganic semiconductor compound interface layer, thus the Seebeek coefficient for reducing thermal conductivity, increasing material,
So that composite thermoelectric material has higher thermoelectric figure of merit, the transfer efficiency of thermal energy and electric energy is effectively raised.
Detailed description of the invention
Fig. 1 is the N-shaped Bi of depositing ultrathin ZnO layer in surface in the embodiment of the present application one2Te2.7Se0.3Composite thermoelectric material
Transmission electron microscope picture；
Fig. 2 is the conductivity test result figure of composite thermoelectric material in the embodiment of the present application, and in figure, ordinate is conductance
Rate, abscissa are the test temperatures of material；
Fig. 3 is the Seebeck coefficient test result figure of composite thermoelectric material in the embodiment of the present application, and in figure, ordinate is plug
Seebeck coefficient, abscissa are the test temperatures of material；
Fig. 4 is the ZT value test result figure of composite thermoelectric material in the embodiment of the present application, and in figure, ordinate is the ZT of material
Value, abscissa is the test temperature of material；
Fig. 5 is TiO in the embodiment of the present application three2Layer cladding N-shaped Bi2Te2.7Se0.3Composite thermoelectric material transmitted electron
Microscope photograph；
Fig. 6 is the conductivity test result figure of composite thermoelectric material in the embodiment of the present application three, and in figure, ordinate is conductance
Rate, abscissa are the test temperatures of material；
Fig. 7 is the Seebeck coefficient test result figure of composite thermoelectric material in the embodiment of the present application three, and in figure, ordinate is
Seebeck coefficient, abscissa are the test temperatures of material；
Fig. 8 is the ZT value test result figure of composite thermoelectric material in the embodiment of the present application three, and in figure, ordinate is material
ZT value, abscissa are the test temperatures of material.
Specific embodiment
The application to thermoelectric material carry out largely study during find, the thermoelectricity transmission characteristic of thermoelectric material with
The interfacial characteristics of material are closely related, and the accurate interfacial structure for controlling material and component are that one for regulating and controlling pyroelectric material performance has
Effect approach.Interface, which can scatter phonon, leads to the reduction of thermal conductivity κ, while introducing interface potential barrier and can use the energy mistake at interface
Filter effect effectively improves the power factor of material.Therefore, the modified method in surface can be effectively improved the pyroelecthc properties of material.
For the studies have shown that of the application for traditional block thermoelectric material, the interface in material is mainly crystal boundary, crystal boundary
The different high preferred orientations of identical phase or different phases are separated.Optimized by reasonable interfacial structure, balances the electrical property at interface
Just become the key that can obtain best thermoelectricity capability with hot property.Quantum size effect can lead to the electronic state near interface
The change dramatically of density causes the absolute value of Seebeck coefficient to increase, meanwhile, for heterogeneous interface, interface potential barrier passes through filtering
Low energy carrier and optimize power factor.This interface interaction mechanism is in superlattice film and the compound thermoelectricity material of block
It is verified extensively in material.Also, the increase at thermoelectric material interface will lead to the scattering process enhancing of phonon, to reduce thermal conductivity
Rate κ, and then effectively improve the thermoelectricity capability of material.Therefore, it by adjustment interface size, is expected to significantly reduce thermal conductivity without shadow
Electron-transport is rung, this is also the main thought that superlattice film or quanta point material can effectively improve ZT value, to current heat
The research of electric material has great importance.It can be seen that for the interfacial structure design of thermoelectric material and the research of optimization, it is main
To include interface band structure matching, electronic structure and doping and interface scale effect be the research direction that possible make a breakthrough it
One.
From theory analysis it is found that interface regulation improves the heat of material by Synchronous fluorimetry Seebeck coefficient and thermal conductivity
Electrical property.The carrier mobility and carrier effective mass for increasing material by quantum scale heterojunction structure, to increase
The Seebeek coefficient of material；The impurity from the lattice disorder of atomic scale to nanoscale is again to the crystal boundary of meso-scale simultaneously
In one, the phon scattering close to complete wavelength range is had effectively achieved, reduces the thermal conductivity of material.
Based on the above research and understanding, the proposition of the application creativeness coats at least one layer of on the surface of thermoelectric material particle
Inorganic semiconductor compound interface layer thus forms a kind of new composite thermoelectric material, and is sintered by the composite thermoelectric material
A kind of new block thermoelectric material has been made.Test result shows, the composite thermoelectric material or block thermoelectric material of the application,
ZT value is up to 0.90, more general Bi2Te2.7Se0.3The 0.7 of thermoelectric material is higher by 20%, effectively raises compound thermoelectricity material
The conversion efficiency of thermoelectric of material.
The application is described in further detail below by specific embodiments and the drawings.Following embodiment is only to the application
It is further described, should not be construed as the limitation to the application.
Embodiment one
This example utilizes the method for atomic layer deposition in the N-shaped Bi of synthesis in solid state2Te2.7Se0.3The surface of thermoelectric material deposits
Ultra-thin ZnO layer, to obtain the composite thermoelectric material of this example.In detail the preparation method is as follows:
Basis material N-shaped Bi2Te2.7Se0.3Preparation: using Bi, Te, Se simple substance as raw material, according to chemical molecular formula
Bi2Te2.7Se0.3Weighing proportion is carried out in glove box；Wherein, glove box water content < 0.1ppm, oxygen content < 0.1ppm；It will
Load weighted raw material is packed into quartz ampoule, using oxyhydrogen flame tube sealing system 1 × 10-3Tube sealing under the high vacuum condition of Pa, is put into horse
10h is not reacted under the conditions of 800 DEG C of furnace, quenching obtains n-Bi2Te2.7Se0.3Alloy block, by alloy block and abrading-ball one in glove box
It rises and is put into ball grinder, using planetary ball mill ball milling, ratio of grinding media to material 10:1,350 revs/min of drum's speed of rotation, Ball-milling Time 1
Hour, that is, obtain the nanometer powder of thermoelectric material alloy block.
Composite thermoelectric material preparation: by N-shaped Bi2Te2.7Se0.3Powder 10g is transferred to the sample room for being equipped with rotary system
In, atomic layer deposition system vacuum degree is less than 1 × 10-3When Pa, high pure nitrogen is passed through as carrier gas and protective gas.It is passed through nitrogen
The vacuum degree of system is 3 × 10 afterwards-1Pa opens heating system, and the temperature to sample cavity is 150 DEG C.With diethyl zinc, water vapour
Respectively source metal and oxygen source, depositing temperature are 150 DEG C.The opening time of trimethyl aluminium valve is controlled, water vapour is controlled, is completed
One deposition cycle, the deposition thickness of every circulation areLeft and right, control loop number accurately adjust interfacial layer thickness
Control；Deposition completes the n-Bi for obtaining ZnO cladding2Te2.7Se0.3Composite thermoelectric material.Circulating ring number in this example is 20 circles,
Prepared composite thermoelectric material powder is observed using transmission electron microscope, as a result as shown in Figure 1, the result of Fig. 1
It has been shown that, ZnO interfacial layer thickness is about 2nm.
The preparation of block thermoelectric material: composite thermoelectric material powder obtained is packed into the graphite jig of diameter 10mm true
Hot pressed sintering is carried out under Altitude, actual conditions include that vacuum degree is 1 × 10-3Pa, pressure 50MPa, 350 DEG C of sintering temperature are protected
Warm time 60min, that is, prepare the block thermoelectric material of this example.The size of thermoelectric block body is the cylinder of diameter 10mm high 7mm.
Long 5.5mm wide 6mm thickness 2mm is cut into along column direction to the thermoelectric block body for the diameter 10mm high 7mm that this example obtains
Piece, its thermal diffusion coefficient D is tested in 300-500K temperature range using laser conductometer LFA-457 after surface polishing.It is logical
The density p and specific heat capacity Cp for crossing block materials calculate thermal conductivity κ=D × ρ × Cp.
The thermoelectric block body obtained to this example is cut into the cuboid of long 3mm wide 3mm high 9.5mm, fortune perpendicular to column direction
With ZEM-3 Thermal Synthetic electrical measurement test system under helium protective condition, its conductivityσ, plug are tested in 300-500K temperature range
Seebeck coefficient S.Pass through formula: ZT=σ2The ZT value of material is calculated in S T/ κ.
The Conductivity Results of block thermoelectric material made from this example are as shown in Fig. 2, Fig. 2 is the conductivity of block thermoelectric material
The curve graph changed with test temperature；Wherein, BTS/ZnO curve is the conductance profile of block thermoelectric material made from this example,
BTS curve is basis material N-shaped Bi2Te2.7Se0.3Conductance profile.The Seebeck coefficient knot of the block thermoelectric material of this example
Fruit is as shown in figure 3, Fig. 3 is the curve graph that Seebeck coefficient changes with test temperature, wherein BTS/ZnO curve is made for this example
Block thermoelectric material Seebeck coefficient curve, BTS curve be basis material N-shaped Bi2Te2.7Se0.3Seebeck coefficient it is bent
Line.According to ZT value calculation formula, calculating its maximum ZT value of block thermoelectric material made from this example is 0.64, than pure
Bi2Te2.7Se0.30.58 be higher by 10%, as shown in figure 4, Fig. 4 is change curve of the ZT value with test temperature.In Fig. 4,
BTS/ZnO curve is the ZT value curve of block thermoelectric material made from this example, and BTS curve is basis material N-shaped Bi2Te2.7Se0.3
ZT value curve.
Embodiment two
This example is using the method for liquid phase coating in n-Bi2Te2.7Se0.3Depositing ultrathin ZnS layers of the surface of thermoelectric material, to obtain
Obtain the composite thermoelectric material of this example.In detail the preparation method is as follows:
Basis material N-shaped Bi2Te2.7Se0.3Preparation and ZnO cladding n-Bi2Te2.7Se0.3It is the same as example 1.
Composite thermoelectric material preparation: the n-Bi that ZnO is coated2Te2.7Se0.3Composite thermoelectric material 10g, be added 2mmol
Sulphur powder, ground and mixed is uniform, mixed raw material is packed into quartz ampoule, using oxyhydrogen flame tube sealing system 1 × 10-3The high vacuum of Pa
Under the conditions of tube sealing, react 2h under the conditions of being put into 400 DEG C of Muffle furnace, be made surface ZnS layer modify Bi2Te2.7Se0.3Thermoelectricity material
Material.Prepared composite thermoelectric material powder is observed using transmission electron microscope, the results show that its ZnS boundary layer
Thickness is about 2nm.
The preparation of block thermoelectric material and thermoelectricity capability test method are identical with embodiment one.
The Conductivity Results of block thermoelectric material made from this example are as shown in Fig. 2, Fig. 2 is the conductivity of block thermoelectric material
The curve graph changed with test temperature；Wherein, BTS/ZnS curve is the conductance profile of block thermoelectric material made from this example,
BTS curve is basis material N-shaped Bi2Te2.7Se0.3Conductance profile.The Seebeck coefficient knot of the block thermoelectric material of this example
Fruit is as shown in figure 3, Fig. 3 is the curve graph that Seebeck coefficient changes with test temperature, wherein BTS/ZnS curve is made for this example
Block thermoelectric material Seebeck coefficient curve, BTS curve be basis material N-shaped Bi2Te2.7Se0.3Seebeck coefficient it is bent
Line.According to ZT value calculation formula, calculating its maximum ZT value of block thermoelectric material made from this example is 0.65, than pure
Bi2Te2.7Se0.30.58 be higher by 12%, as shown in figure 4, Fig. 4 is change curve of the ZT value with test temperature.In Fig. 4,
BTS/ZnS curve is the ZT value curve of block thermoelectric material made from this example, and BTS curve is basis material N-shaped Bi2Te2.7Se0.3
ZT value curve.
Embodiment three
The N-shaped Bi that this example is prepared using the method for atomic layer deposition in liquid phase2Te2.7Se0.3The surface of thermoelectric material deposits
Ultra-thin TiO2Layer, to obtain the composite thermoelectric material of this example.In detail the preparation method is as follows:
Basis material N-shaped Bi2Te2.7Se0.3Preparation use liquid phase preparation process: by sodium hydroxide 4.8g, tellurium dioxide
200mL there-necked flask is added with 120mL ethylene glycol solution in 3.48g, selenium dioxide 0.25g, stirs to clarify under nitrogen protection.Separately
10mL ethylene glycol is added in 7.76g bismuth nitrate, is stirred to clarify.There-necked flask is heated to 160 DEG C, in injection under nitrogen protection
Bismuth nitrate ethylene glycol solution is stated, 2mL hydrazine hydrate is then injected into, grows 3h, generates N-shaped Bi2Te2.7Se0.3Nanometer sheet.Reaction is tied
The colloid obtained after beam carries out centrifuge washing, and 60 DEG C of vacuum dryings obtain Bi2Te2.7Se0.3Nanometer sheet.By gained Bi2Te2.7Se0.3
Nanometer sheet is in tube furnace, in 95%Ar/H2Lower 350 DEG C of annealing 1h is protected to obtain the N-shaped Bi of liquid phase preparation2Te2.7Se0.3Matrix
Material.
Composite thermoelectric material preparation: by n-Bi2Te2.7Se0.3Powder 10g is transferred to the sample room for being equipped with rotary system
In, atomic layer deposition system vacuum degree is less than 1 × 10-3When Pa, high pure nitrogen is passed through as carrier gas and protective gas.It is passed through nitrogen
The vacuum degree of system is 3 × 10 afterwards-1Pa opens heating system, and the temperature to sample cavity is 150 DEG C.With tetrabutyl titanate, water steams
Vapour is respectively source metal and oxygen source, and depositing temperature is 150 DEG C.The opening time of trimethyl aluminium valve is controlled, water vapour is controlled, it is complete
At a deposition cycle, accuracy controlling is carried out to interfacial layer thickness by control loop number；Deposition is completed to obtain TiO2Packet
The n-Bi covered2Te2.7Se0.3Composite thermoelectric material.Circulating ring number in this example is 10 circles, using transmission electron microscope to institute
The composite thermoelectric material powder of preparation is observed, as a result as shown in figure 5, Fig. 5's the results show that its TiO2Interfacial layer thickness is about
For 1nm.
The preparation of block thermoelectric material and thermoelectricity capability test method are identical with embodiment one.
The Conductivity Results of block thermoelectric material made from this example are as shown in fig. 6, Fig. 6 is the conductivity of block thermoelectric material
The curve graph changed with test temperature；Wherein, BTS/TiO2Curve is the conductance profile of block thermoelectric material made from this example,
BTS curve is basis material N-shaped Bi2Te2.7Se0.3Conductance profile.The Seebeck coefficient knot of the block thermoelectric material of this example
Fruit is as shown in fig. 7, Fig. 7 is the curve graph that Seebeck coefficient changes with test temperature, wherein BTS/TiO2Curve is made for this example
Block thermoelectric material Seebeck coefficient curve, BTS curve be basis material N-shaped Bi2Te2.7Se0.3Seebeck coefficient it is bent
Line.According to ZT value calculation formula, calculating its maximum ZT value of block thermoelectric material made from this example is 0.91, purer than this example
Bi2Te2.7Se0.30.7 be higher by 30%, as shown in figure 8, Fig. 8 is change curve of the ZT value with test temperature.In Fig. 8, BTS/
TiO2Curve is the ZT value curve of block thermoelectric material made from this example, and BTS curve is basis material N-shaped Bi2Te2.7Se0.3ZT
It is worth curve.It should be noted that this example uses the N-shaped Bi of liquid phase preparation2Te2.7Se0.3Thermoelectric material, maximum ZT value is compared with solid phase
The N-shaped Bi of synthesis2Te2.7Se0.3Thermoelectric material ZT value is bigger, can achieve 0.7.
The foregoing is a further detailed description of the present application in conjunction with specific implementation manners, and it cannot be said that this Shen
Specific implementation please is only limited to these instructions.For those of ordinary skill in the art to which this application belongs, it is not taking off
Under the premise of from the application design, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the protection of the application
Range.
Claims (10)
1. a kind of composite thermoelectric material, it is characterised in that: the composite thermoelectric material by the surface of thermoelectric material particle coat to
Lack one layer of inorganic semiconductor compound interface layer and formed, the inorganic semiconductor compound interface layer is by ZnO, Al2O3、TiO2、
At least one of ZnS, ZnSe and ZnTe formation.
2. composite thermoelectric material according to claim 1, it is characterised in that: the inorganic semiconductor compound interface layer
With a thickness of 0.1nm-10nm.
3. composite thermoelectric material according to claim 1, it is characterised in that: the thermoelectric material particle is Bi2Te3, N-shaped
Bi2Te2.7Se0.3, p-type Bi2Te2.7Se0.3, at least one of PbTe and SnSe.
4. composite thermoelectric material according to claim 1-3, it is characterised in that: the inorganic semiconductor compound
Boundary layer is formed by the growth in situ method based on atomic layer deposition principle；Preferably, the inorganic semiconductor compound interface
Layer is prepared by least one of liquid phase coating, atomic layer deposition and vapor deposition.
5. a kind of block thermoelectric material, it is characterised in that: the block thermoelectric material is described in any item multiple by claim 1-4
Thermoelectric material is closed to be sintered.
6. block thermoelectric material according to claim 5, it is characterised in that: described to be sintered to plasma hot pressing sintering；
Preferably, it is not less than 8 × 10 that the condition of the plasma hot pressing sintering, which is vacuum degree,-3Pa, pressure 30-60MPa, heating
Speed is 5-200 DEG C/min, sintering temperature is 100-400 DEG C, soaking time 2-100min.
7. composite thermoelectric material according to claim 1-4 or the described in any item block heat of claim 5-6
Application in electric material refrigeration equipment or thermo-electric generation equipment.
8. the preparation method of composite thermoelectric material according to claim 1-4, it is characterised in that: including by thermoelectricity
Ball milling is at nanometer powder under anaerobic for material alloys block, then using in liquid phase coating, atomic layer deposition and vapor deposition
At least one, thermoelectric material nanometer powder surface cladding at least one layer by ZnO, Al2O3、TiO2, ZnS, ZnSe and ZnTe
At least one of formed inorganic semiconductor compound interface layer, that is, obtain the composite thermoelectric material.
9. preparation method according to claim 8, it is characterised in that: the ball milling is high-energy ball milling, three-dimensional vibration ball milling
At least one of with common planetary ball milling；Preferably, the ball milling carries out in glove box, and water content is small in the glove box
In 0.1ppm, oxygen content is less than 0.1ppm.
10. the preparation method of block thermoelectric material according to claim 5 or 6, it is characterised in that: including being wanted using right
Preparation method described in asking 8 or 9 prepares composite thermoelectric material, then is sintered the composite thermoelectric material of preparation to form block thermoelectricity
Material；Preferably, described to be sintered to plasma hot pressing sintering；It is furthermore preferred that the condition of the plasma hot pressing sintering is
Vacuum degree is not less than 8 × 10-3Pa, pressure 30-60MPa, heating rate be 5-200 DEG C/min, sintering temperature 100-400
DEG C, soaking time 2-100min.
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| CN114436639A (en) * | 2020-11-04 | 2022-05-06 | 天津理工大学 | ZnO-based thermoelectric ceramic with high thermoelectric performance 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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