CN107814571A - A kind of SnTe nano composite materials and its preparation method and application - Google Patents

A kind of SnTe nano composite materials and its preparation method and application Download PDF

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CN107814571A
CN107814571A CN201711059730.9A CN201711059730A CN107814571A CN 107814571 A CN107814571 A CN 107814571A CN 201711059730 A CN201711059730 A CN 201711059730A CN 107814571 A CN107814571 A CN 107814571A
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powder
nano composite
composite materials
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snte
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CN107814571B (en
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李洪涛
郅惠博
王彪
赵永胜
杨曼曼
宿太超
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INDUSTRIAL PRODUCTS AND RAW MATERIALS INSPECTION TECHNOLOGY CENTER OF SHANGHAI ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
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Abstract

The present invention provides a kind of SnTe nano composite materials and preparation method thereof, and the preparation method includes：1) Ge, Sn and Te powder raw material mixed by certain mol proportion is placed in closed container；2) into closed container inject absolute ethyl alcohol and deoxygenated and/or protection processing, then closed container is fixed on ball mill, carry out ball milling；3) processing is dried to the product after ball milling, obtains dried powder；4) block is pressed into resulting dried powder；5) block being pressed into is subjected to pressure sintering, obtains fine and close SnTe nano composite materials.The present invention preparation method cost is cheap, short preparation period, technique is simple, synthesis temperature is low, saves the energy, is adapted to large-scale industrial production, and the bulk nano composite material consistency being prepared is high, and thermal conductivity is low.

Description

A kind of SnTe nano composite materials and its preparation method and application
Technical field
The invention belongs to novel energy resource material technology field, and in particular to a kind of SnTe nano composite materials and preparation method thereof And application.
Background technology
Thermoelectric material can realize the direct conversion of heat energy and electric energy, and the thermoelectric generator made using it can be effective Thermo-electric generation is carried out using thermals source such as industrial exhaust heat, automobile exhaust gases.Because without any mechanical moving element, thermo-electric device has The advantages that portable, pollution-free, noiseless.The middle warm area thermoelectric material of suitable thermo-electric generation is mainly using PbTe as representative at present Sulfur family lead compound, but heavy metal Pb to environment and human body harm it is larger.
Find the important directions that unleaded high performance thermoelectric material is current thermoelectricity research field.Sn and the Pb category of non-toxic inexpensive In congeners, and SnTe is identical with PbTe structures, therefore SnTe is considered as the important candidate materials for substituting PbTe.Mesh Before, the preparation methods of SnTe materials is mainly vacuum melting and Mechanical Alloying, it is necessary to high-temperature heating or machine for a long time Tool ball milling can just obtain SnTe materials, so sample prepared by above two method has the shortcomings of long preparation period, cost is high. In addition, the higher property that have impact on it of SnTe intrinsic thermal conductivity and its further application.
The content of the invention
To solve the drawbacks described above of prior art, the invention provides a kind of new SnTe nanometers containing Ge or Ag, Sb Composite (Ge-Sn-Te or Ag-Sb-Sn-Te nano composite materials) and preparation method thereof, method of the invention can reduce Manufacturing cycle, cost is reduced, the nano composite material being prepared is pollution-free and has very low thermal conductivity.
The preparation method of SnTe nano composite materials provided by the invention, the preparation method comprise the following steps：
Step 1) dispensing：Raw material is placed in closed container (such as ball grinder), the raw material includes mixing by certain mol proportion Ge powder, Sn powder and the Te powder of conjunction, or Ag powder, Sb powder, Sn powder and Te powder；
Step 2) wet ball grinding：Organic solvent is injected into closed container, and is deoxygenated and/or protection processing, will be through The closed container of processing is fixed on ball mill, and ball milling, predetermined hold-time are carried out with certain rotating speed；
Step 3) is dried：Processing is dried to the product after step 2) wet ball grinding, obtains dried powder；
Step 4) is suppressed：Dried powder obtained by step 3) is ground, and by the powder briquet after grinding Body；
Step 5) sinters：The block that step 4) is pressed into carries out pressure sintering, obtains fine and close Ge-Sn-Te or Ag-Sb- Sn-Te nano composite materials；Specially：Block sample is applied into predetermined pressure and is heated to the first predetermined temperature, carries out first Stage sinters；After the completion of fast cooling to the second predetermined temperature, carry out second stage sintering；After the completion of be quickly down to room temperature and unload Pressure, obtains Ge-Sn-Te the or Ag-Sb-Sn-Te nano composite materials.
Wherein, in step 1), when raw material is Ge powder, Sn powder and Te powder, mole of the Ge powder, Sn powder and Te powder elements Than for (0.05-0.4):(0.6-0.95):1；Preferably, it is 0.1:0.9:1；When raw material is Ag powder, Sb powder, Sn powder and Te powder When, the mol ratio of Ag, Sb, Sn powder and Te the powder element is (0.05-0.25):(0.05-0.25):(0.5-0.9):1；It is preferred that Ground, it is 0.08:0.08:0.84:1.
Wherein, Ge-Sn-Te the or Ag-Sb-Sn-Te nano composite materials finally prepared are respectively provided with relatively low thermal conductivity.
Wherein, in step 1), ball material mass ratio (mass ratio of abrading-ball and raw material) is (5-20):1；Preferably, it is 15:1、 20:1。
Wherein, in step 1), raw material Sn, Te, Ge, Ag and Sb powder purity is above 99.9%.
Wherein, in step 2), the volume ratio of the raw material and absolute ethyl alcohol is 1:(1-3)；Preferably, it is 1:2.
Wherein, in step 2), one kind or several that the organic solvent includes but is not limited in absolute ethyl alcohol, acetone, ether Kind；Preferably, it is absolute ethyl alcohol.
Wherein, it is described to deoxygenate and/or include the step of protecting processing in step 2)：Height is passed through after ball grinder is vacuumized Pure inert gas, repetition vacuumizes, logical high purity inert gas operates several times.Preferably, deoxygenated and/or protection processing When, the inert gas being passed through is along ball milling tank skin by the top injection ball grinder of ball grinder.Wherein, the inert gas choosing From Ar, He, N2Deng preferably Ar gas.
Wherein, in step 2), the desired speed can be, but not limited to be 200-350 revs/min；Preferably 250 revs/min, 300 revs/min.
Wherein, in step 2), the scheduled time is 30-500 minutes；Preferably, it is 120-300 minutes；It is further preferred that For 200 minutes.
Wherein, in step 3), the drying process can use any commonly employed drying means, include but is not limited to be, Product after step 2) wet-milling is positioned in vacuum drying chamber, vacuum 10-200Pa, preferably 50Pa；Vacuum drying 3-10 hours, preferably 4-8 hour, more preferably 6 hours；Drying temperature be 50-70 DEG C, preferably 50-60 DEG C or 60-70 DEG C of person, more preferably 60 DEG C.
Wherein, in step 4), the compacting can be with any commonly employed drawing method, and it is hydraulic pressure to include but is not limited to.
Wherein, in step 5), the predetermined pressure is 2-5GPa；Preferably, it is 4GPa.
Wherein, in step 5), the heating rate for being heated to the first predetermined temperature is 200~400 DEG C/minute；Preferably, For 300 DEG C/minute.
Wherein, in step 5), first predetermined temperature is 850~1050 DEG C；Preferably, it is 1000 DEG C.
Wherein, in step 5), the first stage sintering time is 3-40 minutes；Preferably, it is 10-15 minutes.
Wherein, in step 5), after the completion of the first stage sintering, cooled with 50-200 DEG C/sec of speed；Preferably, For 60 DEG C/sec, 100 DEG C/sec or 200 DEG C/sec.
Wherein, in step 5), second predetermined temperature is 700-800 DEG C；Preferably, it is 750 DEG C.
Wherein, in step 5), the second stage sintering time is 5-20 minutes；Preferably, it is 10-15 minutes.
Wherein, in step 5), after the completion of the second stage sintering, cooled with 100~200 DEG C/minute of speed；It is preferred that Ground, it is 100 DEG C/minute, 200 DEG C/minute.
In an embodiment, the step 5) includes：Block sample is applied into predetermined pressure and added to first Predetermined temperature, fast cooling is cooled to the second predetermined temperature with 60 DEG C/sec of speed after sintering 10-15 minutes, sinters 10- again 15 minutes, room temperature and release are down to so that 200 DEG C/minute of speed cooling is quick, Ge-Sn-Te or Ag-Sb-Sn-Te nanometers is obtained and answers Condensation material.
In step 5) of the present invention, the heating technique prepared in the sintering process of nano composite material is particularly important, for containing Ge sample the first predetermined temperature heating process is that the second predetermined temperature is rich in order to which Ge, Sn and Te are completely in molten condition (Ge-Te refers to GeTe, GeTe to Ge Ge-Te4) crystallization and freezing, and Sn-Te (Sn-Te refers to SnTe) is still in molten condition mistake Journey, the first predetermined temperature need high-speed to cool to the second predetermined temperature process, promote Ge-Te from the liquid containing three kinds of elements It is middle to separate out and retain nanoscale；The sintering time of second stage need to be controlled within 20 minutes, avoid the easy shape of overlong time Into solid solution alloy.It is in order to which Ag, Sb, Sn and Te locate completely for sample the first predetermined temperature heating process containing Ag, Sb In molten condition, the second predetermined temperature is rich Sn Sn-Te (Sn-Te refers to SnTe phases) crystallization and freezing, and rich Ag and Sb Ag- Sb-Te2(Ag-Sb-Te2Refer to AgSbTe2) still in molten condition process, the first predetermined temperature to the second predetermined temperature process Ag-Sb-Te2Crystallize into nanoscale and be enriched in Sn-Te grain boundaries；The sintering time of second stage still need to control 20 minutes with It is interior, avoid overlong time from easily forming solid solution alloy.
The inventive method uses two benches heating technique, i.e.,：It is first heated on the fusing point of raw material and ensures all elements Fully melting, then cool to matrix phase (referring to SnTe phases) and nano-second-phase compound (refers to Ge-Te phases or AgSbTe2) fusing point Between so that a kind of material first solidifies precipitation, and another kind is still within molten condition.Finally cooling is prepared the nanometer and answered Condensation material.
The invention also provides a kind of SnTe nano composite materials being prepared by above-mentioned preparation method.
The invention also provides a kind of SnTe nano composite materials, its mainly by face-centred cubic structure and crystal grain it is micro- in 2-10 The Sn-Te phases and crystal grain of metrical scale are the Ge-Te phases or Ag-Sb-Te phases of nanoscale, i.e. the present invention prepares product Ge-Sn- Te or Ag-Sb-Sn-Te nano composite materials are the composite containing nano-second-phase, the nanocomposites tool There is very low thermal conductivity, be 1.25-2W/mK.
The invention also provides Ge-Sn-Te the or Ag-Sb-Sn-Te nano composite materials in thermo-electric generation field Using.
The beneficial effects of the present invention are a. costs of raw material are cheap, and mainly lead former material is substituted using glass putty in the present invention Material, its abundance, environmental sound are cheap.B. prepare that material periodicities are short, and technique is simple.The present invention has technique letter Single, synthetic material is rapid, and temperature is low, saves the energy, is adapted to large-scale industrial production.C. the SnTe block nanometers being prepared are answered Condensation material consistency is high, and thermal conductivity is low (1.25-2W/mK).
Other advantages, target and the feature of the present invention will be illustrated in following embodiment with reference to accompanying drawing, And to a certain extent, based on to reading and understanding hereafter, these advantages and features are to those skilled in the art It can be appreciated that.
Brief description of the drawings
Fig. 1 is the X ray diffracting spectrum (XRD) of Ge-Sn-Te nano composite materials prepared by embodiment 1-4.
Fig. 2 is that Ge-Sn-Te prepared by embodiment 1 (contains Ge10%, concrete component Ge0.1Sn0.9Te) nano composite material Electron scanning electromicroscopic photograph (SEM) and electron spectrum.A figures are the SEM spectrum of sample, it is seen that the microscopic appearance of sample mainly wraps The nanocrystal of crystal grain and a large amount of Dispersed precipitates containing micron dimension；B figures are the electronic energies done to micron grain and nanocrystal Spectrum analysis, wherein micron grain is mainly Sn and Te elements, and nanocrystal contains tri- kinds of elements of Ge, Sn, Te.
Fig. 3 is the thermal conductivity comparison diagram of the Ge containing different content prepared by embodiment 1-4 Ge-Sn-Te nano composite materials.
Fig. 4 is the XRD of Ag containing different content prepared by embodiment 9 and Sb Ag-Sb-Sn-Te nano composite materials.
Fig. 5 is that Ag-Sb-Sn-Te prepared by embodiment 9 (contains Ag and Sb each 10%, concrete component is Ag0.1Sb0.1Sn0.8Te) the electron scanning electromicroscopic photograph (SEM) and electron spectrum of nano composite material.A figures are the SEM figures of sample Spectrum, it is seen that the microscopic appearance of sample mainly includes the crystal grain of micron dimension and the nanocrystal in grain boundaries distribution；B figures are A figures The electron spectroscopy analysis of middle white line subregion, it is observed that less in grain boundaries Sn contents and Ag and Sb contents are higher.
Embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail.The process of the implementation present invention, Condition, experimental method etc., it is the universal knowledege and common knowledge of this area in addition to the following content specially referred to, this hair It is bright that content is not particularly limited.
Embodiment 1-4
In this embodiment, by taking the process for preparing Ge-Sn-Te as an example, the preparation process of the thermoelectric material of the present invention is entered Row is described in detail, and preparation process comprises the following steps：1) batching step；2) wet ball grinding step；3) drying steps；4) compacting step Suddenly；5) sintering step.
Five above-mentioned steps will be described in detail respectively below.
1) batching step
With Ge powder, Sn powder and Te powder are primary raw material, and Ge powder, Sn powder and Te powder are mixed with certain mol ratio, put In stainless steel jar mill.The mol ratio of Ge powder, Sn powder and Te powder is (0.05-0.4):(0.6-0.95):1.In the present embodiment, Tested respectively using the mol ratio of different Ge powder, Sn powder and Te powder, and the various aspects of performance of products obtained therefrom is entered Test is gone, as a result as shown in figs. 1-4.
In the present embodiment, raw material uses high-purity Ge powder (purity 99.999%), Sn powder (purity 99.9%) and Te powder 99.9%)；By GexSn1-xTe stoichiometries compare raw material and weighed, gross weight 20g, wherein, (x refers to Ge to x=0-0.5 Molar content relative to Te molar content, 1) Ge and Sn add up to, preferably 0.1.Ratio of grinding media to material is set as 15:1.
2) wet ball grinding
Absolute ethyl alcohol is injected to ball grinder, before the raw material to being added in ball grinder mixes, it usually needs right Raw material is deoxygenated and/or protection processing.Deoxidation and/or protection processing include being passed through high-purity Ar gas after ball grinder is vacuumized, Then, repeat to vacuumize, the operation of logical high-purity Ar several times, ball grinder internal oxygen is drained with guarantee such as 3-5 time.
After deoxygenating and/or protection is handled, ball grinder is fixed on ball mill, with 250 revs/min of progress of desired speed Wet ball grinding, predetermined hold-time 200 minutes.
3) dry
After wet-milling, the sample in ball grinder is collected, then the product after wet-milling is positioned in vacuum drying chamber Processing is dried, vapors away whole absolute ethyl alcohols, obtains dried powder；Wherein, the condition of vacuum is：Vacuum is 50Pa； It is dried in vacuo 6 hours, 60 DEG C of drying temperature.
4) suppress
Obtained dried powder is put into mould and is pressed into block using tablet press machine.
5) sinter
Finally, the block being pressed into is subjected to pressure sintering, obtains fine and close Ge-Sn-Te nano composite materials.By block sample Product apply predetermined pressure 4GPa and are heated to 1000 DEG C of the first predetermined temperature, the first sintering time with 300 DEG C/min of heating rate To be cooled with 60 DEG C/sec of speed after 10 minutes, fast cooling to 750 DEG C of the second predetermined temperature, the second sintering time is 15 points Clock, cooled with 100 DEG C/minute of speed, be quickly down to room temperature and release, obtain Ge-Sn-Te nano composite materials.
It is particularly important that technique is heated in Ge-Sn-Te nano composite materials preparation process of the present invention, the heating of the first predetermined temperature Process is that the second predetermined temperature is rich Sn Sn-Te crystallization and freezings and Ge-Te in order to which Ge, Sn and Te are completely in molten condition Still in molten condition process, the first predetermined temperature needs high-speed to cool to the second predetermined temperature process, promotes Ge-Te from molten Melt and nanoscale is separated out and retained in liquid Ge-Sn-Te.The sintering time of second stage need to be controlled within 20 minutes, avoided Overlong time easily forms solid solution alloy.
By the above process, the Ge-Sn-Te nanometers that Ge mole percents are 0%, 10%, 20%, 30% are prepared for respectively to answer Condensation material.
Fig. 1 and Fig. 2 be respectively embodiment 1 prepare four kinds of Ge-Sn-Te nano composite materials X ray diffracting spectrum and Ge mole percents are 10% nano composite material electron scanning electromicroscopic photograph.Sample after Fig. 1 XRD spectrum display incorporation Ge In there are Ge-Te phases, Fig. 2 SEM results show that sample consistency is higher and it is micro- in 2-5 a large amount of nanocrystal Dispersed precipitates to be present On the crystal boundary and crystal face of rice magnitude SnTe phases；Show with reference to the XRD spectrum of energy spectrum analysis in Fig. 2 and Fig. 1, what the present invention obtained The nanometer of Ge-Sn-Te nano composite materials is mutually Ge-Te phases, i.e., the material that the present invention obtains belongs to micro-nano composite.
In order to verify the performance difference of four kinds of obtained Ge-Sn-Te nano composite materials, obtained Ge-Sn-Te is received Nano composite material is tested the thermal diffusion coefficient of Ge-Sn-Te nano composite materials using LFA-457, entered by cutting and polishing And thermal conductivity is calculated, thermal conductivity rate score is as shown in Figure 3；Wherein, in Fig. 3 legend 0,0.1,0.2,0.3 respectively represent Ge exist Mole percent in Ge-Sn-Te nano composite materials is 0%, 10%, 20%, 30%.From the figure 3, it may be seen that in 300K to 700K In temperature range, the average thermal conductivities of the Ge-Sn-Te nano composite materials containing Ge far below Sn-Te phases (i.e. containing mole Percentage is 0%Ge Ge-Sn-Te nano composite materials), received mainly due to rich Ge Ge-Sn-Te nano composite materials Rice mutually separates out in plane of crystal and grain boundaries, can scatter caused by lattice thermal conductivity caused by intermediate waves phonon reduces；Wherein contain There is the 10%Ge nano composite material thermal conductivity of (300K~700K) in Range of measuring temp to be respectively less than the Sn- without Ge Te, further putting forward the nano composite material of high Ge content, thermal conductivity increases on the contrary under the high temperature conditions, is primarily due to Ge contents Increase sample tends to be decrystallized, destroys the structure of nano composite material.
Embodiment 5-8
By SnTe and Ge0.1Sn0.9(Ge and Sn molar content are respectively 10% He relative to Te molar content to Te 90%) proportioning is prepared for the sample of different sintering pressures, and the sintering pressure of step 5 part is respectively set as 2GPa, 3GPa, 4GPa and 5GPa, other steps are the same as embodiment 1.
It is as shown in table 1 to test the nano composite material thermal conductivity at ambient temperature obtained, in the range of 2-4GPa with The raising of sintering pressure, the thermal conductivity of nano composite material are gradually reduced, in the range of 2-4GPa the reduction of thermal conductivity mainly by The defects of can result in distortion of lattice in high pressure, and then introducing dislocation, the presence of a large amount of defects can cause phon scattering to reduce heat Conductance.Sintering pressure is further improved after 4GPa not to be influenceed on thermal conductivity rate score, the defects of illustrating sample after 4GPa concentration reach To the limit, i.e. 4GPa is optimal sintering pressure.
The thermal conductivity of sample is obtained under the conditions of 1 different sintering pressures of table
Embodiment Sintering pressure (GPa) SnTe thermal conductivity (Wm-1K-1) Ge0.1Sn0.9Te thermal conductivity (Wm-1K-1)
5 2 6.452 2.657
6 3 6.299 2.575
7 4 6.167 2.531
8 5 6.168 2.531
Embodiment 9
Ge is substituted using Ag and Sb, prepares Ag-Sb-Sn-Te composites, element proportioning is (AgSb)xSn1-2xTe, step 5 sintering conditions are：First 1000 DEG C of predetermined temperature, the second 700 DEG C of predetermined temperature, other steps are the same as embodiment 1.
Fig. 4 is the X ray diffracting spectrum of Ag-Sb-Sn-Te nano composite materials prepared by embodiment 9, it is seen that sample contains SnTe and AgSbTe2 phases.Fig. 5 scanning electron micrograph display sample had not only contained micrometer size grains but also had contained nano particle size Little crystal grain, Fig. 5 energy spectrum analysis show that micron is mutually rich Sn phases, and it is rich AgSb phases that crystal boundary, which goes out nano particle size, with reference to Fig. 4 XRD Spectrum shows that micron is mutually SnTe, and nanometer is mutually AgSbTe2.
Table 2 is the thermal conductivity test result of Ag-Sb-Sn-Te nano composite materials prepared by embodiment 9 under room temperature condition, Because grain boundaries enriched nanometer Ag SbTe2, forms the strong scattering to phonon so that SnTe thermal conductivity substantially reduces, its The thermal conductivity of sample is minimum when middle AgSb contents are 0.125.
The thermal conductivity of the different AgSb contents samples of table 2
AgSb contents, x Thermal conductivity (Wm-1K-1)
0 6.167
0.1 3.234
0.125 2.675
0.16 2.847
It is last it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and unrestricted, this area Other modifications or equivalent substitution that those of ordinary skill is made to technical scheme, without departing from the technology of the present invention The spirit and scope of scheme, it all should cover among scope of the presently claimed invention.

Claims (10)

1. a kind of preparation method of SnTe nano composite materials, it is characterised in that the preparation method comprises the following steps：
Raw material is placed in closed container by step 1), and the raw material includes Ge powder, Sn powder and the Te powder by certain mol proportion mixing, Or Ag powder, Sb powder, Sn powder and Te powder；
Step 2) injects organic solvent into closed container, and deoxygenated and/or protection processing, then carry out ball milling；
Processing is dried to the product after ball milling in step 3), obtains dried powder；
Step 4) is ground to resulting dried powder, and polished powder is pressed into block；
The block being pressed into is carried out pressure sintering by step 5), obtains Ge-Sn-Te or Ag-Sb-Sn-Te nano composite materials.
2. the method as described in claim 1, it is characterised in that in step 1), when raw material is Ge powder, Sn powder and Te powder, institute The mol ratio for stating Ge powder, Sn powder and Te powder is (0.05-0.4):(0.6-0.95):1；When raw material is Ag powder, Sb powder, Sn powder and Te During powder, the mol ratio of Ag, Sb, Sn powder and Te powder is (0.05-0.25)：(0.05-0.25):(0.5-0.9):1.
3. the method as described in claim 1, it is characterised in that in step 1), ball material mass ratio is (5-20):1；And/or institute The volume ratio for stating raw material and absolute ethyl alcohol is 1:(1-3).
4. the method as described in claim 1, it is characterised in that in step 2), the organic solvent includes absolute ethyl alcohol, third One or more in ketone, ether；And/or the rotating speed of the ball milling is 200-350 revs/min；And/or the time of the ball milling For 30-500 minutes.
5. the method as described in claim 1, it is characterised in that in step 3), the drying process is by through step 2) wet-milling Product afterwards is positioned in vacuum drying chamber, vacuum 10-200Pa；It is dried in vacuo 3-10 hours；Drying temperature is 50-70 ℃。
6. the method as described in claim 1, it is characterised in that step 5) is specially：Block sample is applied into predetermined pressure simultaneously The first predetermined temperature is heated to, carries out first stage sintering；After the completion of fast cooling to the second predetermined temperature, carry out second stage Sintering；After the completion of be quickly down to room temperature and release, obtain Ge-Sn-Te the or Ag-Sb-Sn-Te nano composite materials.
7. the method as described in claim 1, it is characterised in that in step 5), the predetermined pressure is 2-5GPa；And/or institute State be heated to the first predetermined temperature heating rate be 200~400 DEG C/minute；And/or after the completion of the first stage sintering, with 50-200 DEG C/sec of speed cooling；And/or after the completion of the second stage sintering, cooled with 100~200 DEG C/minute of speed.
8. the method as described in claim 1, it is characterised in that in step 5), first predetermined temperature is 850~1050 DEG C, the first stage sintering time is 3-40 minutes；And/or second predetermined temperature be 700-800 DEG C, described second Stage sintering time is 5-20 minutes.
9. Ge-Sn-Te or the nano combined materials of Ag-Sb-Sn-Te that any one methods described such as claim 1~8 is prepared Material.
10. application of the nano composite material as claimed in claim 9 in thermo-electric generation field.
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