CN103320636A - Novel method for quickly preparing high-performance Mg2Si0.3Sn0.7-based thermoelectric material - Google Patents
Novel method for quickly preparing high-performance Mg2Si0.3Sn0.7-based thermoelectric material Download PDFInfo
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- CN103320636A CN103320636A CN2013102520129A CN201310252012A CN103320636A CN 103320636 A CN103320636 A CN 103320636A CN 2013102520129 A CN2013102520129 A CN 2013102520129A CN 201310252012 A CN201310252012 A CN 201310252012A CN 103320636 A CN103320636 A CN 103320636A
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Abstract
The invention relates to a novel method for quickly preparing a high-performance Mg2Si0.3Sn0.7-based thermoelectric material, which comprises the following steps of: 1) weighing according to the stoichiometric ratio of each atom in a thermoelectric material Mg2(1+0.08)(Si0.3Sn0.7)(1-y)Sby (0<=y<=0.025), uniformly mixing the raw material powder in a mortar, and pressing the uniformly mixed powder into a block; 2) putting the obtained block into a graphite crucible, and performing fusion spin-throwing in melt spin-throwing quenching equipment to obtain a Mg2(Si0.3Sn0.7)(1-y)Sby strip product; and 3) grinding the Mg2(Si0.3Sn0.7)(1-y)Sby strip product into powder, and performing discharge plasma activation sintering to obtain the high-performance Mg2Si0.3Sn0.7-based thermoelectric material. The method provided by the invention has the characteristics of energy saving, short preparation time, simple technological parameters and the like; and the thermoelectric merit figure ZT of the obtained block can reach 1.3.
Description
Technical field
The invention belongs to the new energy materials field, be specifically related to a kind of Mg
2Si
0.3Sn
0.7The preparation method of base thermoelectricity material.
Background technology
The energy and environment play vital effect for the target of reaching Sustainable development.The energy can make social economy obtain significant progress, but also can cause inevitably the deterioration of environment simultaneously.Since present stage the energy short supply state and environmental pollution day by day serious, effectively develop new energy materials and become the topic of paying close attention in the world.Thermoelectric generation technology can realize the direct conversion between heat energy and the electric energy, to the consumption that reduces fossil energy and the deterioration that alleviates social environment, has played the effect that can not be ignored.Thermoelectric material based on the Seebeck effect, can utilize used heat (industrial gaseous waste used heat, waste heat of automotive exhaust gas etc.) to generate electricity, thereby can alleviate the consumption of the energy and the deterioration of environment.
Thermoelectric material can directly become electric energy with thermal power transfer, has the advantages such as, noiselessness little without drive disk assembly, volume, pollution-free, good reliability, recycles in automobile waste heat, huge application prospect is being arranged aspect the industrial afterheat power generation.The efficiency of conversion of thermoelectric material is mainly by the zero dimension thermoelectric figure of merit
ZT(
ZT=
a 2 S T/
k, wherein
aFor the Seebeck coefficient,
sFor specific conductivity,
kFor thermal conductivity,
TBe absolute temperature) determine,
ZTLarger, the conversion efficiency of thermoelectric of material will be higher.
Mg
2Si
0.3Sn
0.7Based solid solution is a cube antifluorite structure, because its raw material reserves are abundant, nontoxic, cheap, density is little, and thermoelectricity capability is excellent, and the n-shaped material thermoelectric figure of merit of this system
ZTReach as high as 1.3, thereby be subject to showing great attention to of international thermoelectric field.
At present, Mg
2Si
0.3Sn
0.7Synthetic main scorification and the solid reaction process of adopting of base thermoelectricity material.Yet, the fusing point difference that component is larger, 232 ℃ of the fusing points of Sn, 649 ℃ of the fusing points of Mg, 1414 ℃ of the fusing points of Si, and the high saturated vapor pressure of Mg and strong reactive behavior (quite serious to the Glass tubing corrosion), so that the accurate control that scorification can not obtain to form (volatilization of Mg and oxidation etc.).Low-temperature solid phase reaction, although improved preferably the volatilization loss of Mg, the reaction times is longer, and reaction times is more, reacting required total time is 48h.Therefore, the synthetic method of a kind of simple and fast, less energy consumption is for Mg
2Si
0.3Sn
0.7Base thermoelectricity material seems extremely important.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of quick preparation high-performance Mg for the deficiency of above-mentioned prior art existence
2Si
0.3Sn
0.7The novel method of base thermoelectricity material, the method technique is simple, and preparation time is short, the compact block distributed components that obtains, thermoelectricity capability excellence.
The present invention is that the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A kind of quick preparation high-performance Mg
2Si
0.3Sn
0.7The novel method of base thermoelectricity material, it comprises the steps:
1) 1) take Mg powder, Si powder, Sn powder and Sb powder as raw material, presses Mg
2 (1+0.08)(Si
0.3Sn
0.7)
1-ySb
yThe stoichiometric ratio of each atom is carried out weighing in (Mg excessive 8% is in order to compensate the volatilization loss of Mg, and Sb is doped element, 0≤y≤0.025) thermoelectric material, and material powder is mixed in mortar, and the powder that mixes is pressed into block;
2) the gained block is placed plumbago crucible after, place again melt to revolve to get rid of fast cooling device to carry out melting and revolve and get rid of, obtain Mg
2(Si
0.3Sn
0.7)
1-ySb
y(0≤y≤0.025) strand of product;
3) with the Mg of previous step gained
2(Si
0.3Sn
0.7)
1-ySb
y(0≤y≤0.025) strand of product grind into powder carries out discharge plasma activation (PAS, Plasma Activated Sintering) sintering to it, obtains high-performance Mg
2(Si
0.3Sn
0.7)
1-ySb
y(0≤y≤0.025) thermoelectric material.
Press such scheme, in the described step 1), the quality purity of Mg powder, Si powder, Sn powder and Sb powder is all more than or equal to 99.9%.
Press such scheme, described step 2) in, melt revolves to get rid of and is argon gas atmosphere in the fast cooling device cavity, relative pressure is-0.05MPa, melt revolves the processing parameter that gets rid of: copper roller rotating speed is 30m/s, it is 0.04MPa that argon gas sprays relative pressure, and induction voltage is 150V, and it is 1-2min that the band time is got rid of in melting.
Press such scheme, in the described step 3), the process that powder carries out discharge plasma activated sintering is: with the powder compacting in the graphite jig of 15mm of packing into, then be to carry out sintering under the 33MPa condition in vacuum less than 10Pa and sintering pressure, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, sintering densification time 7min.
Above-mentioned preparation method has obtained high-performance Mg
2Si
0.3Sn
0.7Base compact block thermoelectric material.
Press such scheme, described high-performance Mg
2Si
0.3Sn
0.7Base compact block thermoelectric material homogeneous chemical composition, the thermoelectricity capability figure of merit
ZTReach 1.3 at 800K.
Among the present invention, utilize high-frequency induction heating that plumbago crucible is rapidly heated, then plumbago crucible carries out rapid heating by multiple thermaltransmission mode (thermal conduction, thermal radiation etc.) to reacting front block, because Mg, Sn fusing point are respectively 649 ℃, 232 ℃, therefore, within very short time, these two kinds of main elements of Mg, Sn just can melting, form liquid phase, element peripheral with it reacts simultaneously.At this moment, spray argon gas in plumbago crucible, air pressure just forces the melt under the current state, is sprayed onto fast the copper roller surface of high speed rotating (30m/s), cools off rapidly, and rate of cooling can reach (10
5~ 10
6K/s), like this, the gained strand of product has just kept the homogeneity of high-temperature molten-state.Simultaneously, preparation technology's simplification and the shortening in reaction times so that the oxidation of Mg has obtained good inhibition, do not have the generation of MgO second-phase substantially, so gained agglomerate body heat electrical property is very excellent.
Compared with prior art, the invention has the beneficial effects as follows:
1. adopt melt to revolve the method for getting rid of.The characteristics such as that the present invention has is energy-efficient, preparation time is extremely short and processing parameter is simple.
2. the prepared Mg of the present invention
2Si
0.3Sn
0.7Base compact block thermoelectric material sintered product distributed components, and thermoelectricity capability can reach the optimum value of this system of present report
ZT~ 1.3.
3. the present invention mainly adopts raw material Mg powder, Si powder, Sn powder and Sb powder, and reserves are abundant, cheap.
Description of drawings
Fig. 1 is step 2 among the embodiment) the XRD figure spectrum of the strand of product fine powder that obtains.
Fig. 2 is the XRD figure spectrum of the block thermoelectric material that step 3) obtains among the embodiment.
Fig. 3 is the micro-structure diagram of the block that step 3) obtains among the embodiment.Wherein Fig. 3 (a) be the agglomerate body section different amplification (from left to right, from top to bottom, be followed successively by amplify 500 times, 1.00 k doubly, 5.00 k doubly and 10.00 k doubly) micro-structure diagram; Fig. 3 (b) is that the elemental map after the polishing of sintering block can spectrogram.
Fig. 4 is the thermoelectricity capability figure of the block that step 3) obtains among the embodiment, wherein 4(a) be the electrical property (specific conductivity of sintering block
s, the Seebeck coefficient
aAnd power factor
PF) temperature variant graph of a relation; 4(b) be the thermal conductivity of sintering block
kWith the zero dimension thermoelectric figure of merit
ZTTemperature variant graph of a relation.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention is not limited only to the following examples.Following embodiment is the Mg of thermoelectricity capability optimum among the present invention
2Si
0.3Sn
0.7The preparation method of base thermoelectricity material, at this moment y=0.02; When 0≤y≤0.025, all can prepare Mg
2Si
0.3Sn
0.7Base thermoelectricity material.
Embodiment:
A kind of quick preparation high-performance Mg
2Si
0.3Sn
0.7The novel method of base thermoelectricity material, it comprises the steps:
1) take Mg powder, Si powder, Sn powder and Sb powder as raw material, presses Mg
2 (1+0.08)(Si
0.3Sn
0.7)
0.98Sb
0.02(Mg excessive 8% is in order to compensate the volatilization loss of Mg) stoichiometric ratio batching, the weighing total amount is 5.5g, in mortar that the material powder manual mixing is even, the powder that obtains mixing, the powder that mixes is pressed into the cylindrical block that diameter is 12.7mm (5MPa pressurize 5min at tabletting machine, then, 8MPa pressurize 10min);
2) above-mentioned cylindrical block is placed in the plumbago crucible, being put in melt revolves to get rid of and carries out melt in the quenching apparatus and revolve and get rid of again, cavity is argon gas atmosphere, relative pressure is-0.05MPa, carry out melt and revolve when getting rid of, induction voltage is 150V, and copper roller rotating speed is 30m/s, it is 0.04MPa that argon gas sprays relative pressure, obtains Mg
2 (1+0.08)(Si
0.3Sn
0.7)
0.98Sb
0.02Strand of product;
3) with step 2) gained Mg
2 (1+0.08)(Si
0.3Sn
0.7)
0.98Sb
0.02Strand of product is ground, again the gained fine powder is carried out discharge plasma activated sintering (PAS): with the powder compacting in the graphite jig of 15mm of packing into, then be to carry out sintering under the 33MPa condition in vacuum less than 10Pa and sintering pressure, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, the sintering densification time is 7min, obtains Mg
2(Si
0.3Sn
0.7)
0.98Sb
0.02The compact block thermoelectric material.
The XRD figure spectrum that strand of product is ground to form fine powder is seen Fig. 1, as seen from Figure 1, melting revolve get rid of the strand of product powder of gained behind the chilling XRD spectrum peak position in Mg
2Si and Mg
2Between the Sn, simultaneously, the spectrum peak is broadening comparatively, illustrates that this product is amorphous or nanocrystalline single phase solid solution.
The XRD figure spectrum of gained sintering block thermoelectric material is seen Fig. 2, and as shown in Figure 2, the powder X-ray RD of the block that obtains behind PAS spectrum peak position is in Mg
2Si and Mg
2Between the Sn, simultaneously, the spectrum peak very sharp-pointed, sintering is described after block crystal grain well grown, be single phase solid solution.
The microtexture of gained sintering block thermoelectric material is seen Fig. 3.Wherein Fig. 3 (a) be the agglomerate body section different amplification (from left to right, from top to bottom, be followed successively by amplify 500 times, 1.00 k doubly, 5.00 k doubly and 10.00 k doubly) micro-structure diagram, can find out among the figure, this fracture mode is transgranular fracture, thermoelectric material block intercrystalline that the method obtains is described in conjunction with closely, block is very fine and close.Fig. 3 (b) is that the elemental map after the sintering block polishing can spectrogram, and as can be seen from the figure, Mg, Si, Sn element evenly distribute, and illustrates that the thermoelectric material composition profiles that the method obtains is very even.
The thermoelectricity capability of gained sintering block materials is seen Fig. 4.Wherein Fig. 4 (a) is the electrical property (specific conductivity of sintering block
s, the Seebeck coefficient
aAnd power factor
PF) temperature variant graph of a relation.Fig. 4 (b) is the thermal conductivity of sintering block
kWith the zero dimension thermoelectric figure of merit
ZTTemperature variant graph of a relation, described high-performance Mg
2Si
0.3Sn
0.7The thermal conductivity of base compact block thermoelectric material raises with temperature, reduces gradually; The thermoelectricity capability figure of merit
ZTRaise with temperature, raise gradually, reach 1.3 at 800K.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and bound, the interval value of processing parameter (such as melting voltage etc.) can both realize the present invention, do not enumerate one by one embodiment at this.
Claims (6)
1. one kind prepares high-performance Mg fast
2Si
0.3Sn
0.7The novel method of base thermoelectricity material is characterized in that it comprises the steps:
1) take Mg powder, Si powder, Sn powder and Sb powder as raw material, presses Mg
2(Si
0.3Sn
0.7)
1-ySb
yThe stoichiometric ratio of each atom is carried out weighing in (0≤y≤0.025) thermoelectric material, and material powder is mixed in mortar, and the powder that mixes is pressed into block;
2) the gained block is placed plumbago crucible after, place melt to revolve to get rid of fast cooling device to carry out melting and revolve and get rid of, obtain Mg
2(Si
0.3Sn
0.7)
1-ySb
y(0≤y≤0.025) strand of product;
3) with the Mg of previous step gained
2(Si
0.3Sn
0.7)
1-ySb
y(0≤y≤0.025) strand of product grind into powder carries out discharge plasma activated sintering to it, obtains high-performance Mg
2(Si
0.3Sn
0.7)
1-ySb
y(0≤y≤0.025) thermoelectric material.
2. a kind of quick preparation high-performance Mg according to claim 1
2Si
0.3Sn
0.7The novel method of base thermoelectricity material is characterized in that in the described step 1) that the quality purity of Mg powder, Si powder, Sn powder and Sb powder is all more than or equal to 99.9%.
3. a kind of quick preparation high-performance Mg according to claim 1
2Si
0.3Sn
0.7The novel method of base thermoelectricity material, it is characterized in that described step 2) in, melt revolves to get rid of and is argon gas atmosphere in the fast cooling device cavity, relative pressure is-0.05MPa, melt revolves the processing parameter that gets rid of: copper roller rotating speed is 30m/s, it is 0.04MPa that argon gas sprays relative pressure, and induction voltage is 150V, and it is 1-2min that the band time is got rid of in melting.
4. a kind of quick preparation high-performance Mg according to claim 1
2Si
0.3Sn
0.7The novel method of base thermoelectricity material, it is characterized in that: in the described step 3), the process that powder carries out discharge plasma activated sintering is: with the powder compacting in the graphite jig of 15mm of packing into, then be to carry out sintering under the 33MPa condition in vacuum less than 10Pa and sintering pressure, temperature rise rate with 100 ℃/min is warmed up to 650 ℃, sintering densification time 7min.
5. preparation method as claimed in claim 1 has obtained high-performance Mg
2Si
0.3Sn
0.7Base compact block thermoelectric material.
6. high-performance Mg as claimed in claim 1
2Si
0.3Sn
0.7Base compact block thermoelectric material is characterized in that gained Mg
2Si
0.3Sn
0.7Base compact block thermoelectric material distributed components, the thermoelectricity capability figure of merit
ZTReach 1.3 at 800K.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109785A (en) * | 2014-04-16 | 2014-10-22 | 中国科学院上海高等研究院 | Mg-Si-Sn-based nano-composite thermoelectric material and preparation method thereof |
| CN104109770A (en) * | 2014-07-18 | 2014-10-22 | 太原理工大学 | Method for preparing Mg2SixSn[1-x]Biy-base thermoelectric material by microwave-assisted MgH2 solid reaction process |
| CN104232960A (en) * | 2014-09-03 | 2014-12-24 | 武汉理工大学 | Method of quickly preparing Mg-Si-Sn-based thermoelectric material in controllable manner |
| CN111712937A (en) * | 2018-02-20 | 2020-09-25 | 三菱综合材料株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric conversion module |
| JPWO2019039320A1 (en) * | 2017-08-22 | 2020-12-24 | 株式会社白山 | Thermoelectric materials and thermoelectric modules |
| CN112279652A (en) * | 2020-10-29 | 2021-01-29 | 南京工程学院 | Rapid non-equilibrium preparation method for Mg-Si-Sn-Sb based thermoelectric material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693962A (en) * | 2009-10-19 | 2010-04-14 | 武汉理工大学 | Method for preparing p-type filling type skutterudite compound thermoelectric material |
-
2013
- 2013-06-24 CN CN201310252012.9A patent/CN103320636B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101693962A (en) * | 2009-10-19 | 2010-04-14 | 武汉理工大学 | Method for preparing p-type filling type skutterudite compound thermoelectric material |
Non-Patent Citations (1)
| Title |
|---|
| 童吉楚: "Mg2Si0.3Sn0.7固体热电性能及其结构微细化探索", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, 15 March 2012 (2012-03-15) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109785A (en) * | 2014-04-16 | 2014-10-22 | 中国科学院上海高等研究院 | Mg-Si-Sn-based nano-composite thermoelectric material and preparation method thereof |
| CN104109770A (en) * | 2014-07-18 | 2014-10-22 | 太原理工大学 | Method for preparing Mg2SixSn[1-x]Biy-base thermoelectric material by microwave-assisted MgH2 solid reaction process |
| CN104109770B (en) * | 2014-07-18 | 2016-05-11 | 太原理工大学 | Microwave is assisted MgH2Solid reaction process is prepared Mg2SixSn1-xBiyThe method of base thermoelectricity material |
| CN104232960A (en) * | 2014-09-03 | 2014-12-24 | 武汉理工大学 | Method of quickly preparing Mg-Si-Sn-based thermoelectric material in controllable manner |
| JPWO2019039320A1 (en) * | 2017-08-22 | 2020-12-24 | 株式会社白山 | Thermoelectric materials and thermoelectric modules |
| JP7228844B2 (en) | 2017-08-22 | 2023-02-27 | 株式会社白山 | Thermoelectric materials and thermoelectric modules |
| CN111712937A (en) * | 2018-02-20 | 2020-09-25 | 三菱综合材料株式会社 | Thermoelectric conversion material, thermoelectric conversion element, and thermoelectric conversion module |
| CN112279652A (en) * | 2020-10-29 | 2021-01-29 | 南京工程学院 | Rapid non-equilibrium preparation method for Mg-Si-Sn-Sb based thermoelectric material |
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