CN101654747B - Preparation method of AgPb10SbTe12 thermoelectric material - Google Patents

Preparation method of AgPb10SbTe12 thermoelectric material Download PDF

Info

Publication number
CN101654747B
CN101654747B CN2009100726830A CN200910072683A CN101654747B CN 101654747 B CN101654747 B CN 101654747B CN 2009100726830 A CN2009100726830 A CN 2009100726830A CN 200910072683 A CN200910072683 A CN 200910072683A CN 101654747 B CN101654747 B CN 101654747B
Authority
CN
China
Prior art keywords
thermoelectric material
agpb
sbte
preparation
mixing solutions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2009100726830A
Other languages
Chinese (zh)
Other versions
CN101654747A (en
Inventor
陈刚
王群
王琳
陈大宏
孟祥彬
冷先勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Institute of Technology
Original Assignee
Harbin Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Institute of Technology filed Critical Harbin Institute of Technology
Priority to CN2009100726830A priority Critical patent/CN101654747B/en
Publication of CN101654747A publication Critical patent/CN101654747A/en
Application granted granted Critical
Publication of CN101654747B publication Critical patent/CN101654747B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Powder Metallurgy (AREA)

Abstract

The invention provides a preparation method of an AgPb10SbTe12 thermoelectric material, which relates to a preparation method of thermoelectric materials. The invention solves the problem that the thermoelectric material prepared by the prior method has the defects of high required temperature, expensive and complicated equipment, low product yield and poor thermoelectric performance in the preparation process. The preparation method comprises the following steps: (1) preparing a mixture; (2) preparing a mixed solution; (3) preparing the precursor of the AgPb10SbTe12 thermoelectric material; and (4) filtering, washing and drying the precursor of the AgPb10SbTe12 thermoelectric material. The invention adopts the method synthesized by the hydro-thermal method to achieve the purpose of preparing the AgPb10SbTe12 thermoelectric material under the conditions of low temperature and friendly environment. The product prepared by the invention has high purity, high yield and good thermoelectric performance. The invention has the advantages of cheap price of raw materials, simple processes, simple equipment and low manufacturing cost of the equipment.

Description

A kind of AgPb 10SbTe 12The preparation method of thermoelectric material
Technical field
The present invention relates to a kind of preparation method of thermoelectric material.
Background technology
Since Science in 2004 has reported AgPb mSbTe M+2The system thermoelectric alloy material, so thermoelectricity capability material preferably in high-temperature zone in just becoming is AgPb in recent years mSbTe M+2The system thermoelectric alloy material is applied in the fields such as thermoelectric refrigeration and thermo-electric generation widely.Prepare AgPb at present mSbTe M+2The method of system thermoelectric alloy material is a lot, but the preparation method all exists in temperature required height in the preparation process, apparatus expensive and complexity, obtains the problem of the few and thermoelectricity capability difference of the output of product.
Summary of the invention
The present invention seeks in order to solve thermoelectric material temperature required height in preparation process that existing method is prepared, apparatus expensive and complexity, obtain the problem of the few and thermoelectricity capability difference of the output of product, and a kind of AgPb is provided 10SbTe 12The preparation method of thermoelectric material.
AgPb 10SbTe 12The preparation of thermoelectric material realizes according to the following steps: the AgNO that, takes by weighing 0.22～0.44g 3, 4.6～9.2g Pb (CH 3COO) 23H 2The K of O, 0.40～0.80g (SbO) C 4H 4O 60.5H 2The Na of O and 3.2～6.4g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol, be placed on then and stir 30～60min on the magnetic stirring apparatus, get mixture; Two, KOH is joined in the mixture, and then add the polyvinylpyrrolidone of 0～0.4g, the diamine mixing and stirring of 0.6g, get mixing solutions; Three, mixing solutions has been joined in the teflon-lined autoclave, sealing is thermal treatment 12～24h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10SbTe 12The thermoelectric material precursor; Four, with AgPb 10SbTe 12The thermoelectric material precursor filters, washing 3～5 times, and under temperature was 60 ℃ condition, dry 5～10h promptly got AgPb then 10SbTe 12Thermoelectric material; Wherein KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 10～25: 1 mol ratio; The add-on of mixing solutions is a teflon-lined autoclave volumetrical 60%～80% in the step 3.
The AgPb that the present invention obtains 10SbTe 12Thermoelectric material can obtain the powder of different-shape (cubic and flower-shaped) according to the addition of control polyvinylpyrrolidone; As adding the AgPb that polyvinylpyrrolidone can generate cubic powder in the present invention 10SbTe 12Thermoelectric material is not as adding the AgPb that polyvinylpyrrolidone can generate flower-shaped powder in the present invention 10SbTe 12Thermoelectric material.
The AgPb that the present invention obtains 10SbTe 12Thermoelectric material is the powder of better crystallinity degree, narrow particle size distribution, the AgPb that the present invention obtains 10SbTe 12Thermoelectric material purity is up to more than 99%.
The product favorable dispersity that the present invention obtains need not to grind, and avoided the textural defect that is caused by grinding and introduced impurity, and output reaches more than 98%, and thermoelectricity capability is good.
The AgPb that the present invention adopts Hydrothermal Preparation to go out 10SbTe 12The thermoelectric material generated time is short, and with regard to may command, low and the simple to operate and easy realization of equipment manufacturing cost obtains different pattern materials under cold condition.
Description of drawings
Fig. 1 is products therefrom AgPb in the embodiment 21 10SbTe 12The X-ray diffraction analysis collection of illustrative plates of thermoelectric material, Fig. 2 are embodiment 20 resultant AgPb 10SbTe 12The TEM photo of cube pattern, Fig. 3 is embodiment 20 resultant AgPb 10SbTe 12The EDX power spectrum of cube pattern, Fig. 4 is embodiment 21 resultant AgPb 10SbTe 12The TEM photo of floriform appearance, Fig. 5 are embodiment 21 resultant AgPb 10SbTe 12The EDX power spectrum of cube pattern.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment AgPb 10SbTe 12The preparation of thermoelectric material realizes according to the following steps: the AgNO that, takes by weighing 0.22～0.44g 3, 4.6～9.2g Pb (CH 3COO) 23H 2The K of O, 0.40～0.80g (SbO) C 4H 4O 60.5H 2The Na of O and 3.2～6.4g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol, be placed on then and stir 30～60min on the magnetic stirring apparatus, get mixture; Two, KOH is joined in the mixture, and then add the polyvinylpyrrolidone of 0～0.4g, the diamine mixing and stirring of 0.6g, get mixing solutions; Three, mixing solutions has been joined in the teflon-lined autoclave, sealing is thermal treatment 12～24h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10SbTe 12The thermoelectric material precursor; Four, with AgPb 10SbTe 12The thermoelectric material precursor filters, washing 3～5 times, and under temperature was 60 ℃ condition, dry 5～10h promptly got AgPb then 10SbTe 12Thermoelectric material; Wherein KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 10～25: 1 mol ratio; The add-on of mixing solutions is a teflon-lined autoclave volumetrical 60%～80% in the step 3.
Present embodiment is to adopt the AgPb of hydrothermal method controlledly synthesis cube and floriform appearance 10SbTe 12Powder.Hydrothermal method is as reaction system with the aqueous solution, by reaction system is heated, pressurizes, create a relatively-high temperature, highly compressed reaction environment, make common indissoluble or insoluble substance dissolves and recrystallization prepare material, because reaction is to carry out in the aqueous environment of a sealing, so just can make the novel substance that other method can't prepare under lesser temps, non-pressurized external environment.
Embodiment two: that present embodiment and embodiment one are different is the AgNO that takes by weighing 0.28～0.40g in the step 1 3, 5.8～8.4g Pb (CH 3COO) 23H 2The K of O, 0.50～0.70g (SbO) C 4H 4O 60.5H 2The Na of O and 4.2～5.6g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol.Other step and parameter are identical with embodiment one.
Employed raw material market can be bought in the present embodiment, greatly reduces production cost.
Embodiment three: that present embodiment and embodiment one are different is the AgNO that takes by weighing 0.32g in the step 1 3, 7.4g Pb (CH 3COO) 23H 2The K of O, 0.60g (SbO) C 4H 4O 60.5H 2The Na of O and 4.8g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol.Other step and parameter are identical with embodiment one.
Embodiment four: that present embodiment and embodiment one are different is the AgNO that takes by weighing 0.36g in the step 1 3, 8.2g Pb (CH 3COO) 23H 2The K of O, 0.62g (SbO) C 4H 4O 60.5H 2The Na of O and 5.2g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol.Other step and parameter are identical with embodiment one.
Embodiment five: present embodiment and embodiment one to four are different be in the step 1 in the step 1 churning time be 40～50min.Other step and parameter are identical with embodiment one to four.
Embodiment six: present embodiment and embodiment one to four are different be in the step 1 in the step 1 churning time be 45min.Other step and parameter are identical with embodiment one to four.
Embodiment seven: what present embodiment was different with embodiment five or six is that stirring velocity is 4000～8000r/min in the step 1.Other step and parameter are identical with embodiment five or six.
Embodiment eight: what present embodiment was different with embodiment five or six is that stirring velocity is 5000～7000r/min in the step 1.Other step and parameter are identical with embodiment one.
Embodiment nine: what present embodiment was different with embodiment five or six is that stirring velocity is 6000r/min in the step 1.Other step and parameter are identical with embodiment five or six.
Embodiment ten: present embodiment and embodiment one, two, three, four, seven, eight or nine are different is that the add-on of polyvinylpyrrolidone in the step 2 is 0.1～0.3g.Other step and parameter are identical with embodiment one.
Embodiment 11: present embodiment and embodiment one, two, three, four, seven, eight or nine are different is that the add-on of polyvinylpyrrolidone in the step 2 is 0.2g.Other step and parameter are identical with embodiment one.
Embodiment 12: that present embodiment is different with embodiment ten or 11 is KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 14～18: 1 mol ratio.Other step and parameter are identical with embodiment ten or 11.
Embodiment 13: that present embodiment is different with embodiment ten or 11 is KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 16: 1 mol ratio.Other step and parameter are identical with embodiment ten or 11.
Embodiment 14: what present embodiment and embodiment one, two, three, four, seven, eight, nine, 12 or 13 were different is that heat treatment time is 14～20h in the step 3.Other step and parameter are identical with embodiment one, two, three, four, seven, eight, nine, 12 or 13.
Embodiment 15: what present embodiment and embodiment one, two, three, four, seven, eight, nine, 12 or 13 were different is that heat treatment time is 16h in the step 3.Other step and parameter are identical with embodiment one, two, three, four, seven, eight, nine, 12 or 13.
Embodiment 16: present embodiment is different with embodiment 14 or 15 is that the add-on of mixing solutions in the step 3 is a teflon-lined autoclave volumetrical 65%～75%.Other step and parameter are identical with embodiment 14 or 15.
Embodiment 17: present embodiment is different with embodiment 14 or 15 is that the add-on of mixing solutions in the step 3 is a teflon-lined autoclave volumetrical 70%.Other step and parameter are identical with embodiment 14 or 15.
Embodiment 18: what present embodiment and embodiment one, two, three, four, seven, eight, nine, 12,13,16 or 17 were different is that washing times is 4 times in the step 4.Other step and parameter are identical with embodiment one, two, three, four, seven, eight, nine, 12,13,16 or 17.
Embodiment 19: present embodiment and embodiment 18 are different be in the step 4 time of drying be 6～9h.Other step and parameter are identical with embodiment 18.
Embodiment 20: present embodiment and embodiment 18 are different be in the step 4 time of drying be 8h.Other step and parameter are identical with embodiment 18.
Embodiment 21: present embodiment AgPb 10SbTe 12The preparation of thermoelectric material realizes according to the following steps: the AgNO that, takes by weighing 0.30g 3, 4.8g Pb (CH 3COO) 23H 2The K of O, 0.56g (SbO) C 4H 4O 60.5H 2The Na of O and 4.8g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol, be placed on then and stir 40min on the magnetic stirring apparatus, get mixture; Two, KOH is joined in the mixture, add the diamine mixing and stirring of 0.6g then, get mixing solutions; Three, mixing solutions has been joined in the teflon-lined autoclave, sealing is thermal treatment 18h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10SbTe 12The thermoelectric material precursor; Four, with AgPb 10SbTe 12The thermoelectric material precursor filters, washing 4 times, and under temperature was 60 ℃ condition, dry 8h promptly got AgPb then 10SbTe 12Thermoelectric material; Wherein KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 16: 1 mol ratio; The add-on of mixing solutions is a teflon-lined autoclave volumetrical 70% in the step 3.
The AgPb that adopts present embodiment to prepare 10SbTe 12Thermoelectric material is a meal, and the AgPb that obtains of present embodiment 10SbTe 12The pattern of thermoelectric material is flower-shaped particle.
The AgPb that present embodiment obtains 10SbTe 12The thermoelectric material agent is 99.48% through recording purity.
The AgPb that present embodiment obtains 10SbTe 12The X-ray diffraction analysis of thermoelectric material (XRD) collection of illustrative plates as shown in Figure 1, as can be seen from Figure 1 present embodiment gained AgPb 10SbTe 12Thermoelectric material has the cubic plane core structure and does not contain impurity.
The AgPb that present embodiment obtains 10SbTe 12The TEM photo of thermoelectric material as shown in Figure 2, as can be seen from Figure 2 present embodiment gained AgPb 10SbTe 12The perfection of thermoelectric material crystal formation, particle size dispersion is even and be cubic, the about 100nm of the cubes length of side.
The AgPb that present embodiment obtains 10SbTe 12The EDX power spectrum of thermoelectric material as shown in Figure 3, Zhi Bei AgPb as can be seen from Figure 3 10SbTe 12Thermoelectric material contains Ag, Pb, four kinds of elements of Sb, Te.
Embodiment 22: present embodiment AgPb 10SbTe 12The preparation of thermoelectric material realizes according to the following steps: the AgNO that, takes by weighing 0.30g 3, 4.8g Pb (CH 3COO) 23H 2The K of O, 0.56g (SbO) C 4H 4O 60.5H 2The Na of O and 4.8g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol, be placed on then and stir 40min on the magnetic stirring apparatus, get mixture; Two, KOH is joined in the mixture, and then add the polyvinylpyrrolidone of 0.2g, the diamine mixing and stirring of 0.6g, get mixing solutions; Three, mixing solutions has been joined in the teflon-lined autoclave, sealing is thermal treatment 18h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10SbTe 12The thermoelectric material precursor; Four, with AgPb 10SbTe 12The thermoelectric material precursor filters, washing 4 times, and under temperature was 60 ℃ condition, dry 8h promptly got AgPb then 10SbTe 12Thermoelectric material; Wherein KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 16: 1 mol ratio; The add-on of mixing solutions is a teflon-lined autoclave volumetrical 70% in the step 3.
The AgPb that adopts present embodiment to prepare 10SbTe 12Thermoelectric material is a meal, and the AgPb that obtains of present embodiment 10SbTe 12The pattern of thermoelectric material is a cube particle.
The AgPb that present embodiment obtains 10SbTe 12The thermoelectric material agent is 99.52% through recording purity.
The AgPb that present embodiment obtains 10SbTe 12The TEM photo of thermoelectric material as shown in Figure 2, as can be seen from Figure 4 present embodiment gained AgPb 10SbTe 12The perfection of thermoelectric material crystal formation, particle size dispersion evenly and have the flower-shaped particle of eight hemp nettle lobes, and the length of every hemp nettle lobe is at 1～1.5 μ m.
The AgPb that present embodiment obtains 10SbTe 12The EDX power spectrum of thermoelectric material as shown in Figure 5, Zhi Bei AgPb as can be seen from Figure 3 10SbTe 12Thermoelectric material contains Ag, Pb, four kinds of elements of Sb, Te.

Claims (10)

1. AgPb 10SbTe 12The preparation method of thermoelectric material is characterized in that AgPb 10SbTe 12The preparation of thermoelectric material realizes according to the following steps: the AgNO that, takes by weighing 0.22～0.44g 3, 4.6～9.2g Pb (CH 3COO) 23H 2The K of O, 0.40～0.80g (SbO) C 4H 4O 60.5H 2The Na of O and 3.2～6.4g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol, be placed on then and stir 30～60min on the magnetic stirring apparatus, get mixture; Two, KOH is joined in the mixture, and then add the polyvinylpyrrolidone of 0～0.4g, the diamine mixing and stirring of 0.6g, get mixing solutions; Three, mixing solutions has been joined in the teflon-lined autoclave, sealing is thermal treatment 12～24h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10SbTe 12The thermoelectric material precursor; Four, with AgPb 10SbTe 12The thermoelectric material precursor filters, washing 3～5 times, and under temperature was 60 ℃ condition, dry 5～10h promptly got AgPb then 10SbTe 12Thermoelectric material; Wherein KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 10～25: 1 mol ratio; The add-on of mixing solutions is a teflon-lined autoclave volumetrical 60%～80% in the step 3.
2. a kind of AgPb according to claim 1 10SbTe 12The preparation method of thermoelectric material is characterized in that taking by weighing in the step 1 AgNO of 0.28～0.40g 3, 5.8～8.4g Pb (CH 3COO) 23H 2The K of O, 0.50～0.70g (SbO) C 4H 4O 60.5H 2The Na of O and 4.2～5.6g 2TeO 3Be dissolved in the mixing solutions of 4mL deionized water and 6mL alcohol.
3. a kind of AgPb according to claim 1 and 2 10SbTe 12The preparation method of thermoelectric material is characterized in that churning time is 40～50min in the step 1.
4. a kind of AgPb according to claim 3 10SbTe 12The preparation method of thermoelectric material is characterized in that stirring velocity is 4000～8000r/min in the step 1.
5. according to claim 1,2 or 4 described a kind of AgPb 10SbTe 12The preparation method of thermoelectric material, the add-on that it is characterized in that polyvinylpyrrolidone in the step 2 is 0.1～0.3g.
6. a kind of AgPb according to claim 5 10SbTe 12The preparation method of thermoelectric material is characterized in that KOH and Pb (CH in the step 2 3COO) 23H 2O adds KOH by 14～18: 1 mol ratio.
7. according to claim 1,2,4 or 6 described a kind of AgPb 10SbTe 12The preparation method of thermoelectric material is characterized in that heat treatment time is 14～20h in the step 3.
8. a kind of AgPb according to claim 7 10SbTe 12The preparation method of thermoelectric material, the add-on that it is characterized in that mixing solutions in the step 3 are teflon-lined autoclave volumetrical 65%～75%.
9. according to claim 1,2,4,6 or 8 described a kind of AgPb 10SbTe 12The preparation method of thermoelectric material is characterized in that washing times is 4 times in the step 4.
10. a kind of AgPb according to claim 9 10SbTe 12The preparation method of thermoelectric material is characterized in that be 6～9h time of drying in the step 4.
CN2009100726830A 2009-08-14 2009-08-14 Preparation method of AgPb10SbTe12 thermoelectric material Expired - Fee Related CN101654747B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009100726830A CN101654747B (en) 2009-08-14 2009-08-14 Preparation method of AgPb10SbTe12 thermoelectric material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009100726830A CN101654747B (en) 2009-08-14 2009-08-14 Preparation method of AgPb10SbTe12 thermoelectric material

Publications (2)

Publication Number Publication Date
CN101654747A CN101654747A (en) 2010-02-24
CN101654747B true CN101654747B (en) 2011-01-05

Family

ID=41709196

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009100726830A Expired - Fee Related CN101654747B (en) 2009-08-14 2009-08-14 Preparation method of AgPb10SbTe12 thermoelectric material

Country Status (1)

Country Link
CN (1) CN101654747B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101906665B (en) * 2010-09-09 2011-12-28 哈尔滨工业大学 Method for preparing silver-lead-lanthanum-tellurium thermoelectric material
CN102583274B (en) * 2012-03-30 2014-04-02 哈尔滨工业大学 Method for preparing silver telluride thermoelectric material by using ordinary pressure microwave synthesis method
CN115285945A (en) * 2022-08-04 2022-11-04 安徽工程大学 Antimony-silver ditelluride nanocrystal and phosphine-free liquid phase synthesis method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6596226B1 (en) * 1999-08-27 2003-07-22 5Nplus Inc. Process for producing thermoelectric material and thermoelectric material thereof
EP1930960A1 (en) * 2006-12-04 2008-06-11 Aarhus Universitet Use of thermoelectric materials for low temperature thermoelectric purposes
CN101486450A (en) * 2008-10-21 2009-07-22 同济大学 Preparation of lead telluride base block thermoelectric material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6596226B1 (en) * 1999-08-27 2003-07-22 5Nplus Inc. Process for producing thermoelectric material and thermoelectric material thereof
EP1930960A1 (en) * 2006-12-04 2008-06-11 Aarhus Universitet Use of thermoelectric materials for low temperature thermoelectric purposes
CN101486450A (en) * 2008-10-21 2009-07-22 同济大学 Preparation of lead telluride base block thermoelectric material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JP特开2002-270907A 2002.09.20
Lin Wang, Gang Chen, Qun Wang, Hongjie Zhang, Rencheng Jin, Dah.Shape-Controlled Synthesis and Electrical Conductivities of AgPb10SbTe12 Materials.《phys.chem.c》.2010,第114卷(第13期),5827-5834. *

Also Published As

Publication number Publication date
CN101654747A (en) 2010-02-24

Similar Documents

Publication Publication Date Title
CN105417570B (en) Method for preparing spinel-type complex oxide through co-precipitation, homogenization and spray drying
Bhavani et al. Okra (Abelmoschus esculentus) plant extract-assisted combustion synthesis and characterization studies of spinel ZnAl2O4 nano-catalysts
CN102211790B (en) Salicylate intercalation layered metal hydroxide nano rod and preparation method thereof
CN102180509B (en) Method for preparing hollow CuO/Cu2O spheres with controllable ingredients
CN101654747B (en) Preparation method of AgPb10SbTe12 thermoelectric material
CN101602944A (en) A kind of production method of rare earth ion doped yttrium aluminum garnet nano phosphor powder
CN102583499A (en) Preparation method for cuprous oxide micron/nano crystal with controllable morphology
CN101157483B (en) Transition metal composite oxides preparation method
CN101913575B (en) Method for preparing In4Se3 thermoelectric compound powder
CN104031647A (en) Preparation method for circular disk-like europium-doped lanthanum vanadate red phosphors
CN103121665A (en) Three-dimensional flower-like salicylic acid radical intercalation layered hydroxide nano material and preparation method thereof
CN101759162B (en) Low-temperature liquid phase synthesizing method of monodisperse square crystalline phase ferrous selenide square nanometer sheet
CN103740366A (en) Method for preparing bread-ring-like CaMoO4 and Eu<3+> doped CaMoO4 luminous materials
CN113461054B (en) BiOCl powder and preparation method and application thereof
CN101412544B (en) Preparation of layered cobalt oxide
CN101906665B (en) Method for preparing silver-lead-lanthanum-tellurium thermoelectric material
CN104108739A (en) Preparation method of particle size-controllable spherical copper oxide
CN101914812B (en) Method for preparing silver-lead-bismuth-tellurium thermoelectric material
CN102309962A (en) Preparation method of data cake-shaped Bi2W0.5Mo0.5O6 nanometer powder
CN105218076B (en) One kind prepares SrMnO using sol-gal process3The method of ceramic powder
CN102730760A (en) Preparation method of 1*1-type manganese oxide octahedral molecular sieves
CN102502763B (en) Method for preparing lanthanum copper oxide (La2CuO4) powder by sol gel-ultrasonic chemical method
CN101559968A (en) Preparation method of high-purity nano yttrium-based oxide powder
CN101654228A (en) Preparation method of nano-Cu7Te4 semiconductor material
CN103449512A (en) Method for preparing monodisperse and cuboid nano-barium titanate powder by virtue of microwave hydrothermal method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20110105

Termination date: 20110814