CN101914812A - Method for preparing silver-lead-bismuth-tellurium thermoelectric material - Google Patents

Method for preparing silver-lead-bismuth-tellurium thermoelectric material Download PDF

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CN101914812A
CN101914812A CN 201010276952 CN201010276952A CN101914812A CN 101914812 A CN101914812 A CN 101914812A CN 201010276952 CN201010276952 CN 201010276952 CN 201010276952 A CN201010276952 A CN 201010276952A CN 101914812 A CN101914812 A CN 101914812A
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thermoelectric material
bismuth
lead
silver
preparation
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CN101914812B (en
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陈刚
王群
陈大宏
王琳
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention discloses a method for preparing a silver-lead-bismuth-tellurium thermoelectric material, which relates to a method for preparing a thermoelectric material and solves the problems of high temperature required for preparing the conventional thermoelectric material, expensive raw materials, low yield and disadvantage of expanded production. The method comprises the following steps of: 1, preparing a mixture A; 2, preparing mixed solution B; 3, preparing a AgPb10BiTe12 thermoelectric material precursor; and 4, filtering and washing the AgPb10BiTe12 thermoelectric material precursor, and then drying the AgPb10BiTe12 thermoelectric material precursor in vacuum to obtain the silver-lead-bismuth-tellurium thermoelectric material. The method does not need high temperature, the used raw materials are simple and easily obtained, the obtained AgPb10BiTe12 thermoelectric material is powder with good crystallinity and narrow particle size distribution, the purity of the AgPb10BiTe12 thermoelectric material reaches over 99 percent, and the method is favorable for expanded production.

Description

The preparation method of a kind of silver-lead-bismuth-tellurium thermoelectric material
Technical field
The present invention relates to a kind of preparation method of thermoelectric material.
Background technology
In April, 2008, reported on the Chem.Mater. about synthesizing Ag with solid phase method 1-xPb 18MTe 20(M=Bi, article Sb), wherein Ag 1-xPb 18BiTe 20The ZT value a little less than Ag 1-xPb 18SbTe 20, very big application prospect is arranged.Prepare AgPb at present mBiTe M+2The method of system thermoelectric alloy material is mainly solid phase method, and the preparation method exists in temperature required height in the preparation process, and reaction raw materials is metal simple-substance, and apparatus expensive and complexity, the output that obtains product are few, is unfavorable for enlarging the shortcoming of production.
Summary of the invention
The objective of the invention is in order to solve the temperature required height of existing preparation thermoelectric material, raw material costliness, output fewly, be unfavorable for enlarging the problem of production, the preparation method of a kind of silver-lead-bismuth-tellurium thermoelectric material is provided.
The preparation method of a kind of silver-lead of the present invention-bismuth-tellurium thermoelectric material is as follows: one, with 0～0.2g polyvinylpyrrolidone, 0.01～0.03g AgNO 3, 0.4～0.5g Pb (CH 3COO) 23H 2O, 0.05～0.07g Bi (NO 3) 35H 2O and 0.3～0.4gNa 2TeO 3Be dissolved in 8～11mL deionized water, the stirring velocity with 4000～8000r/min stirs 30～60min on magnetic stirring apparatus then, gets mixture A; Two, 0～2.0gKOH and 0.2～0.5g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 12～24h under 110 ℃～210 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 3～6 times, then under temperature is 60 ℃ condition, and vacuum-drying 5～10h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material (AgPb 10BiTe 12Thermoelectric material); The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 60%～80% in the step 3.
The temperature required high temperature that do not need of the inventive method, used starting material are simple and easy to, the AgPb that obtains 10BiTe 12Thermoelectric material is the powder of better crystallinity degree, narrow particle size distribution, AgPb 10BiTe 12Thermoelectric material purity helps enlarging and produces up to more than 99%.
The good product dispersibility that the present invention obtains need not to grind, and textural defect and the impurity having avoided being caused by grinding are introduced, and good thermoelectricity capability is arranged.
The AgPb that the present invention adopts Hydrothermal Preparation to go out 10BiTe 12Thermoelectric material synthesis condition gentleness, pollution-free, the time is short, and equipment manufacturing cost is low, and is simple to operate and realize that easily the control of different-shape material is synthetic.
The AgPb that the present invention obtains 10BiTe 12Thermoelectric material can obtain the powder of different-shape (eight hemp nettle shapes of zig-zag petal and eight hemp nettle shapes of smooth petal) according to the addition of control polyvinylpyrrolidone; In the process of preparation, add the AgPb that polyvinylpyrrolidone can generate eight hemp nettle shape powders of zig-zag petal 10BiTe 12Thermoelectric material does not add the AgPb that polyvinylpyrrolidone can generate cubic powder in the process of preparation 10BiTe 12Thermoelectric material.
Description of drawings
Fig. 1 is embodiment 18 gained AgPb 10BiTe 12The XRD figure spectrum of thermoelectric material; Fig. 2 is embodiment 18 gained AgPb 10BiTe 12The SEM photo of thermoelectric material; Fig. 3 is embodiment 18 gained AgPb 10BiTe 12The EDS energy spectrogram of thermoelectric material; Fig. 4 is embodiment 19 gained AgPb 10BiTe 12The XRD figure spectrum of thermoelectric material; Fig. 5 is embodiment 19 gained AgPb 10BiTe 12The SEM photo of thermoelectric material; Fig. 6 is embodiment 19 gained AgPb 10BiTe 12The EDS of thermoelectric material can spectrogram.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0～0.2g polyvinylpyrrolidone, 0.01～0.03g AgNO 3, 0.4～0.5g Pb (CH 3COO) 23H 2O, 0.05～0.07gBi (NO 3) 35H 2O and 0.3～0.4g Na 2TeO 3Be dissolved in 8～11mL deionized water, the stirring velocity with 4000～8000r/min stirs 30～60min on magnetic stirring apparatus then, gets mixture A; Two, 0～2.0gKOH and 0.2～0.5g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 12～24h under 110 ℃～210 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 3～6 times, then under temperature is 60 ℃ condition, and vacuum-drying 5～10h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being 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 10BiTe 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.
Employed raw material market can be bought in the present embodiment, greatly reduces production cost.
Embodiment two: what present embodiment and embodiment one were different is with 0.2g polyvinylpyrrolidone, 0.02g AgNO in the step 1 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in 8～11mL deionized water.Other is identical with embodiment one.
Embodiment three: what present embodiment was different with one of embodiment one or two is with 0.2g polyvinylpyrrolidone, 0.02g AgNO in the step 1 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32gNa 2TeO 3Be dissolved in the 10mL deionized water.Other is identical with one of embodiment one or two.
Embodiment four: what present embodiment was different with one of embodiment one to three is that the churning time described in the step 1 is 40～50min.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is different with one of embodiment one to four is that the add-on of KOH in the step 2 is 0.5g～1.5g.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different with one of embodiment one to five is that thermal treatment temp is 120 ℃～200 ℃ in the step 3.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different with one of embodiment one to six is that heat treatment time is 14～20h in the step 3.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is different with one of embodiment one to seven is that the add-on of mixing solutions B in the step 3 is for there being teflon-lined autoclave volumetrical 65%～75%.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is that washing times is 4 times in the step 4.Other is identical with one of embodiment one to eight.
Embodiment ten: present embodiment is different with one of embodiment one to nine be in the step 4 time of drying be 6～9h.Other is identical with one of embodiment one to nine.
Embodiment 11: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.01g AgNO 3, 0.4g Pb (CH 3COO) 23H 2O, 0.05g Bi (NO 3) 35H 2O and 0.3g Na 2TeO 3Be dissolved in the 8mL deionized water, the stirring velocity with 4000r/min stirs 30min on magnetic stirring apparatus then, gets mixture A; Two, the 0.2g diamine is joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 12h under 110 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 3 times, then under temperature is 60 ℃ condition, and vacuum-drying 5h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 60% in the step 3.
Embodiment 12: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.03g AgNO 3, 0.5g Pb (CH 3COO) 23H 2O, 0.07g Bi (NO 3) 35H 2O and 0.4g Na 2TeO 3Be dissolved in the 11mL deionized water, the stirring velocity with 8000r/min stirs 60min on magnetic stirring apparatus then, gets mixture A; Two, 2.0gKOH and 0.5g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 24h under 210 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 6 times, then under temperature is 60 ℃ condition, and vacuum-drying 10h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 80% in the step 3.
Embodiment 13: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in the 9mL deionized water, the stirring velocity with 6000r/min stirs 40min on magnetic stirring apparatus then, gets mixture A; Two, 1.0gKOH and 0.3g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 13h under 120 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 4 times, then under temperature is 60 ℃ condition, and vacuum-drying 6h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 70% in the step 3.
Embodiment 14: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.45g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.35g Na 2TeO 3Be dissolved in the 10mL deionized water, the stirring velocity with 7000r/min stirs 40min on magnetic stirring apparatus then, gets mixture A; Two, 1.0gKOH and 0.4g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 14h under 130 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 5 times, then under temperature is 60 ℃ condition, and vacuum-drying 7h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 65% in the step 3.
Embodiment 15: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.4g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.3g Na 2TeO 3Be dissolved in the 10mL deionized water, the stirring velocity with 7000r/min stirs 40min on magnetic stirring apparatus then, gets mixture A; Two, 1.5gKOH and 0.4g diamine are joined among the mixture A, stir, get mixing solutions B;
Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 18h under 160 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 6 times, then under temperature is 60 ℃ condition, and vacuum-drying 9h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 68% in the step 3.
Embodiment 16: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in 8～11mL deionized water, the stirring velocity with 5000～7000r/min stirs 50min on magnetic stirring apparatus then, gets mixture A; Two, 0.5g～1.5g KOH and 0.3～0.4g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 20h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 3～6 times, then under temperature is 60 ℃ condition, and vacuum-drying 6h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 69%～72% in the step 3.
Embodiment 17: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.01g AgNO 3, 0.4g Pb (CH 3COO) 23H 2O, 0.07g Bi (NO 3) 35H 2O and 0.4g Na 2TeO 3Be dissolved in the 11mL deionized water, the stirring velocity with 4000～8000r/min stirs 50min on magnetic stirring apparatus then, gets mixture A; Two, 0.5g～1.5g KOH and 0.3～0.4g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 20h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 3～6 times, then under temperature is 60 ℃ condition, and vacuum-drying 5～10h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 62%～76% in the step 3.
Embodiment 18: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in the 10mL deionized water, the stirring velocity with 6000r/min stirs 45min on magnetic stirring apparatus then, gets mixture A; Two, 0.9gKOH and 0.3g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 20h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 4 times, then under temperature is 60 ℃ condition, and vacuum-drying 6h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material (AgPb 10BiTe 12Thermoelectric material); The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 75% in the step 3.
The AgPb that adopts present embodiment to prepare 10BiTe 12Thermoelectric material is a meal, and the AgPb that obtains of present embodiment 10BiTe 12The pattern of thermoelectric material is eight hemp nettle shapes of zig-zag petal.
The AgPb that present embodiment obtains 10BiTe 12Thermoelectric material is 99.57% through recording purity.
The AgPb that present embodiment obtains 10BiTe 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 10BiTe 12Thermoelectric material has NaCl profile heart cubic structure and does not contain impurity.
The AgPb that present embodiment obtains 10BiTe 12The SEM photo of thermoelectric material as shown in Figure 2, as can be seen from Figure 2 present embodiment gained AgPb 10BiTe 12The thermoelectric material crystallization is better, and particle size dispersion is than eight hemp nettle shapes of even and indention petal, and petal is along＜111〉crystal orientation growths, and petal length is about 1 μ m.
The AgPb that present embodiment obtains 10BiTe 12The EDS power spectrum of thermoelectric material as shown in Figure 3, Zhi Bei AgPb as can be seen from Figure 3 10BiTe 12Thermoelectric material contains Ag, Pb, four kinds of elements of Bi, Te.
Embodiment 19: the preparation method of a kind of silver-lead in the present embodiment-bismuth-tellurium thermoelectric material is as follows: one, with 0.02g AgNO 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in the 10mL deionized water, the stirring velocity with 6000r/min stirs 45min on magnetic stirring apparatus then, gets mixture A; Two, 0.9gKOH and 0.3g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 20h under 180 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 4 times, then under temperature is 60 ℃ condition, and vacuum-drying 6h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material (AgPb 10BiTe 12Thermoelectric material); The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 75% in the step 3.
The AgPb that adopts present embodiment to prepare 10BiTe 12Thermoelectric material is a meal, and the AgPb that obtains of present embodiment 10BiTe 12The pattern of thermoelectric material is eight hemp nettle shapes of smooth petal.
The AgPb that present embodiment obtains 10BiTe 12Thermoelectric material is 99.42% through recording purity.
The AgPb that present embodiment obtains 10BiTe 12The X-ray diffraction analysis of thermoelectric material (XRD) collection of illustrative plates as shown in Figure 4, as can be seen from Figure 4 present embodiment gained AgPb 10BiTe 12Thermoelectric material has NaCl profile heart cubic structure and does not contain impurity.
The AgPb that present embodiment obtains 10BiTe 12The SEM photo of thermoelectric material as shown in Figure 5, as can be seen from Figure 5 present embodiment gained AgPb 10BiTe 12Thermoelectric material crystallization perfection, particle size dispersion evenly are the particles with eight hemp nettle shapes of smooth petal, and each petal is along the dendrite of＜111〉crystal orientation growths, and it is 1.5 μ m that every hemp nettle lobe is about.
The AgPb that present embodiment obtains 10BiTe 12The EDS power spectrum of thermoelectric material as shown in Figure 6, Zhi Bei AgPb as can be seen from Figure 6 10BiTe 12Thermoelectric material contains Ag, Pb, four kinds of elements of Bi, Te.

Claims (10)

1. the preparation method of silver-lead-bismuth-tellurium thermoelectric material is characterized in that the preparation method of a kind of silver-lead-bismuth-tellurium thermoelectric material is as follows: one, with 0～0.2g polyvinylpyrrolidone, 0.01～0.03g AgNO 3, 0.4～0.5gPb (CH 3COO) 23H 2O, 0.05～0.07g Bi (NO 3) 35H 2O and 0.3～0.4g Na 2TeO 3Be dissolved in 8～11mL deionized water, the stirring velocity with 4000～8000r/min stirs 30～60min on magnetic stirring apparatus then, gets mixture A; Two, 0～2.0gKOH and 0.2～0.5g diamine are joined among the mixture A, stir, get mixing solutions B; Three, mixing solutions B has been joined in the teflon-lined autoclave, sealing is thermal treatment 12～24h under 110 ℃～210 ℃ the condition in temperature then, naturally cools to room temperature, AgPb 10BiTe 12The thermoelectric material precursor; Four, with AgPb 10BiTe 12The thermoelectric material precursor filters also and washs 3～6 times, then under temperature is 60 ℃ condition, and vacuum-drying 5～10h, i.e. De Yin-lead-bismuth-tellurium thermoelectric material; The add-on of mixing solutions B is for there being teflon-lined autoclave volumetrical 60%～80% in the step 3.
2. according to the preparation method of the described a kind of silver-lead of claim 1-bismuth-tellurium thermoelectric material, it is characterized in that in the step 1 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in 8～11mL deionized water.
3. according to the preparation method of the described a kind of silver-lead of claim 2-bismuth-tellurium thermoelectric material, it is characterized in that in the step 1 0.2g polyvinylpyrrolidone, 0.02g AgNO 3, 0.44g Pb (CH 3COO) 23H 2O, 0.06g Bi (NO 3) 35H 2O and 0.32g Na 2TeO 3Be dissolved in the 10mL deionized water.
4. according to the preparation method of claim 1 or 2 described a kind of silver-lead-bismuth-tellurium thermoelectric materials, it is characterized in that the churning time described in the step 1 is 40～50min.
5. according to the preparation method of the described a kind of silver-lead of claim 4-bismuth-tellurium thermoelectric material, the add-on that it is characterized in that KOH in the step 2 is 0.5g～1.5g.
6. according to the preparation method of claim 1,2 or 5 described a kind of silver-lead-bismuth-tellurium thermoelectric materials, it is characterized in that thermal treatment temp is 120 ℃～200 ℃ in the step 3.
7. according to the preparation method of the described a kind of silver-lead of claim 6-bismuth-tellurium thermoelectric material, it is characterized in that heat treatment time is 14～20h in the step 3.
8. according to the preparation method of claim 1,2,5 or 7 described a kind of silver-lead-bismuth-tellurium thermoelectric materials, the add-on that it is characterized in that mixing solutions B in the step 3 is for there being teflon-lined autoclave volumetrical 65%～75%.
9. the preparation method of described according to Claim 8 a kind of silver-lead-bismuth-tellurium thermoelectric material is characterized in that washing times is 4 times in the step 4.
10. according to the preparation method of claim 1,2,5,7 or 9 described a kind of silver-lead-bismuth-tellurium thermoelectric materials, it is characterized in that be 6～9h time of drying in the step 4.
CN2010102769528A 2010-09-09 2010-09-09 Method for preparing silver-lead-bismuth-tellurium thermoelectric material Expired - Fee Related CN101914812B (en)

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