CN1796271A - Method for preparing Nano lead telluride doped with silver and stibium or silver and bismuth - Google Patents
Method for preparing Nano lead telluride doped with silver and stibium or silver and bismuth Download PDFInfo
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- CN1796271A CN1796271A CN 200410099007 CN200410099007A CN1796271A CN 1796271 A CN1796271 A CN 1796271A CN 200410099007 CN200410099007 CN 200410099007 CN 200410099007 A CN200410099007 A CN 200410099007A CN 1796271 A CN1796271 A CN 1796271A
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- silver
- bismuth
- antimony
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Abstract
This invention refers a method to prepare lead telluride based thermoelectrical material. The preparation of lead telluride thermoelectrical material AgnPbMnTe1+2n in the presence of nanosilver and nanoantimony or silver and bismuth adulterant is as follows: Te powder was added to deionized water of silver, lead, antimony nitrate or bismuth chloride or nitrate, followed by adding reducing agent, then heated to 100-200 DEG C, and it is not allowed to cool the mixture to room temperature until keeping warm for 1-20 hours. After filtration and dryness in vacuum, the desire product was obtained. The mol ratio of silver, lead, antimony nitrate or bismuth chloride or nitrate, Te powder, reducing agent respectively was n:1:n:1+2n:2+4n, 0<=n<=0.2. The material used in this invention is easy to obtain, low temperature was adopted, and the technology and the requirement of equipment is simple, what's more, the granularity of thermoelectrical material is very fine with high purification.
Description
Technical field
The present invention relates to a kind of preparation method of thermoelectric material, relate in particular to the preparation method of a kind of lead telluride for the thermoelectric material of base.
Background technology
The pyroelectric material Ag that has the excellent heat electrical property at present
nPbM
nTe
1+2nThe preparation of (M is Sb or Bi) is that to adopt corresponding simple substance be raw material, obtains in middle temperature (450 ℃) long heat treatment by after high temperature (850 ℃) fusion a few hours, as " science " 303 (2004) 818-821 (Science again, 303 (2004) 818-821, K.F.Hsu, et al, Cubic AgPb
mSbTe
2+mBulk thermoelectric materials with high figure of merit).There are shortcomings such as the temperature height, the raw material that need employing are expensive in its preparation method, and therefore the preparation method of existing above-mentioned thermoelectric material haves much room for improvement.
Summary of the invention
Purpose of the present invention just provides that a kind of raw material cheaply is easy to get, equipment is simple, synthesis temperature is low, and the simple lead telluride of technology is the pyroelectric material Ag of base
nPbM
nTe
1+2nThe preparation method of (M is Sb or Bi).
Nanometer-level silver and antimony or silver and the adulterated lead telluride pyroelectric material Ag of bismuth among the present invention
nPbM
nTe
1+2nThe preparation method of (wherein 0≤n≤0.2, M is Sb or Bi) is as follows:
(1), the tellurium powder is joined in the deionized water solution of the chlorate of Silver Nitrate, lead, antimony or bismuth or nitrate, add reductive agent again, wherein the mol ratio of the chlorate of Silver Nitrate, lead, antimony or bismuth or nitrate, tellurium powder, reductive agent is respectively n: 1: n: 1+2n: 2+4n, 0≤n≤0.2;
(2), be heated to 1-20 hour postcooling of 100-200 ℃ of insulation to room temperature;
(3), will carry out vacuum drying treatment behind the product filtration washing, can obtain nanometer-level silver and antimony or silver and the adulterated lead telluride thermoelectric material of bismuth.
Reaction vessel among the present invention needs corrosion-resistant and High Temperature High Pressure, is preferably polytetrafluoroethyltank tank.
Reductive agent described in the present invention is alkali-metal hydroborate or diamine, is preferably sodium borohydride or POTASSIUM BOROHYDRIDE.
Cleaning step described in the present invention is that the product washing is extremely neutral, preferably adopts dilute hydrochloric acid or rare nitric acid, deionized water, dehydrated alcohol alternately to clean described product repeatedly until being neutral.
Vacuum drying treatment condition described in the present invention is vacuum tightness＜133Pa, and temperature is a room temperature, 2～6 hours time.
Beneficial effect of the present invention: the present invention adopts the chlorate or the nitrate of Silver Nitrate, lead, antimony or bismuth, and raw material cheaply is easy to get.The temperature that the present invention adopts is 100-200 ℃, thereby synthesis temperature is reduced greatly, and equipment requirements is simplified, and technology is easier.The lead telluride that the present invention produces is that the thermoelectric material granularity of base only is several nanometers～tens nanometers, product fine size, purity height.
Description of drawings
The Ag that Fig. 1 the present invention produces
0.05PbSb
0.05Te
1.1The transmission electron microscope of powder shows powder particle size 15nm as synoptic diagram 1 among the figure.
The Ag that Fig. 2 the present invention produces
0.05PbBi
0.05Te
1.1The transmission electron microscope of powder shows powder particle size 25nm as synoptic diagram 2 among the figure.
Embodiment
Be described in further detail below in conjunction with example, the example of being lifted below being to be understood that does not comprise all the elements of the present invention just in order to explain the present invention:
Embodiment 1
Preparation Ag
nPbM
nTe
1+2nN=0 is PbTe
Take by weighing lead nitrate and simple substance tellurium powder and be 0.00597 mole, the tellurium powder is put into polytetrafluoroethyltank tank, lead nitrate is added in the polytetrafluoroethyltank tank after with deionized water dissolving, in polytetrafluoroethyltank tank, add 0.01194 mole of sodium borohydride again, add deionized water in the polytetrafluoroethyltank tank and make the 80-90% that reaches the tetrafluoroethylene tank volume, add a cover be placed in the autoclave airtight.Autoclave is put into stove be heated to 10 hours postcooling of 100 ℃ of insulations to room temperature; Product is filtered with funnel, and replace wash products repeatedly until being neutral with dilute hydrochloric acid, deionized water, dehydrated alcohol.With after filtration the washing product in vacuum drying oven in vacuum tightness＜133Pa, room temperature treatment 4 hours, get final product the PbTe thermoelectric material.Recording its median size is 8nm.
Implementation column 2
Preparation Ag
nPbM
nTe
1+2n, M is Sb, n=0.05, i.e. Ag
0.05PbSb
0.05Te
1.1
Take by weighing Silver Nitrate, lead nitrate, nitric acid antimony, simple substance tellurium powder and be respectively 0.0002785,0.005570,0.0002785,0.006128 mole, the tellurium powder is put into polytetrafluoroethyltank tank, with lead nitrate, nitric acid antimony, Silver Nitrate respectively with being added in the reaction vessel successively behind the deionized water dissolving, in reaction vessel, add 0.01226 mole of sodium borohydride again, add deionized water in the reaction vessel and make the 80-90% that reaches container volume, add a cover be placed in the autoclave airtight.Autoclave is put into stove be heated to 5 hours postcooling of 150 ℃ of insulations to room temperature; Product is filtered with funnel, and replace wash products repeatedly until being neutral with dilute hydrochloric acid, deionized water, dehydrated alcohol.With filtered product in vacuum drying oven in vacuum tightness＜133Pa, room temperature treatment got final product in 2 hours.Recording its median size is 15nm.
Implementation column 3
Preparation Ag
nPbM
nTe
1+2n, M is Sb, n=0.1, i.e. Ag
0.1PbSb
0.1Te
1.2
Take by weighing Silver Nitrate, lead nitrate, nitric acid antimony, simple substance tellurium powder and be respectively 0.000510,0.00510,0.000510,0.00612 mole, the tellurium powder is put into reaction vessel, with lead nitrate, nitric acid antimony, Silver Nitrate respectively with being added in the reaction vessel successively behind the deionized water dissolving, in reaction vessel, add 0.01224 mole of sodium borohydride again, add deionized water in the reaction vessel and make the 80-90% that reaches container volume, add a cover be placed in the autoclave airtight.Autoclave is put into stove be heated to 1 hour postcooling of 200 ℃ of insulations to room temperature; Product is filtered with funnel, and replace wash products repeatedly until being neutral with dilute hydrochloric acid, deionized water, dehydrated alcohol.With filtered product in vacuum drying oven in vacuum tightness＜133Pa, room temperature treatment got final product in 4 hours.Recording its median size is 65nm.
Embodiment 4
Preparation Ag
nPbM
nTe
1+n, M is Bi, n=0.05, i.e. Ag
0.05PbBi
0.05Te
1.1
Take by weighing Silver Nitrate, lead chloride, Bismuth trinitrate, simple substance tellurium powder and be respectively 0.0002785,0.005570,0.0002785,0.006128 mole, the tellurium powder is put into reaction vessel, with lead chloride, Bismuth trinitrate, Silver Nitrate respectively with being added in the reaction vessel successively behind the deionized water dissolving, in reaction vessel, add 0.01226 mole of POTASSIUM BOROHYDRIDE again, add deionized water in the reaction vessel and make the 80-90% that reaches container volume, add a cover be placed in the autoclave airtight.Autoclave is put into stove be heated to 20 hours postcooling of 100 ℃ of insulations to room temperature; Product is filtered with funnel, and replace wash products repeatedly until being neutral with dilute hydrochloric acid, deionized water, dehydrated alcohol.With filtered product in vacuum drying oven in vacuum tightness＜133Pa, room temperature treatment got final product in 6 hours.Recording median size is 25nm.
Embodiment 5
Preparation Ag
nPbM
nTe
1+2n, M is Bi, n=0.2, i.e. Ag
0.2PbBi
0.2Te
1.4
Take by weighing Silver Nitrate, lead chloride, bismuth chloride, simple substance tellurium powder and be respectively 0.0009265,0.004632,0.0009265,0.006485 mole, the tellurium powder is put into reaction vessel, with lead chloride, bismuth chloride, Silver Nitrate respectively with being added in the reaction vessel successively behind the deionized water dissolving, in reaction vessel, add 0.01297 mole of sodium borohydride again, add deionized water in the reaction vessel and make the 80-90% that reaches container volume, add a cover be placed in the autoclave airtight
Autoclave is put into stove be heated to 10 hours postcooling of 100 ℃ of insulations to room temperature; Product is filtered with funnel, and replace wash products repeatedly until being neutral with dilute hydrochloric acid, deionized water, dehydrated alcohol.With filtered product in vacuum drying oven in vacuum tightness＜133Pa, room temperature treatment got final product in 4 hours.Recording its median size is 20nm.
Claims (6)
1, the preparation method of nanometer-level silver and antimony or silver and the adulterated lead telluride of bismuth, this method steps is as follows:
(1), the tellurium powder is joined in the deionized water solution of the chlorate of Silver Nitrate, lead, antimony or bismuth or nitrate, add reductive agent again, wherein the mol ratio of the chlorate of Silver Nitrate, lead, antimony or bismuth or nitrate, tellurium powder, reductive agent is respectively n: 1: n: 1+2n: 2+4n, 0≤n≤0.2;
(2), be heated to 1-20 hour postcooling of 100-200 ℃ of insulation to room temperature;
(3), will product filter, carry out vacuum drying treatment after the washing, can obtain nanometer-level silver and antimony or silver and the adulterated lead telluride thermoelectric material of bismuth.
2, the preparation method of nanometer-level silver as claimed in claim 1 and antimony or silver and the adulterated lead telluride of bismuth is characterized in that described reductive agent is alkali-metal hydroborate or diamine.
3, the preparation method of nanometer-level silver as claimed in claim 1 and antimony or silver and the adulterated lead telluride of bismuth is characterized in that described reductive agent is sodium borohydride or POTASSIUM BOROHYDRIDE.
4, the preparation method of nanometer-level silver as claimed in claim 1 and antimony or silver and the adulterated lead telluride of bismuth is characterized in that used reaction vessel is a polytetrafluoroethyltank tank.
5, the preparation method of arbitrary nanometer-level silver of claim 1～4 and antimony or silver and the adulterated lead telluride of bismuth is characterized in that described cleaning step is to adopt dilute hydrochloric acid or rare nitric acid, deionized water, dehydrated alcohol alternately to clean described product repeatedly until being neutral.
6, the preparation method of arbitrary nanometer-level silver of claim 1～4 and antimony or silver and the adulterated lead telluride of bismuth is characterized in that described vacuum drying treatment condition is vacuum tightness＜133Pa, and temperature is a room temperature, 2～6 hours time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410099007XA CN100355645C (en) | 2004-12-24 | 2004-12-24 | Method for preparing Nano lead telluride doped with silver and stibium or silver and bismuth |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410099007XA CN100355645C (en) | 2004-12-24 | 2004-12-24 | Method for preparing Nano lead telluride doped with silver and stibium or silver and bismuth |
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|---|---|
| CN1796271A true CN1796271A (en) | 2006-07-05 |
| CN100355645C CN100355645C (en) | 2007-12-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107954467A (en) * | 2017-11-03 | 2018-04-24 | 畅的新材料科技（上海）有限公司 | A kind of silver, bismuth doping cadmium oxide near-infrared high reflection raw powder's production technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000106460A (en) * | 1998-07-27 | 2000-04-11 | Komatsu Ltd | Thermoelectric semiconductor material and manufacture thereof |
| CN1159212C (en) * | 2002-06-21 | 2004-07-28 | 清华大学 | Nano level metal telluride preparing process |
| CN1230377C (en) * | 2003-08-20 | 2005-12-07 | 中国科学院上海硅酸盐研究所 | Method for preparing bismuth telluride base thermoelectric material |
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2004
- 2004-12-24 CN CNB200410099007XA patent/CN100355645C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107954467A (en) * | 2017-11-03 | 2018-04-24 | 畅的新材料科技（上海）有限公司 | A kind of silver, bismuth doping cadmium oxide near-infrared high reflection raw powder's production technology |
| CN107954467B (en) * | 2017-11-03 | 2019-06-07 | 畅的新材料科技（上海）有限公司 | A kind of silver-colored, bismuth doping cadmium oxide near-infrared high reflection raw powder's production technology |
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| CN100355645C (en) | 2007-12-19 |
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Granted publication date: 20071219 Termination date: 20101224 |