CN100384718C - Nano lead selenide doped with silver and stibium or silver and bismuth, and preparation method - Google Patents
Nano lead selenide doped with silver and stibium or silver and bismuth, and preparation method Download PDFInfo
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- CN100384718C CN100384718C CNB2004100990050A CN200410099005A CN100384718C CN 100384718 C CN100384718 C CN 100384718C CN B2004100990050 A CNB2004100990050 A CN B2004100990050A CN 200410099005 A CN200410099005 A CN 200410099005A CN 100384718 C CN100384718 C CN 100384718C
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- silver
- bismuth
- antimony
- thermoelectric material
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Abstract
The present invention relates to a thermoelectric material and a preparing method thereof, which takes lead selenide as a base. A nano stage silver and antimony or a selenizing heat lead electric material which is doped by silver or bismuth is Ag< n >PbM< n >Se< 1+2n >, M is antimony or bismuth, and 0< n< =0.2. The present invention comprises two preparation methods: 1, reductant is added in selenium powder, so the selenium powder is reduced to selenium ions; a deionized water solution of soluble salts and silver nitrate of lead, antimony or bismuth is added after heating the selenium ions, and the mixture is filtered, cleaned and dried in room temperature vacuum after mixing or ultrasonic treatment. 2, the selenium powder is added into deionized water solution of chloride salts and nitrates of silver nitrate, lead, antimony or bismuth, the reductant is added subsequently, the mixture is heated to 100 to 200 DEG C and is cooled to room temperature after 1 to 20 hours heat preservation, and product is dried in vacuum after filtering and washing. The new lead selenide thermoelectric material prepared by the present invention has the advantages of fine granularity, high purity, low raw material price, easy raw material obtaining and simple process.
Description
Technical field
The present invention relates to a kind of thermoelectric material and preparation method thereof field, relate in particular to a kind of lead selenide and be basic thermoelectric material and preparation method thereof.
Background technology
The thermoelectric material that has the excellent heat electrical property at present has PtSb, Ag
nPbBi
nTe
1+2n, PbSe, CoSb
3Deng, and Ag
nPbM
nSe
1+2n(M is Sb or Bi) this thermoelectric material does not also occur now.Ag in the prior art
nPbM
nTe
1+2nThermoelectric material synthetic 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 (K.F.Hsu, et al, Cubic AgPb again
mSbSe
2+m: bulkthermoelectric materials with high figure of merit, Science, 303 (2004) 818-821).Therefore temperature height, raw material that this preparation method need adopt are expensive, and be also high to the requirement of equipment, need seek also that a kind of raw material cheaply is easy to get, technology simply is easy to control, the preparation Ag that equipment requirements is low
nPbM
nSe
1+2nThe method of (M is Sb or Bi).
Summary of the invention
One of purpose of the present invention just provides a kind of nanometer-level silver and antimony or silver and adulterated lead selenide thermoelectric material of bismuth with excellent heat electrical property.
Another object of the present invention just provides this preparation methods.
The plumbous electric material of the adulterated selenizing heat of nanometer-level silver described in the present invention and antimony or silver and bismuth is meant Ag
nPbM
nSe
1+2n, M is Sb or Bi, 0＜n≤0.2, preferably 0.05≤n≤0.1.
The preparation method of nanometer-level silver and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is as follows among the present invention:
Method one: in selenium powder, add reductive agent and make selenium powder all be reduced into plasma selenium (Se
2-), be heated to 30-80 ℃, constantly stir, add lead, antimony or the soluble salt of bismuth, the deionized water solution of Silver Nitrate then, continuation is stirred or after ultrasonication 1-6 hour, is filtered, cleans, and the room temperature vacuum drying gets final product again, the mol ratio of the soluble salt of the selenium powder that is added, reductive agent, Silver Nitrate, lead, antimony or bismuth is respectively 1+2n: 2+4n: n: 1: n, 0＜n≤0.2.
Reductive agent described in the present invention is alkali-metal hydroborate, is preferably sodium borohydride or POTASSIUM BOROHYDRIDE.
The soluble salt of the lead described in the present invention, antimony or bismuth is meant chlorate, nitrate, vitriol, acetate, is preferably nitrate.
Plumbous among the present invention, the antimony or the soluble salt of bismuth, the addition sequence of Silver Nitrate are: add and wait behind the plumbiferous soluble salt solution to become black to add while stirring and contain antimony or bismuth, silver-colored solution.
Method two, step is as follows:
(1), selenium 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, selenium 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 selenide thermoelectric material of bismuth.
Reductive agent described in present method is alkali-metal hydroborate or diamine, is preferably sodium borohydride.
Reaction vessel among the present invention needs corrosion-resistant and High Temperature High Pressure, is preferably polytetrafluoroethyltank tank.
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, 2～4 hours time.
Beneficial effect of the present invention: the plumbous electric material of the adulterated selenizing heat of new nanometer-level silver that the present invention is prepared and antimony or silver and bismuth has and Ag
nPbM
nTe
1+2nSimilar thermoelectricity capability, fine size, purity height, only be several nanometers～tens nanometers, the chlorate of its preparation method employing Silver Nitrate, lead, antimony or bismuth or nitrate etc., raw material cheaply is easy to get, and the temperature of employing is 30～80 ℃, thereby synthesis temperature is reduced greatly, equipment requirements is simplified, and technology is simpler.
Description of drawings
The Ag that Fig. 1 the present invention produces
0.1PbSb
0.1Se
1.2The transmission electron microscope of powder shows among the figure that as synoptic diagram the powder particle granularity is 8nm.
The Ag that Fig. 2 the present invention produces
0.1PbBi
0.1Se
1.2The transmission electron microscope of powder shows among the figure that as synoptic diagram the powder particle granularity is 10nm.
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
nPbSb
nSe
1+2n(n=0.1) thermoelectric material, i.e. Ag
0.1PbSb
0.1Se
1.2
(1) gets the 100ml beaker, taking by weighing 0.014774 mole of adding of borane reducing agent potassium hydride KH appropriate amount of deionized water fully dissolves sodium borohydride, add 0.007387 mole of selenium powder then, be heated to 50 ℃, and make selenium powder fully be reduced into plasma selenium (Se with continuous stirring of magnetic agitation instrument
2-);
(2) take by weighing lead chloride, antimony chloride, Silver Nitrate and be respectively 0.006156 mole, 0.0006156 mole, 0.0006156 mole, and with deionized water their are fully joined after the dissolving respectively in the above-mentioned solution that contains plasma selenium more successively;
(3) after 6 hours the black product being filtered, clean back room temperature vacuum drying in stirring or ultrasonication under the said temperature condition gets final product.
Embodiment 2
Preparation Ag
nPbBi
nSe
1+2n(n=0.1) thermoelectric material, i.e. Ag
0.1PbBi
0.1Se
1.2
(1), get the 100ml beaker, take by weighing 0.014774 mole of adding of borane reducing agent sodium hydride appropriate amount of deionized water sodium borohydride is fully dissolved, add 0.007387 mole of selenium powder then, be heated to 30 ℃, with the stirring of magnetic agitation instrument selenium divided and fully be reduced into plasma selenium (Se
2-);
(2) take by weighing lead nitrate, nitric acid antimony, Silver Nitrate and be respectively 0.006156 mole, 0.0006156 mole, 0.0006156 mole, and with deionized water their are fully joined after the dissolving respectively in the above-mentioned solution that contains plasma selenium more successively;
(3) after 2 hours the black product being filtered, clean back room temperature vacuum drying in stirring on one side or ultrasonication under the said temperature condition gets final product.
Embodiment 3
Preparation Ag
nPbSb
nSe
1+2n, n=0.2 thermoelectric material, i.e. Ag
0.2PbSb
0.2Se
1.4
(1), gets the 100ml beaker, take by weighing 0.01420 mole of adding of borane reducing agent sodium hydride appropriate amount of deionized water sodium borohydride is fully dissolved, add 0.00710 mole of selenium powder then, be heated to 80 ℃, with the stirring of magnetic agitation instrument selenium is divided and fully be reduced into plasma selenium (Se
2-);
(2) take by weighing lead nitrate, nitric acid antimony, Silver Nitrate and be respectively 0.005071 mole, 0.0001014 mole, 0.0001014 mole, and with deionized water their are fully joined after the dissolving respectively in the above-mentioned solution that contains plasma selenium more successively;
(3) after 4 hours the black product being filtered, clean back room temperature vacuum drying in stirring or ultrasonication under the said temperature condition gets final product.
Embodiment 4
Preparation Ag
nPbSb
nSe
1+2n(n=0.05) thermoelectric material, i.e. Ag
0.05PbSb
0.05Se
1.1
Take by weighing Silver Nitrate, lead nitrate, nitric acid antimony, simple substance selenium powder and be respectively 0.0002785,0.005570,0.0002785,0.006128 mole, selenium 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 0.01226 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 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 4 hours.
Embodiment 5
Preparation Ag
nPbBi
nSe
1+2n(n=0.05) thermoelectric material, i.e. Ag
0.05PbBi
0.05Se
1.1
Take by weighing Silver Nitrate, lead chloride, Bismuth trinitrate, simple substance selenium powder and be respectively 0.0002785,0.005570,0.0002785,0.006128 mole, selenium 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 about 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 10 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.
Embodiment 6
Preparation Ag
nPbBi
nSe
1+2n(n=0.2) pyroelectric material Ag
0.2PbBi
0.2Se
1.4
Take by weighing Silver Nitrate, lead chloride, bismuth chloride, simple substance selenium powder and be respectively 0.0009265,0.004632,0.0009265,0.006485 mole, selenium 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 about 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 2 hours 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.
Claims (10)
1. nanometer-level silver and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth contain Ag
nPbM
nSe
1+2n, M is Sb or Bi, 0＜n≤0.2.
2. nanometer-level silver as claimed in claim 1 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is characterized in that 0.05≤n≤0.1.
3. the preparation method of nanometer-level silver as claimed in claim 1 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth, this method comprise the steps: to add reductive agent in selenium powder makes selenium powder all be reduced into plasma selenium Se
2-Be heated to 30-80 ℃, constantly stir, add the deionized water solution of soluble salt of deionized water solution, antimony or bismuth of plumbous soluble salt and the deionized water solution of Silver Nitrate then, continuation is stirred or after ultrasonication 1-6 hour, is filtered, cleans, and the room temperature vacuum drying gets final product again, the mol ratio of the soluble salt of soluble salt, antimony or the bismuth of the selenium powder that is added, reductive agent, Silver Nitrate, lead is respectively 1+2n: 2+4n: n: 1: n, 0＜n≤0.2.
4. the preparation method of nanometer-level silver as claimed in claim 3 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is characterized in that described reductive agent is alkali-metal hydroborate.
5. the preparation method of nanometer-level silver as claimed in claim 3 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is characterized in that the soluble salt of soluble salt, antimony or the bismuth of described lead is meant its corresponding chlorinated salt, nitrate, vitriol or acetate.
6. nanometer-level silver as claimed in claim 3 and antimony or the silver and the preparation method of the adulterated lead selenide thermoelectric material of bismuth is characterized in that the soluble salt of plumbous soluble salt, antimony or bismuth, the addition sequence of Silver Nitrate are: solution such as add behind the deionized water solution of soluble salt of lead and become black and add the deionized water solution of soluble salt of antimony or bismuth and the deionized water solution of Silver Nitrate more while stirring.
7. the preparation method of nanometer-level silver as claimed in claim 1 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth, this method comprises the steps:
(1), selenium powder is joined in the deionized water solution of the chlorate of Silver Nitrate, plumbous chlorate or nitrate and antimony or bismuth or nitrate, add reductive agent again, wherein the mol ratio of the chlorate of the chlorate of Silver Nitrate, lead or nitrate, antimony or bismuth or nitrate, selenium 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 selenide thermoelectric material of bismuth.
8. the preparation method of nanometer-level silver as claimed in claim 7 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is characterized in that described reductive agent is alkali-metal hydroborate or diamine.
9. the preparation method of nanometer-level silver as claimed in claim 7 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is characterized in that described vacuum drying treatment condition is vacuum tightness＜133Pa, and temperature is a room temperature, 2～4 hours time.
10. the preparation method of nanometer-level silver as claimed in claim 7 and antimony or silver and the adulterated lead selenide thermoelectric material of bismuth is characterized in that the washing in the described step (3) is to neutral with the product washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100990050A CN100384718C (en) | 2004-12-24 | 2004-12-24 | Nano lead selenide doped with silver and stibium or silver and bismuth, and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100990050A CN100384718C (en) | 2004-12-24 | 2004-12-24 | Nano lead selenide doped with silver and stibium or silver and bismuth, and preparation method |
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|---|---|
| CN1796270A CN1796270A (en) | 2006-07-05 |
| CN100384718C true CN100384718C (en) | 2008-04-30 |
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| CN101871097B (en) * | 2010-06-10 | 2012-05-16 | 浙江工业大学 | Simple preparation method of compact PbSe polycrystal film |
| CN113263184B (en) * | 2021-04-13 | 2022-11-08 | 上海大学 | Selenium-doped nano antimony, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000106460A (en) * | 1998-07-27 | 2000-04-11 | Komatsu Ltd | Thermoelectric semiconductor material and manufacture thereof |
| US6379635B2 (en) * | 1995-09-15 | 2002-04-30 | Imperial College Of Science, Technology & Medicine | Process for preparing a nanocrystalline material |
| CN1384047A (en) * | 2002-06-07 | 2002-12-11 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
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2004
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6379635B2 (en) * | 1995-09-15 | 2002-04-30 | Imperial College Of Science, Technology & Medicine | Process for preparing a nanocrystalline material |
| JP2000106460A (en) * | 1998-07-27 | 2000-04-11 | Komatsu Ltd | Thermoelectric semiconductor material and manufacture thereof |
| CN1384047A (en) * | 2002-06-07 | 2002-12-11 | 清华大学 | Synthesis of several metal selenides and tellurides as semiconductor material |
Non-Patent Citations (1)
| Title |
|---|
| 特开JP2000-106460A 2000.04.11 |
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