CN104925854A - PbS thermoelectric compound preparation method - Google Patents
PbS thermoelectric compound preparation method Download PDFInfo
- Publication number
- CN104925854A CN104925854A CN201510364643.9A CN201510364643A CN104925854A CN 104925854 A CN104925854 A CN 104925854A CN 201510364643 A CN201510364643 A CN 201510364643A CN 104925854 A CN104925854 A CN 104925854A
- Authority
- CN
- China
- Prior art keywords
- preparation
- pbs
- solution
- sintering
- powder
- 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.)
- Granted
Links
Landscapes
- Powder Metallurgy (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention provides a PbS thermoelectric compound preparation method. The preparation method includes the following steps of 1), evenly mixing a Pb-contained compound and S powder and configuring the compound and the powder into a solution; 2), subjecting the solution to hydrothermal reaction; 3), subjecting the solution subjected to reaction to drying treatment; 4), subjecting a dried object to pressure sintering. In the method, lead salt and powdered sulfur are taken as raw materials which are rich in resource and low in cost; the materials for preparation are short in period and simple in process; the method has the advantages of rapid material composing, energy conservation and fitness for large-scale industrial production; the powder material prepared is even in particle, good in repeatability, high in density of block materials and high thermoelectric performance, dimensionless quality factor is up to 0.76 which is equivalent to commercially applied PbTe materials, however, the latter contains the element of Te which is high in price.
Description
Technical field
The invention belongs to novel energy resource material technology field, specifically, the present invention relates to the preparation method of PbS thermoelectric compound.
Background technology
PbS is a kind of thermoelectric material of good performance, has good application prospect in thermo-electric generation field, and because starting material are cheap, is subject to extensive concern.At present, preparation method's mainly scorification of PbS material, needs long heat just can obtain pure phase PbS material, and because the fusing point difference of Pb and S is larger, the boiling point of S, less than 450 DEG C, causes the volatilization loss of S in reaction process serious, is difficult to the content of accurately control S.So there is the shortcomings such as preparation cycle is long, cost is high, repeatability is bad in sample prepared by melting method.
The people such as Poud have reported for work the nano PbS powder that utilized solvent process for thermosynthesizing to prepare, but they adopt poisonous, taste is smelly, price 21 trimethyl silicon based sulphur costly as raw material, preparation technology is comparatively complicated, and the cycle is longer.In addition, the preparation method of the not mentioned block PbS of this article, in the actual application of thermoelectric material, must be prepared into the high compact block with certain mechanical property by material, is therefore necessary the preparation method exploring a kind of high fine and close PbS block materials.
The carrier concentration of intrinsic PbS is lower, and cause its resistivity higher, thermoelectricity capability is poor, needs to adulterate other element to improve its carrier concentration in actual application.Contriver notices that the PbS material prepared with hydro-thermal or solvent thermal process at present mainly concentrates on and controls its microscopic appearance, and the regulation and control its thermoelectricity capability being played to the carrier concentration of decisive role there is no report.
Summary of the invention
For the problems referred to above, the present invention improves Hydrothermal Synthesis PbS technique and optimizes, and adopts elemental sulfur and Pb salt (lead nitrate or lead acetate) as main raw material, and prepares PbS base block thermoelectric material in conjunction with ultra-high pressure sintering technique.Feature of the present invention is that work prepares skill simply, and preparation process is without the need to any organic solvent, and sample granularity is even, purity is high, and block materials density is high, and carrier concentration is controlled.
Specifically, the invention provides a kind of preparation method of PbS thermoelectric compound, it is characterized in that, described preparation method comprises the steps:
Step 1) get compound containing Pb and S powder, mix, be configured to solution;
Step 2) hydro-thermal reaction is carried out to described solution;
Step 3) drying treatment is carried out to reacted solution;
Step 4) pressure sintering is carried out to dried product.
In the preferred implementation of one, described step 1) comprising: by the Pb (NO by certain mol proportion
3)
2, S powder and doped element muriate put into beaker, and injects a certain amount of deionized water and form solution, and ultrasonic vibration, continued for first scheduled time to make it dissolve completely.
In the preferred implementation of one, described step 2) comprising: will prepare and shake uniform solution and pour in hydrothermal reaction kettle, continue the second predetermined amount of time.
In the preferred implementation of one, described step 3) comprise the product of hydro-thermal reaction is washed, drying treatment, obtain dried powder.
In the preferred implementation of one, described step 4) comprise the dried powder obtained in step 3 is pressed into block, and the block be pressed into is assembled laggard horizontal high voltage sintering.
In the preferred implementation of one, described step 1) also comprise and regulate the pH value of described solution to 9-12.
In the preferred implementation of one, described first predetermined amount of time is 0.3 ~ 1.5 hour, and described second predetermined amount of time is 3 ~ 15 hours.
In the preferred implementation of one, in described step 3) in, washing process utilizes distilled water wash 5-7 time; Described drying treatment comprises Hydrothermal Synthesis product and is positioned in vacuum drying oven, and vacuum-drying 5-10 hour, drying temperature was 50-60 DEG C or 60-70 DEG C.
In the preferred implementation of one, in described step 4) in sintering process in, the sintering pressure of employing is 2GPa, and sintering temperature is 400 ~ 700 DEG C, and sintering time is 15 ~ 50 minutes.
In the preferred implementation of one, in described step 1) in, add NaOH and NaBH in the solution
4.
In the preferred implementation of one, the present invention is with SbCl
3or BiCl
3for as doping agent, in step 1) in add.
In another kind of implementation, described raw material also comprises Bi, Sb or Ag for the doping of Pb position, and doping is 0 ~ 2% of S element.
In addition, in another kind of implementation, described raw material also comprises BiCl
3, SbCl
3and/or AgNO
3powder, doping is 0 ~ 4% of S element.Preferably, described raw material comprises for S element, the Sb of mol ratio 1 ~ 3%, the Bi of mol ratio 0.8 ~ 1.2%.Further preferably, described raw material also comprises the Sb relative to S elemental mole ratios 2%.Present inventor finds, after interpolation above-mentioned substance, the thermoelectricity capability of material has and promotes further.
The beneficial effect that the present invention brings at least comprise following in one:
A. material cost is cheap, and in the present invention, main employing lead salt and sulphur powder are starting material, and its abundance is cheap.
B. prepare material periodicities short, technique is simple.It is simple that the present invention has technique, and synthetic materials is rapid, save energy, is applicable to large-scale commercial production.
C. the powder body material particle prepared is divided equally, reproducible, and block materials density is high, has higher thermoelectricity capability, and its dimensionless figure factor is up to 0.76, suitable with the PbTe material of commercial applications, but the latter contains expensive Te element.
Other advantages of the present invention, target and feature are set forth by reference to the accompanying drawings by embodiment below, and to a certain extent, and based on to reading hereafter and understanding, these advantages and feature can understand to those skilled in the art.
Accompanying drawing explanation
Fig. 1 is the xrd collection of illustrative plates of Hydrothermal Synthesis PbS powder and high-pressure sinter block PbS.
Fig. 2 is the stereoscan photograph of Hydrothermal Synthesis PbS powdered sample.
Fig. 3 is the scanned photograph of high-pressure sinter block PbS sample.
Fig. 4 is the xrd collection of illustrative plates of PbS and doped samples thereof.
Fig. 5 is the resistivity variation with temperature of PbS and doped samples thereof.
Fig. 6 is the ZT value variation with temperature of PbS and doped samples thereof.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the present invention is described in detail.
In one embodiment of the invention, adopt such method to prepare PbS thermoelectric material, the method comprises the steps: 1) batching; 2) Hydrothermal Synthesis; 3) washing is dry; 4) sinter.
Above-mentioned four steps are described in detail.
1) with lead salt (lead acetate or lead nitrate) and sulphur (S) powder for main raw material, preferably, adopt lead nitrate (Pb (NO
3)
2).By Pb (NO
3)
2to be placed in beaker with certain mol ratio with S powder and to stir.Preferably, Pb (NO
3)
2being 0.75:1.15 to 1.15:0.85 with the mol ratio of S powder, is more preferably 1:1.In actually operating, consider the loss of S powder, can by Pb (NO
3)
2the mol ratio of powder and S powder is set to 1:1.06.
Preferably, raw material adopts high-purity Pb (NO
3)
2(purity >99%) and S powder (purity >99.99%); Weigh by PbS stoichiometry comparison raw material.
Preferably, in order to increase the performance of gained compound, can add in the feed for the doping of Pb position Sb, Bi or Ag, doping agent is BiCl
3, SbCl
3or AgNO
3, doping is the molar percentage 0 ~ 3% of S element.
2) at Pb (NO
3)
2with add a small amount of alkali (NaOH or KOH, preferred NaOH) and NaBH in the beaker of S powder
4, and shake certain hour with ultrasonic cleaner, move in autoclave after dissolving completely.And put into baking oven and heat.Be heated to preset temperature, the insulation scheduled time.
Preset temperature mentioned here is preferably 90 ~ 200 degrees Celsius, and predetermined amount of time is preferably 3 ~ 15 hours.
3) collect black powder sample bottom reactor, utilize distilled water wash 5-7 time.Subsequently drying treatment is carried out to product, vacuum-drying for some time, obtain dry powder.In the present embodiment, the drying treatment process adopted is: will be positioned in vacuum drying oven through washing after product, vacuum-drying 5-10 hour, drying temperature was 50-60 DEG C or 60-70 DEG C, preferably 60 DEG C.Contriver is found by test, and when the hydro-thermal reaction time was more than 3 hours, temperature, more than 100 degree, can obtain single-phase PbS powdered material (as Fig. 1), and sample granularity relatively evenly (as Fig. 2).
4) after drying, powder put into steel die and utilize tabletting machine that the powder compression after grinding is become block.The pressure that pressing process adopts is 10 ~ 20MPa.Sample is loaded in high pressure assembly block and carry out high-pressure sinter process, obtain compact block, be i.e. PbS electric heating electric material.Preferably, the sintering pressure adopted in sintering process is 2-3GPa.Sintering temperature is 400 ~ 700 DEG C, and temperature rise rate is 10 ~ 100 DEG C/min, and sintering time is 15 ~ 50min.After sintering, densified sample (as Fig. 3) will be obtained.
In order to verify the performance of obtained sample, by the sample after sintering through cutting, utilizing LSR-3 to test resistivity, Seebeck (Seebeck) coefficient of PbS sample after polishing, utilizing LFA-457 to test the thermal conductivity of sample.
As shown in table 1, higher sintering temperature contribute to reduce resistivity, reason mainly: first, the density of sample increases along with the rising of sintering temperature, the resistivity that high-compactness sample is corresponding lower, secondly, a small amount of lattice imperfection can be produced under hot conditions, improve carrier concentration.But the too high meeting of sintering temperature causes decomposed sample to cause resistivity to increase, Seebeck coefficient reduces.So PbS sample corresponds to the highest power factor when sintering temperature is at 600 DEG C.
The electronic transport performance of the PbS obtained is sintered under the different sintering temperature condition of table 1
| Sintering temperature | Resistivity | Seebeck coefficient | Power factor |
| (℃) | (Ωcm) | (μV/K) | (μW/cmK2) |
| 400 | 1.080 | 248.5 | 0.06 |
| 500 | 0.017 | 223.8 | 2.95 |
| 600 | 0.007 | 220.4 | 6.94 |
| 700 | 0.12 | 95.6 | 0.08 |
In the Synthesis and applications process of thermoelectric material, the regulation and control of carrier concentration are most important for thermoelectricity capability impact, contriver finds to utilize the doping of Sb or Bi Substitute For Partial Pb formation instead type effectively can modulate the carrier concentration of PbS, and little concern utilizes hydrothermal synthesis method to prepare doping PbS and other system thermoelectric material, the preferred SbCl of the present invention before technician
3and BiCl
3achieve the continuously adjustabe of PbS carrier concentration as doping agent, table 2 be doping different element and doping on the impact of PbS carrier concentration.A small amount of Sb and Bi of visible doping effectively can improve carrier concentration and the carrier mobility of PbS.
Table 2 adulterates the impact of Sb and Bi on PbS carrier concentration and hall mobility
| Sample | Carrier concentration(10 18cm -) | Hall mobility(CmVS) |
| PbS | 7.355 | 94.121 |
| Sb 0.01Pb 0.99S | 28.629 | 144.6 |
| Sb 0.02Pb 0.99S | 37.318 | 147.74 |
| Bi 0.005Pb 0.995S | 26.309 | 3.3133 |
| Bi 0.01Pb 0.99S | 45.215 | 133.99 |
| Bi 0.015Pb 0.985S | 45.382 | 126.83 |
Fig. 4 is the Sb that Hydrothermal Synthesis obtains in conjunction with high-pressure sinter
xpb
1-xthe X ray diffracting spectrum of S (x=0,0.01,0.02) sample.In this figure illustrated embodiment, the Hydrothermal Synthesis temperature adopted is 180 DEG C, and the time is 12 hours, and sintering pressure and temperature are respectively 3GPa and 600 DEG C.Along with the increase of Sb content, all diffraction peaks offset to the right, illustrate that Sb that atomic radius is less instead of the position of Pb.
Fig. 5 is Sb
xpb
1-xthe resistivity variation with temperature of S (x=0,0.01,0.02) sample, the resistivity of the sample after visible doping is all lower than PbS sample in Range of measuring temp, and visible Sb doping effectively reduces the resistivity of PbS.
Fig. 6 is Sb
xpb
1-xs (x=0,0.01,0.02) the quality factor variation with temperature of sample, the sample of the doping 2%Sb of the sample after visible doping has higher thermoelectricity capability, its maximum dimensionless figure factor is up to 0.76, suitable with the PbTe material of commercial applications, but the latter contains expensive Te element.
Finally it should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, other amendments that those of ordinary skill in the art make technical scheme of the present invention or equivalently to replace, only otherwise depart from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of right of the present invention.
Claims (9)
1. a preparation method for PbS thermoelectric compound, is characterized in that, described preparation method comprises the steps:
Step 1) get compound containing Pb and S powder, mix, be configured to solution;
Step 2) hydro-thermal reaction is carried out to described solution;
Step 3) drying treatment is carried out to reacted solution;
Step 4) pressure sintering is carried out to dried product.
2. the preparation method of PbS thermoelectric compound according to claim 1, is characterized in that, described step 1) comprising: by the Pb (NO by certain mol proportion
3)
2, S powder puts into container, and injects a certain amount of deionized water and forms solution, carries out ultrasonic vibration to solution, continued for first scheduled time to make it dissolve completely.
3. the preparation method of PbS thermoelectric compound according to claim 2, is characterized in that, described step 2) comprising: will prepare and shake uniform solution and pour in hydrothermal reaction kettle, continue the second predetermined amount of time.
4. the preparation method of PbS thermoelectric material according to claim 3, is characterized in that, described step 3) comprise the product of hydro-thermal reaction is washed, drying treatment, obtain dried powder.
5. the preparation method of PbS thermoelectric material according to claim 4, is characterized in that, described step 4) comprise the dried powder obtained in step 3 is pressed into block, and the block be pressed into is assembled laggard horizontal high voltage sintering.
6. the preparation method of PbS thermoelectric compound according to claim 1, is characterized in that,
Described step 1) also comprise the pH value that regulates described solution to >=10.
7. the preparation method of PbS thermoelectric compound according to claim 1, is characterized in that, described first predetermined amount of time is 0.3 ~ 1.5 hour, and described second predetermined amount of time is 3 ~ 15 hours.
8. the preparation method of PbS thermoelectric compound according to claim 4, is characterized in that, in described step 3) in, washing process utilizes distilled water wash 5-7 time; Described drying treatment comprises Hydrothermal Synthesis product and is positioned in vacuum drying oven, and vacuum-drying 5-10 hour, drying temperature was 50-60 DEG C or 60-70 DEG C.
9. the preparation method of PbS thermoelectric compound according to claim 1, is characterized in that, in described step 4) in sintering process in, the sintering pressure of employing is 2GPa, and sintering temperature is 400 ~ 700 DEG C, and sintering time is 15 ~ 50 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510364643.9A CN104925854B (en) | 2015-06-26 | 2015-06-26 | A kind of preparation method of PbS thermoelectric compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510364643.9A CN104925854B (en) | 2015-06-26 | 2015-06-26 | A kind of preparation method of PbS thermoelectric compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104925854A true CN104925854A (en) | 2015-09-23 |
| CN104925854B CN104925854B (en) | 2016-10-19 |
Family
ID=54113326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510364643.9A Expired - Fee Related CN104925854B (en) | 2015-06-26 | 2015-06-26 | A kind of preparation method of PbS thermoelectric compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104925854B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006574A (en) * | 2016-05-11 | 2016-10-12 | 河南理工大学 | Rapid preparation method for thermoelectric compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907863A (en) * | 2006-08-24 | 2007-02-07 | 同济大学 | Method of preparing sulfide nano material of lead with calixarene adjusting solvent thermal system |
| CN103787406A (en) * | 2014-02-17 | 2014-05-14 | 河南理工大学 | Preparation method for PbS thermoelectric compound |
| CN103818948A (en) * | 2014-02-17 | 2014-05-28 | 河南理工大学 | Preparation method of thermoelectric compound |
-
2015
- 2015-06-26 CN CN201510364643.9A patent/CN104925854B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1907863A (en) * | 2006-08-24 | 2007-02-07 | 同济大学 | Method of preparing sulfide nano material of lead with calixarene adjusting solvent thermal system |
| CN103787406A (en) * | 2014-02-17 | 2014-05-14 | 河南理工大学 | Preparation method for PbS thermoelectric compound |
| CN103818948A (en) * | 2014-02-17 | 2014-05-28 | 河南理工大学 | Preparation method of thermoelectric compound |
Non-Patent Citations (2)
| Title |
|---|
| 谢淑红等: ""水热法制备PbS及其热电性能研究"", 《湘潭大学自然科学学报》 * |
| 邱玉章: ""金属硫化物水热合成及光催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006574A (en) * | 2016-05-11 | 2016-10-12 | 河南理工大学 | Rapid preparation method for thermoelectric compound |
| CN106006574B (en) * | 2016-05-11 | 2019-02-26 | 河南理工大学 | A kind of thermoelectric compound fast preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104925854B (en) | 2016-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Goto et al. | Effect of Sn-substitution on thermoelectric properties of copper-based sulfide, famatinite Cu3SbS4 | |
| Cheng et al. | Role of cation vacancies in Cu2SnSe3 Thermoelectrics | |
| Li et al. | N-type Bi-doped SnSe thermoelectric nanomaterials synthesized by a facile solution method | |
| CN102655204A (en) | Sr-doping oxide BiCuSeO thermoelectric material and preparation method thereof | |
| CN107946450B (en) | A kind of doping valence variation element collaboration optimization BiCuSeO base thermoelectricity material | |
| CN101157483B (en) | Transition metal composite oxides preparation method | |
| CN108588838A (en) | A method of preparing the SnSe polycrystalline bulks with high thermoelectricity capability | |
| CN103787406B (en) | Preparation method for PbS thermoelectric compound | |
| CN102867905A (en) | Sn-S-based thermoelectric compound and preparation method thereof | |
| CN103213956A (en) | Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles | |
| CN102643085A (en) | Bi Cu 1-x SeO-based oxide thermoelectric ceramic material and preparation method thereof | |
| CN107176589B (en) | It is a kind of to prepare nanosizing Mg3Sb2The method of thermoelectric material | |
| CN103818948B (en) | Preparation method of thermoelectric compound | |
| CN101157482A (en) | Modified Ca-Co-O system doped transition metal composite oxides and preparation method thereof | |
| CN106829884B (en) | A kind of thermoelectric material preparation method based on Te simple substance | |
| CN104925854A (en) | PbS thermoelectric compound preparation method | |
| CN108395254B (en) | Composite material and preparation method and application thereof | |
| CN110218888A (en) | A kind of novel Zintl phase thermoelectric material and preparation method thereof | |
| CN105803532A (en) | Thermoelectric material, preparation method and application thereof | |
| CN109626446B (en) | Preparation method of cubic CoSbS thermoelectric compound | |
| CN109250692B (en) | Autocatalysis low-temperature rapid synthesis of Cu 2 Method for preparing Se-based thermoelectric material | |
| CN107507910B (en) | Low-resistivity CaMnO3Preparation method of composite thermoelectric material | |
| Li et al. | Improved Thermoelectric Performance of P-type SnTe through Synergistic Engineering of Electronic and Phonon Transports | |
| CN104998593B (en) | A kind of Hydrothermal Synthesiss processing technology | |
| CN105932148A (en) | Ag-doped cubic-phase Ca2Si thermoelectric material |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161019 Termination date: 20190626 |