CN104925854B - A kind of preparation method of PbS thermoelectric compound - Google Patents
A kind of preparation method of PbS thermoelectric compound Download PDFInfo
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Abstract
The present invention provides the preparation method of a kind of PbS thermoelectric compound, and described preparation method comprises the steps: step 1) take the compound containing Pb and S powder, mix homogeneously, it is configured to solution；Step 2) described solution is carried out hydro-thermal reaction；Step 3) reacted solution is dried process；Step 4) dried product is carried out pressure sintering.In the present invention, main employing lead salt and sulfur powder are raw material, and its abundance is cheap.It is short that the present invention prepares material periodicities, and technique is simple.It is rapid that the present invention has synthetic material, saves the energy, is suitable for the feature of large-scale industrial production.The powder body material granule that the present invention prepares is divided equally, reproducible, and block materials consistency is high, there is higher thermoelectricity capability, its dimensionless figure factor is up to 0.76, suitable with the PbTe material of commercial applications, but the latter contains expensive Te element.
Description
Technical field
The invention belongs to novel energy resource material technology field, specifically, the present invention relates to the preparation side of PbS thermoelectric compound
Method.
Background technology
PbS is a kind of thermoelectric material of good performance, has a good application prospect in thermo-electric generation field, and because
Raw material is cheap, receives significant attention.At present, the preparation method of PbS material is mainly fusion method, needs long high temperature to add
Heat just can obtain pure phase PbS material, and because the fusing point difference of Pb and S is relatively big, the boiling point of S, less than 450 DEG C, causes reacting
In journey, the volatilization loss of S is serious, is difficult to accurately control the content of S.So sample prepared by melting method exist manufacturing cycle length,
The shortcomings such as cost is high, repeatability is bad.
Poud et al. has reported for work and has utilized solvent process for thermosynthesizing to be prepared for nano PbS powder, but they use poisonous, taste
Smelly, price 21 silica-based sulfur of trimethyl costly are as raw material, and preparation technology is complex, and the cycle is longer.It addition, this article
The preparation method of not mentioned block PbS, in the actual application of thermoelectric material, it is necessary to material is prepared as have certain force
Learn the high compact block of performance, it is therefore necessary to explore the preparation method of a kind of high fine and close PbS block materials.
The carrier concentration of intrinsic PbS is relatively low, causes its resistivity higher, and thermoelectricity capability is poor, in actual application
Need to adulterate other element to improve its carrier concentration.Inventor notices and at present prepares with hydro-thermal or solvent thermal process
PbS material focuses primarily upon its microscopic appearance of control, and its thermoelectricity capability plays the tune of the carrier concentration of decisive role
Control there is no report.
Summary of the invention
For the problems referred to above, Hydrothermal Synthesis PbS technique is improved and has been optimized by the present invention, uses elemental sulfur and Pb salt
(plumbi nitras or lead acetate) is as primary raw material, and combines ultra-high pressure sintering technique and prepare PbS base block thermoelectric material.The present invention
Feature to be that work prepares skill simple, preparation process is without any organic solvent, and sample granularity is uniform, purity is high, and block materials causes
Density is high, and carrier concentration is controlled.
Specifically, the invention provides the preparation method of a kind of PbS thermoelectric compound, it is characterised in that described preparation
Method comprises the steps:
Step 1) take the compound containing Pb and S powder, mix homogeneously, it is configured to solution；
Step 2) described solution is carried out hydro-thermal reaction；
Step 3) reacted solution is dried process；
Step 4) dried product is carried out pressure sintering.
In a kind of preferred implementation, described step 1) including: by by the Pb (NO of certain mol proportion3)2, S powder and doping
Element chloride is put in beaker, and injects a certain amount of deionized water formation solution, and ultrasonic vibration, continues the first pre-timing
Chien shih its be completely dissolved.
In a kind of preferred implementation, described step 2) including: preparing and shake uniform solution, to pour hydro-thermal into anti-
Answer in still, continue the second predetermined amount of time.
In a kind of preferred implementation, described step 3) include the product of hydro-thermal reaction is washed, dried,
Obtain dried powder.
In a kind of preferred implementation, described step 4) include dried powder briquet obtained in step 3
Body, and the block being pressed into is assembled laggard horizontal high voltage sintering.
In a kind of preferred implementation, described step 1) also include that the pH value regulating described solution is to 9-12.
In a kind of preferred implementation, described first predetermined amount of time is 0.3～1.5 hour, the described second pre-timing
Between section be 3～15 hours.
In a kind of preferred implementation, in described step 3) in, washing process utilizes distilled water wash 5-7 time；Described
Dried includes that Hydrothermal Synthesis product is positioned in vacuum drying oven, and vacuum drying 5-10 hour, baking temperature is 50-60
DEG C or 60-70 DEG C.
In a kind of preferred implementation, in described step 4) in sintering process in, the sintering pressure of employing is 2GPa,
Sintering temperature is 400～700 DEG C, and sintering time is 15～50 minutes.
In a kind of preferred implementation, in described step 1) in, add NaOH and NaBH in the solution4。
In a kind of preferred implementation, the present invention is with SbCl3Or BiCl3For as adulterant, in step 1) in add.
In another kind of implementation, described raw material also includes Bi, Sb or the Ag for the doping of Pb position, and doping is S unit
The 0～2% of element.
Additionally, in another kind of implementation, described raw material also includes BiCl3、SbCl3And/or AgNO3Powder, doping is
The 0～4% of S element.Preferably, described raw material includes for S element, the mol ratio 1～Sb of 3%, mol ratio 0.8～
The Bi of 1.2%.It is further preferred that described raw material also includes the Sb relative to S elemental mole ratios 2%.Present inventor
Finding, adding after above-mentioned substance, the thermoelectricity capability of material has and promotes further.
The beneficial effect that the present invention is brought at least include following in one:
A. the cost of raw material is cheap, and in the present invention, main employing lead salt and sulfur powder are raw material, and its abundance, price is low
Honest and clean.
B. preparing material periodicities short, technique is simple.It is simple that the present invention has technique, and synthetic material is rapid, saves the energy, suitable
Close large-scale industrial production.
C. the powder body material granule prepared is divided equally, reproducible, and block materials consistency is high, has higher thermoelectricity
Performance, its dimensionless figure factor is up to 0.76, suitable with the PbTe material of commercial applications, but the latter is contained price and held high
Expensive Te element.
Other advantages, target and the feature of the present invention is illustrated combining accompanying drawing in following detailed description of the invention,
And to a certain extent, based on to reading hereafter and understanding, these advantages and feature are to those skilled in the art
Be it can be appreciated that.
Accompanying drawing explanation
Fig. 1 is Hydrothermal Synthesis PbS powder and the xrd collection of illustrative plates of high-pressure sinter block PbS.
Fig. 2 is the stereoscan photograph of Hydrothermal Synthesis PbS powder 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.
Detailed description of the invention
Below in conjunction with accompanying drawing, embodiments of the present invention is described in detail.
In one embodiment of the invention, using such method to prepare PbS thermoelectric material, the method includes as follows
Step: 1) dispensing；2) Hydrothermal Synthesis；3) washing is dried；4) sintering.
Four above-mentioned steps are described in detail.
1) with lead salt (lead acetate or plumbi nitras) and sulfur (S) powder as primary raw material, it is preferable that use plumbi nitras (Pb
(NO3)2).By Pb (NO3)2It is placed in beaker with certain mol ratio with S powder and stirs.Preferably, Pb (NO3)2With S powder
Mol ratio is 0.75:1.15 to 1.15:0.85, more preferably 1:1.In practical operation, it is contemplated that the loss of S powder, permissible
By Pb (NO3)2The mol ratio of powder and S powder is set to 1:1.06.
Preferably, raw material uses high-purity Pb (NO3)2(purity > 99%) and S powder (purity > 99.99%)；Based on PbS chemistry
Amount comparison raw material weighs.
Preferably, in order to increase the performance of gained compound, can add in the feed for Pb position doping Sb, Bi or
Ag, adulterant is BiCl3、SbCl3Or AgNO3, doping is the molar percentage 0～3% of S element.
2) at Pb (NO3)2With the beaker of S powder adds a small amount of alkali (NaOH or KOH, preferably NaOH) and NaBH4, and with super
Sound wave washer concussion certain time, move in autoclave after being completely dissolved.And put into heating in baking oven.It is heated to making a reservation for
Temperature, is incubated the scheduled time.
Predetermined 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 product is dried place
Reason, is vacuum dried a period of time, obtains the powder being dried.In the present embodiment, the dried process used is: will be through washing
Washing afterproduct to be positioned in vacuum drying oven, vacuum drying 5-10 hour, baking temperature is 50-60 DEG C or 60-70 DEG C, excellent
Select 60 DEG C.Inventor is found by test, and when the hydro-thermal reaction time is little more than 3, temperature, more than 100 degree, i.e. can get single-phase
PbS dusty material (such as Fig. 1), and sample granularity is than more uniform (such as Fig. 2).
4) powder is put in steel die and utilizes tablet machine that polished powder is pressed into block after drying.Pressure
The pressure that process processed is used is 10～20MPa.Sample is loaded in high pressure assembling block and carry out high-pressure sinter process, obtain densification
Block, i.e. PbS electric heating electric material.Preferably, the sintering pressure used in sintering process is 2-3GPa.Sintering temperature is
400～700 DEG C, heating rate is 10～100 DEG C/min, and sintering time is 15～50min.After sintering, fine and close sample will be obtained
Product (such as Fig. 3).
In order to verify the performance of obtained sample, by the sample after sintering through cutting, LSR-3 after polishing, is utilized to test
The resistivity of PbS sample, Seebeck (Seebeck) coefficient, utilize LFA-457 to test the thermal conductivity of sample.
As shown in table 1, higher sintering temperature contributes to reducing resistivity, and reason is mainly: first, the consistency of sample
Increase along with the rising of sintering temperature, the corresponding relatively low resistivity of high-compactness sample, secondly, can produce few under hot conditions
The lattice defect of amount, improves carrier concentration.But the too high meeting of sintering temperature causes sample to decompose causes resistivity to increase,
Seebeck coefficient reduces.So, when sintering temperature is at 600 DEG C, PbS sample is corresponding to the highest power factor.
The electronic transport performance of the PbS obtained is sintered under the conditions of the different sintering temperature 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 preparation and application process of thermoelectric material, the regulation and control of carrier concentration affect to closing weight for thermoelectricity capability
, inventor finds that utilizing Sb or Bi Substitute For Partial Pb to form instead type doping can effectively modulate the carrier concentration of PbS,
And seldom pay close attention to before technical staff and utilize hydrothermal synthesis method preparation doping PbS and other system thermoelectric material, the present invention is excellent
Select SbCl3And BiCl3Achieve the continuously adjustabe of PbS carrier concentration as adulterant, table 2 is the different element of doping and doping
The amount impact on PbS carrier concentration.A small amount of Sb and Bi of visible doping can effectively improve carrier concentration and the current-carrying of PbS
Transport factor.
Table 2 adulterates Sb and Bi to PbS carrier concentration and the impact of hall mobility
| Sample | Carrier concentration(1018cm-) | Hall mobility(CmVS) |
| PbS | 7.355 | 94.121 |
| Sb0.01Pb0.99S | 28.629 | 144.6 |
| Sb0.02Pb0.99S | 37.318 | 147.74 |
| Bi0.005Pb0.995S | 26.309 | 3.3133 |
| Bi0.01Pb0.99S | 45.215 | 133.99 |
| Bi0.015Pb0.985S | 45.382 | 126.83 |
Fig. 4 is the Sb that Hydrothermal Synthesis combines that high-pressure sinter obtainsxPb1-xThe X-ray of S (x=0,0.01,0.02) sample is spread out
Penetrate collection of illustrative plates.In this figure illustrated embodiment, the Hydrothermal Synthesis temperature used is 180 DEG C, and the time is 12 hours, sintering pressure and
Temperature is respectively 3GPa and 600 DEG C.Along with the increase of Sb content, all diffraction peaks offset to the right, illustrate that atomic radius is less
Sb instead of the position of Pb.
Fig. 5 is SbxPb1-xThe resistivity variation with temperature of S (x=0,0.01,0.02) sample, it is seen that the sample after doping
The resistivity of product is below PbS sample in Range of measuring temp, it is seen that Sb doping effectively reduces the resistivity of PbS.
Fig. 6 is SbxPb1-xThe quality factor variation with temperature of S (x=0,0.01,0.02) sample, it is seen that after doping
The sample of the doping 2%Sb of sample has higher thermoelectricity capability, and its maximum dimensionless figure factor is up to 0.76, and engages in trade
The PbTe material of industryization application is suitable, but the latter contains expensive Te element.
Last it should be noted that above example is only in order to illustrate technical scheme and unrestricted, this area
Other amendment or equivalents that technical scheme is made by those of ordinary skill, without departing from the technology of the present invention
The spirit and scope of scheme, all should contain in the middle of scope of the presently claimed invention.
Claims (6)
1. the preparation method of a PbS thermoelectric compound, it is characterised in that described preparation method comprises the steps:
Step 1) take the compound containing Pb and S powder, mix homogeneously, it is configured to solution；
Step 2) described solution is carried out hydro-thermal reaction；
Step 3) reacted solution is dried process；
Step 4) dried product carried out pressure sintering, described step 4) include step 3) and in obtained by dried powder
Be pressed into block, and the block that will be pressed into assemble laggard horizontal high voltage sintering, in described step 4) in sintering process in, adopt
Sintering pressure be 2GPa, sintering temperature is 500～700 DEG C, and sintering time is 15～50 minutes,
Wherein, in described step 1) in also include add BiCl3、SbCl3And/or AgNO3Powder, doping be S element 0～
4%.
The preparation method of PbS thermoelectric compound the most according to claim 1, it is characterised in that described step 1) including: will
By the Pb (NO of certain mol proportion3)2, S powder put in container, and inject a certain amount of deionized water formed solution, solution is carried out
Ultrasonic vibration, persistently first scheduled time made it be completely dissolved.
The preparation method of PbS thermoelectric compound the most according to claim 2, it is characterised in that described step 2) including: will
Preparing and shaking uniform solution pours in hydrothermal reaction kettle, continues the second predetermined amount of time.
The preparation method of PbS thermoelectric compound the most according to claim 3, it is characterised in that described step 3) include right
The product of hydro-thermal reaction carries out washing, dried, obtains dried powder.
The preparation method of PbS thermoelectric compound the most according to claim 1, it is characterised in that described step 1) also include
Regulate the pH value of described solution to >=10.
The preparation method of PbS thermoelectric compound the most according to claim 4, it is characterised in that in described step 3) in, wash
The process of washing utilizes distilled water wash 5-7 time；Described dried includes that Hydrothermal Synthesis product is positioned in vacuum drying oven, vacuum
Being dried 5-10 hour, baking temperature is 50-60 DEG C or 60-70 DEG C.
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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 |
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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 |
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| "水热法制备PbS及其热电性能研究";谢淑红等;《湘潭大学自然科学学报》;20140915;第36卷(第3期);第13页第2段 * |
| "金属硫化物水热合成及光催化性能研究";邱玉章;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140315(第3期);第32页第3段样品制备 * |
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