CN107265412A - A kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound - Google Patents

A kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound Download PDF

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Publication number
CN107265412A
CN107265412A CN201710479649.XA CN201710479649A CN107265412A CN 107265412 A CN107265412 A CN 107265412A CN 201710479649 A CN201710479649 A CN 201710479649A CN 107265412 A CN107265412 A CN 107265412A
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thermal conductivity
pbse
preparation
lower thermal
thermoelectric compound
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CN201710479649.XA
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朱红玉
宿太超
胡强
胡美华
李尚升
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Henan University of Technology
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Henan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/007—Tellurides or selenides of metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention provides a kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound, the preparation method comprises the following steps：Step 1) metal simple-substance and a non-metal simple-substance are placed in ball grinder by predetermined molar ratio mixing；Step 2) absolute ethyl alcohol is injected to ball grinder, and deoxygenated and/or protection processing, ball grinder is fixed on ball mill, the wet-milling scheduled time；Step 3) block is pressed into resulting dried powder；Step 4) block being pressed into is subjected to high-pressure synthesis.For existing method, the thermal conductivity of thermoelectric compound prepared by the method for the present invention is low by 20% 40%, and, many experiments obtain material thermal conductivity change of floating and are far smaller than material prepared by existing method, are more beneficial for stablize, the thermoelectric material for the lower thermal conductivity that height is repeatable.

Description

A kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound
Technical field
The invention belongs to field of thermoelectric material technique.Specifically related to PbSe2Compound, using Pb, Se as raw material, utilizes high pressure Method prepares the PbSe with lower thermal conductivity2。
Background technology
Exhaustion and environmental problem recently as fossil energy go from bad to worse, countries in the world to the exploitation of new energy and The research of new energy materialses is increasingly paid attention to.Thermoelectric material is a kind of can to realize the new energy material that heat energy and electric energy are directly changed Material, the thermoelectric generation based on thermoelectric material is entered currently with low-grade heat sources such as industrial exhaust heat, vehicle exhaust and underground heat The optimal selection that row generates electricity.The operating efficiency of thermoelectric material depends primarily on its electroacoustic and transports performance, that is, require material have compared with High electrical conductivity, Seebeck coefficients and relatively low thermal conductivity.The raising of electronic transport performance can pass through doping or adjustment of formula etc. Means optimize carrier concentration to realize.The optimization of phonon transport performance is mainly two kinds of approach, and one is in conventional thermoelectric materials On the basis of adulterated by solid solution, prepare the technology such as nanocrystalline or nano combined increase phon scattering reduction thermal conductivity；It is another heavy It is to excavate the material with intrinsic lower thermal conductivity to want approach, and it has turned into a kind of important directions that thermoelectric material is studied.
In recent years, sulfur family lead compound PbSe is received significant attention as thermoelectric material, it have carrier concentration it is controllable, The advantages of component is cheap, heat endurance is good.But PbSe thermal conductivity is higher, it is necessary to more multiple by nano combined grade Miscellaneous technique reduces its thermal conductivity.
American scholar Bremholm (Solide state Science, 13 (2011) 38-41) and Jilin University Wang Xin (one Plant and directly prepare Tetragonal PbSe2The method CN 105016316A of compound) it is utilized respectively vacuum melting combination high pressure and machinery Alloy combination high pressure method is prepared for the PbSe of tetragonal phase structure2Compound.Both of which is to prepare Emission in Cubic first High-pressure sinter just obtains the PbSe of Tetragonal after PbSe is mixed with a certain amount of Se again2.So existing PbSe2Preparation method is deposited Long preparation period, cost it is high, it is repeated bad the shortcomings of.Moreover, PbSe2Thermotransport performance (thermal conductivity) there is no report.
A kind of directly system is disclosed in Application No. 201510489779.2, Publication No. CN 105016316A patent Standby Tetragonal PbSe2Method, this method is raw material using Pb powder and Se powder, utilizes dry grinding, wet-milling that powdered precursor is made PbSe, then, PbSe is synthesized using high pressure synthesis method again2.But, the preparation method in documents 1 have to pass through dry grinding, Wet-milling twice program, synthesis PbSe recycles intermediate product further to pass through high-pressure synthesis PbSe as intermediate product2.But This method can not directly obtain PbSe2, in addition, the Tetragonal PbSe that this method is obtained2Thermal conductivity is higher, real by multi-stage synthesis Test, the thermal conductivity of its prepared material is simultaneously unstable, and thermal conductivity rate of change and variance are higher, it is impossible to which meeting in industrial production pair can The requirement of repeatability.
The content of the invention
In view of the above-mentioned problems, the present invention is more simple desirable to provide a kind of technique of the preparation process without Emission in Cubic PbSe Single tetragonal phase structure PbSe2Preparation method.To reduce manufacturing cycle, to reduce cost, and, it is desirable to obtain one kind and prepare Method, it results in lower thermal conductivity PbSe2, and it is desirable that the repeatability height of the preparation method, the PbSe of prepared acquisition2 Thermal conductivity index is stable.
Specifically, the present invention provides a kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound, it is characterised in that The preparation method comprises the following steps：
Step 1) metal simple-substance and a non-metal simple-substance are placed in ball grinder by predetermined molar ratio mixing；
Step 2) absolute ethyl alcohol is injected to ball grinder, and deoxygenated and/or protection processing, ball grinder is fixed on ball milling On machine, the wet-milling scheduled time；
Step 3) block is pressed into resulting dried powder；
Step 4) block being pressed into is subjected to high-pressure synthesis.
Preferably, the metal simple-substance is Pb powder, and the non-metal simple-substance includes Se powder.
Preferably, the high-pressure synthesis in the step (4) is carried out in high temperature high pressure device, the synthesis pressure of use For 4~5GPa, heating rate is 200-400 DEG C/min, and soaking time is 10-20min.
Preferably, the lower thermal conductivity thermoelectric compound is PbSe2。
Preferably, deoxidation and/or the protection processing includes being passed through high-purity Ar gas after ball grinder is vacuumized, and repetition is taken out true Empty, logical high-purity Ar operation is several times.
Preferably, Pb, Se purity are more than 99.9% in selected raw material.
Preferably, methods described has high repeatability.
Described drying, can be dried 4 hours under 60 degree.
The ball milling experiment of invention can be carried out in planetary ball mill, and high-pressure synthesis is tested on domestic cubic hinge press Complete.Optimal synthesis pressure is 4-5GPa, and optimum synthesising temperature is 650-750 degree, and the heat-insulation pressure keeping time is 10-30 minutes.
In addition, for the preparation method disclosed in patent application 201510489779.2, method of the invention The low 20%-40% of thermal conductivity of prepared thermoelectric compound, also, many experiments obtain material thermal conductivity floating change far The material prepared much smaller than method disclosed in patent application 201510489779.2, is more beneficial for stablize, height is repeated Property acquisition lower thermal conductivity thermoelectric material.
In a kind of preferred implementation, methods described carries out following step after being additionally included in step (3)：
Step 3.1) sample broke after high-pressure synthesis, grinding and utilization carbon disulfide are washed 3-5 times；
Step 3.2) processing is dried in the product after washing, obtain dried powder；
Step 3.3) dried powder is pressed into block and secondary high-pressure sintering is carried out, obtain PbSe2Compound.
In the preferred implementation, sintered by washing and secondary high-pressure, obtain PbSe2The purity of compound can be with Further improve, improve to more than 99.9%, repeatability is improved.
The beneficial effect brought of the present invention at least include it is following in one：
A. prepare that material periodicities are short, technique is simple.The present invention has technique simple, and synthetic material is rapid, saves the energy, fits Close the advantage of large-scale industrial production.
b.PbSe2The thermal conductivity of compound is smaller, only the 1/2 of cubic structure PbSe.
Other advantages, target and the feature of the present invention will be illustrated in following embodiment with reference to accompanying drawing, And to a certain extent, based on to reading and understanding hereafter, these advantages and features are to those skilled in the art It can be appreciated that.
Brief description of the drawings
Fig. 1 is the PbSe prepared using method described in embodiment 12X ray diffracting spectrum
Fig. 2 is using the PbSe that described in embodiment 1 and embodiment 2 prepared by method2And Bi doping PbSe2Thermal conductivity
Fig. 3 is the PbS prepared using method described in embodiment 32With PbSeS thermal conductivity
Embodiment
Embodiment 1：
Using lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:2.1 are mixed, and are placed on In stainless steel jar mill.Absolute ethyl alcohol is injected, is vacuumized, leads to protection gas.With 300 turns per minute of speed ball milling 2 hours, collect 60 degree of dryings 4 hours, vapor away whole absolute ethyl alcohols, obtain dry powder forerunner under sample in ball grinder, vacuum condition Thing.
Powdered precursor is put into steel die and predecessor is pressed into block using tablet press machine.In domestic cubic apparatus High-pressure synthesis is carried out in high-tension apparatus.Synthesis pressure is 4.5GPa, and temperature is 700 degree, and heat-insulation pressure keeping 20 minutes is obtained containing few Measure the PbSe of impurity2Compound.After a high-pressure synthesis sample broke grinding, 3-5 removing is washed using carbon disulfide Impurity component, then dried and high-pressure sinter by identical process conditions.Obtain high-purity Tetragonal PbSe2Compound, specific X Ray diffraction results are shown in Fig. 1.Its thermal diffusion coefficient is tested out using laser thermal conductivity LFA457, and calculates thermal conductivity.Such as Fig. 2 It is shown, Tetragonal PbSe2Thermal conductivity be only the 1/2 of cubic structure PbSe.Shown using Density function theory：Same cube Structure PbSe is compared, Tetragonal PbSe2With smaller Young's modulus and bigger Green's parameter, therefore illustrate Tetragonal PbSe2 With weaker chemical bond, its lattice vibration anharmonicity is stronger simultaneously, and this is to cause PbSe2The reason for compared with lower thermal conductivity.
The inventive method obtains the thermal conductivity of sample than utilizing mechanical alloying (dry method in patent CN 105016316A Ball milling+wet-milling mixing) combine PbSe prepared by high pressure method2It is lower, it is applicant's understanding that this is primarily due to the inventive method system Standby technique more simplicity eliminates ma process, it is to avoid the contaminated probability of sample, while utilizing CS2Washing can Effectively to remove impurity component, PbSe is kept2Relatively low intrinsic thermal conductivity.
Thermal conductivity of the inventive method of table 1 with product prepared by existing method at different temperatures changes
Table 2 is under mutually synthermal (373K), and the inventive method is contrasted with existing method repeatability
Data comparison in upper table is it can be found that the repeatability of method can not show a candle to the inventive method employed in prior art Reproducible, the fluctuating range and variance of thermal conductivity are much larger than the inventive method.
Embodiment 2：
In the present embodiment, using identical preparation technology flow in embodiment 1, part Pb is substituted by the use of Bi as doped chemical It is prepared for BixPb1-xSe2, adding the thermal conductivity of 5mol%Bi sample can further reduce, and be primarily due to Bi and Pb original Protonatomic mass and ionic radius differ greatly, and Bi can cause distortion of lattice after entering lattice, cause phon scattering.And improve mixing for Bi Miscellaneous (10mol%) can separate out impurities phase, and thermal conductivity is raised on the contrary.Thermal conductivity result is as shown in Figure 2.
Embodiment 3：
In the present embodiment, using identical preparation technology flow in embodiment 1, substitute Se using S and be prepared for the phase isomorphous Body structure PbS2And PbSeS, the PbS of tetragonal phase structure2With the thermal conductivity smaller than cubic structure PbS.Thermal conductivity result is as schemed Shown in 3.In addition, applicant is to PbS2Repeatable experiment has been carried out respectively with PbSeS, compared for dry grinding+wet-milling, wet-milling, wet The repeatability of three kinds of situations of mill+double sintering, it is found that wet-milling+double sintering can not significantly improve both thermoelectric compounds Thermal conductivity repeatability, but the purity of reaction product can be improved.
Embodiment 4：
Using lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:2 are mixed, and are placed on not In steel ball grinding jar of becoming rusty.Absolute ethyl alcohol is injected, is vacuumized, leads to protection gas.With 300 turns per minute of speed ball milling 2 hours, ball is collected 60 degree of dryings 4 hours, vapor away whole absolute ethyl alcohols, obtain dry powdered precursor under sample in grinding jar, vacuum condition.
Powdered precursor is put into steel die and predecessor is pressed into block using tablet press machine.In domestic cubic apparatus High-pressure synthesis is carried out in high-tension apparatus.Synthesis pressure is 4.5GPa, and temperature is 700 degree, and heat-insulation pressure keeping 20 minutes obtains PbSe2 Compound.
The present embodiment can equally obtain PbSe2Compound, simply the Tetragonal PbSe in the present embodiment2Compound purity Less than embodiment 1, its thermal conductivity still be less than existing method, simply repeatability with existing method substantially close to.
It is last it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and unrestricted, this area Other modifications or equivalent substitution that those of ordinary skill is made to technical scheme, without departing from the technology of the present invention The spirit and scope of scheme, all should cover among scope of the presently claimed invention.

Claims (8)

1. a kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound, it is characterised in that the preparation method includes following step Suddenly：
Step 1) metal simple-substance and a non-metal simple-substance are placed in ball grinder by predetermined molar ratio mixing；
Step 2) absolute ethyl alcohol is injected to ball grinder, and deoxygenated and/or protection processing, ball grinder is fixed on ball mill On, the wet-milling scheduled time；
Step 3) block is pressed into resulting dried powder；
Step 4) block being pressed into is subjected to high-pressure synthesis.
2. lower thermal conductivity PbSe according to claim 12The preparation method of thermoelectric compound, it is characterised in that the metal Simple substance is Pb powder, and the non-metal simple-substance includes Se powder.
3. lower thermal conductivity PbSe according to claim 12The preparation method of thermoelectric compound, it is characterised in that wherein, High-pressure synthesis in the step (4) is carried out in high temperature high pressure device, and the synthesis pressure used is 4~5GPa, heating speed Rate is 200-400 DEG C/min, and soaking time is 10-20min.
4. lower thermal conductivity PbSe according to claim 12The preparation method of thermoelectric compound, it is characterised in that the low-heat Conductance thermoelectric compound is PbSe2。
5. lower thermal conductivity PbSe according to claim 12The preparation method of thermoelectric compound, it is characterised in that the deoxidation And/or protection processing includes being passed through high-purity Ar gas after ball grinder is vacuumized, repetition vacuumizes, leads to high-purity Ar operation several times.
6. lower thermal conductivity PbSe according to claim 12The preparation method of thermoelectric compound, it is characterised in that selected Pb, Se purity are more than 99.9% in raw material.
7. lower thermal conductivity PbSe according to claim 12The preparation method of thermoelectric compound, it is characterised in that methods described With high repeatability.
8. a kind of PbSe of lower thermal conductivity2Thermoelectric compound, it is characterised in that the PbSe2Thermoelectric compound uses following manner Prepare,
Step 1) metal simple-substance and a non-metal simple-substance are placed in ball grinder by predetermined molar ratio mixing；
Step 2) absolute ethyl alcohol is injected to ball grinder, and deoxygenated and/or protection processing, ball grinder is fixed on ball mill On, the wet-milling scheduled time；
Step 3) block is pressed into resulting dried powder；
Step 4) block being pressed into is subjected to high-pressure synthesis.
CN201710479649.XA 2017-06-22 2017-06-22 A kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound Pending CN107265412A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626446A (en) * 2019-01-22 2019-04-16 河南理工大学 A kind of preparation method of cubic structure CoSbS thermoelectric compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101549405A (en) * 2009-05-19 2009-10-07 燕山大学 High-pressure sintering preparation method of high-densification high-performance nano crystal block thermoelectric material
CN105016316A (en) * 2015-08-11 2015-11-04 吉林大学 Method for preparing square-phase Pb Se2 compound directly
CN106006574A (en) * 2016-05-11 2016-10-12 河南理工大学 Rapid preparation method for thermoelectric compound

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101549405A (en) * 2009-05-19 2009-10-07 燕山大学 High-pressure sintering preparation method of high-densification high-performance nano crystal block thermoelectric material
CN105016316A (en) * 2015-08-11 2015-11-04 吉林大学 Method for preparing square-phase Pb Se2 compound directly
CN106006574A (en) * 2016-05-11 2016-10-12 河南理工大学 Rapid preparation method for thermoelectric compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109626446A (en) * 2019-01-22 2019-04-16 河南理工大学 A kind of preparation method of cubic structure CoSbS thermoelectric compound
CN109626446B (en) * 2019-01-22 2021-05-18 河南理工大学 Preparation method of cubic CoSbS thermoelectric compound

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Application publication date: 20171020