CN105016316B - One kind directly prepares Tetragonal PbSe2The method of compound - Google Patents
One kind directly prepares Tetragonal PbSe2The method of compound Download PDFInfo
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- CN105016316B CN105016316B CN201510489779.2A CN201510489779A CN105016316B CN 105016316 B CN105016316 B CN 105016316B CN 201510489779 A CN201510489779 A CN 201510489779A CN 105016316 B CN105016316 B CN 105016316B
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Abstract
The present invention provides one kind directly to prepare Tetragonal PbSe2The method of compound, belongs to the technical field of functional material preparation.Preparation method, with Pb powder and Se powder as raw material, has dry ball milling, wet ball grinding, powdered precursor, the process of high-pressure synthesis is obtained；Particularly Pb powder and half amount Se powder are mixed, with 350～450 revs/min of rotating speed ball millings 1～2.5 hour in the ball grinder fill protective gas；Add remaining Se powder and ethanol, wet ball grinding in the ball grinder fill protective gas；Make block after product dried and carry out high-pressure synthesis, heat-insulation pressure keeping 40min at 3.8～5GPa, 600～800 DEG C, obtain tetragonal phase structure PbSe2Compound.The preparation method of the present invention is with low cost, short preparation period, process is simple, energy saving, need not the high-purity compact block material that obtains of follow-up remove impurity operation, be therefore suitable for large-scale industrial production.
Description
Technical field
The invention belongs to the technical field of functional material preparation.It is specifically related to the Tetragonal of lead selenide, be former with Pb, Se
Material, the method using high-energy ball milling and high-pressure synthesis prepares PbSe2The method of Tetragonal.
Background technology
With social continuous development and progress, people are also more deep to the cognition of material, and lead selenide becomes wide already
A class material of critical role is occupied in general application.Cubic structure lead selenide (PbSe) as infrared detector material, photosensitive biography
Sensor material, has obtained important application.Go from bad to worse recently as fossil energy increasingly depleted and environment, PbSe is as the sun
Energy battery and thermoelectric material also receive significant attention.Changes in crystal structure is larger for the electronic structure impact of material, and then
Affect the physical parameters such as its calorifics, electricity and optics.Research currently for lead selenide focuses primarily upon cubic structure PbSe's
Synthesis, physical property and device functionization research, the increasingly complex tetragonal phase structure PbSe of crystal structure2Research less, its pole
It is possible to produce different from the new light of cubic structure, electricity, heat effect.And PbSe2Belong to Nonequilibrium Materials, synthesis is more difficult,
Existing method technique is extremely complex, and preparation cost is high.Develop a kind of high-purity Tetragonal PbSe of process is simple2Preparation
Method, contributes to increasing lead selenide as the potential application of functional material, expands its application.
Synthesis tetragonal phase structure PbSe at present2Method Solid State is disclosed in by American scholar Bremholm et al.
Sciences 13 (2011) 38-41, the method utilizes vacuum melting to combine the PbSe of high-pressure sinter method preparation2Material, but its
Technique and its complexity.Vacuum high-temperature heat treatment firstly the need of 12 hours prepares cubic structure PbSe, then presses PbSe：Se=
1:The laggard horizontal high voltage of 2 mix homogeneously synthesizes, and after high-pressure synthesis, sample contains a large amount of Se impurity, needs Na2S cleaning could remove Se
Impurity obtains the PbSe compared with high-purity2Sample, in order to further characterize its physical property and application, also needs to do high-pressure molding further
And sintering processes make its densification.So existing Tetragonal PbSe2There is synthesis cycle length, complex process, one-tenth in preparation method
The shortcomings of this height, poor repeatability.
Content of the invention
The technical problem to be solved in the present invention is the shortcoming overcoming background technology, provides technique more simple Tetragonal knot
Structure PbSe2The preparation method of block materials, to reduce manufacturing cycle, reduces cost and to improve repeatability.
Specifically, the invention provides one kind directly prepares Tetragonal PbSe2The method of compound, walks including following
Suddenly：
Step 1) raw material is placed in ball grinder, described raw material includes Pb powder and Se powder by certain mol proportion mixing；
Step 2) ball grinder is carried out deoxygenating protection process, and treated ball grinder is fixed on ball mill, dry method
The ball milling scheduled time；The purpose of dry ball milling is mainly and forms cube phase structure PbSe compound.
Step 3) add certain Se powder in ball grinder and inject dehydrated alcohol, the wet grinding scheduled time；Wet grinding is mainly
After dry grinding, cubic structure PbSe powder is mixed homogeneously with Se powder, it is possible to additionally incorporate dehydrated alcohol wet grinding and is also possible to prevent raw material and glues
Attached with abrading-ball and ball grinder on.
Step 4) process is dried to the product after wet grinding, obtain dried powder predecessor；
Step 5) block is pressed into obtained dried powder；
Step 6) block being pressed into is carried out high-pressure synthesis, obtain Tetragonal PbSe2Compound；Described high-pressure synthesis,
It is to carry out in high temperature high pressure device, block sample wraps up boron nitride insulation tube, load in pyrophillite Synthetic block, the synthesis of employing
Pressure is 3～5GPa, and synthesis temperature is 600～800 DEG C, and heating rate is 200～400 DEG C/min, and the heat-insulation pressure keeping time is
40min.
In described step 2) and 3) in, ball material quality is respectively than for 20:1 and 15:1, rotating speed is respectively 400 revs/min and 300
Rev/min, the ball milling scheduled time is respectively 2 hours and 0.5 hour.The dry grinding time is not less than 1 hour, and rotating speed is not less than 350r/
Min, you can obtain and make Pb and Se alloying form cubic structure PbSe predecessor.Wet grinding rotating speed is not less than 200r/min, wet grinding
Time got final product mix homogeneously not less than 30 minutes.Rotational speed of ball-mill is not less than 350 revs/min (dry grinding) and 200r/min (wet grinding),
Time is not less than 1 hour (dry grinding) and 0.5 hour (wet grinding), does not interfere with follow-up result.Wet ball grinding ratio of grinding media to material does not include second
The quality of alcohol, during wet grinding, the requirement to ratio of grinding media to material is not strict, as long as ratio of grinding media to material is not less than 10 can achieve sample mix
Uniformly.
The ball milling experiment of invention can be carried out in planetary ball mill, and high-pressure synthesis are tested on domestic cubic hinge press
Complete.Dry ball milling time and rotating speed, and high-pressure synthesis temperature and pressure be impact PbSe2The key factor of purity, most preferably
Dry ball milling speed and time are respectively 400 revs/min and 2 hours；Optimal synthesis pressure is 4GPa, and optimum synthesising temperature is 700
DEG C, the heat-insulation pressure keeping time is 40 minutes.Synthesis temperature at 700 ± 50 degree, synthesis pressure 4GPa, all can obtain highly purified four directions
Phase structure PbSe2.The too high PbSe of temperature2Can decompose precipitation Se and Emission in Cubic PbSe, temperature too low containing Se impurity, pressure is less than
The sample that 3.8GPa synthesizes at different temperatures all has dephasign.
Summary, the technical scheme that the present invention is claimed is summarized as follows.
One kind directly prepares Tetragonal PbSe2The method of compound, with Pb powder and Se powder as raw material, has dry ball milling, wet
Method ball milling, prepared powdered precursor, the process of high-pressure synthesis；
Described dry ball milling, is that 1: 1 mixing is placed in the ball grinder filling protective gas in molar ratio by Se powder and Pb powder,
Ball material mass ratio is 20: 1, with 350～450 revs/min of rotating speed ball millings 1～2.5 hour, obtains a cube phase structure PbSe compound；
Described wet ball grinding, is to add Se powder after dry ball milling in ball grinder, addition and Pb powder mole
Than for 1～1.03: 1；Injection dehydrated alcohol, injection rate is to cover whole ball material in ball grinder；It is milled to vertical after filling protective gas
Square phase structure PbSe compound is mixed homogeneously with Se powder；
Described prepared powdered precursor, is to be dried process to the product after wet grinding, vapors away all anhydrous second
Alcohol, obtains dried powder predecessor；
Described high-pressure synthesis, are pressed into block to dried powder predecessor and carry out high-pressure synthesis, synthesis pressure be 3.8～
5GPa, synthesis temperature is 600～800 DEG C, heat-insulation pressure keeping 40～45min, and cooling release obtains Tetragonal PbSe2Compound.
In the process of dry ball milling and wet ball grinding, described fill protective gas, be high-purity by being passed through after ball grinder evacuation
Ar gas, repeats evacuation, logical high-purity Ar operates 3～6 times.For discharging the oxygen in ball grinder.
Optimal dry ball milling speed and time are 400 revs/min and 2 hours.
Described wet ball grinding, can be 10～15: 1 using ratio of grinding media to material, and little with 200～300 revs/min of rotating speed ball millings 0.5
When." the expecting " of wherein ratio of grinding media to material does not contain dehydrated alcohol.
Described dried, can be the lower 60 DEG C of dryings of vacuum condition 4 hours.
Optimal synthesis pressure is 4GPa, and preferred synthesis temperature is 650～750 DEG C, and optimum synthesising temperature is 700 DEG C,
The good heat-insulation pressure keeping time is 40 minutes；Preferably it was warming up to 700 with the heating rate of 200～400 DEG C/min before heat-insulation pressure keeping
℃.
The quality purity of described Pb powder and Se powder is not less than 99.9%.
The beneficial effect that the present invention is brought：
A. prepare Tetragonal PbSe2Compound-material cycle is short, process is simple, synthetic material is rapid, energy saving, is suitable for
Large-scale industrial production.
B. the high-purity compact block material that can directly prepare, need not follow-up remove impurity operation, element ratio is controlled.
Brief description
The Tetragonal PbSe of Fig. 1 embodiment 1 preparation2X ray diffracting spectrum.
The Tetragonal PbSe of Fig. 2 embodiment 2 preparation2X ray diffracting spectrum.
The Tetragonal PbSe of Fig. 3 embodiment 3 preparation2X ray diffracting spectrum.
The Tetragonal PbSe of Fig. 4 embodiment 4 preparation2X ray diffracting spectrum.
The Tetragonal PbSe of Fig. 5 embodiment 5 preparation2X ray diffracting spectrum.
Specific embodiment
The method of the present invention, prepared product and its feature are explained combining accompanying drawing in following specific embodiment
State, and to a certain extent, based on to reading hereafter and understanding, these products and its feature are for those skilled in the art
For be apparent.
Embodiment 1：
With lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:1 is mixed, and is placed on not
In rust steel ball grinding jar.Evacuation, logical shielding gas, more than 3 times repeatedly.With 400 turns per minute of speed ball milling 2 hours, backward
Add the Se powder with equal in quality during dry grinding in ball grinder, and add dehydrated alcohol to all pellets of submergence, evacuation is simultaneously passed through
High-purity Ar gas continues ball milling 30 minutes, and rotating speed is 300 revs/min.After wet grinding, collect the sample in ball grinder, subsequently right
Product after wet grinding is dried process, the lower 60 DEG C of dryings of vacuum condition 4 hours, vapors away whole dehydrated alcohol, is done
Dry powdered precursor.
Powdered precursor is put in steel die and using tablet machine, predecessor is pressed into block.Block sample is put into
In boron nitride insulation tube, then it is loaded in pyrophillite synthetic cavity, use graphite as heating tube in synthetic cavity, pyrophillite is made
For insulation and pressure transmission material.Synthesis pressure is 4GPa, and temperature is 700 degree, 40 minutes heat-insulation pressure keeping time, stops heating nature cold
But release after 2 minutes.The Tetragonal PbSe of this condition preparation2Better crystallinity degree, purity is high, and specific X-ray diffraction structure is shown in figure
1.
Embodiment 2：
With lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:1 is mixed, and is placed on not
In rust steel ball grinding jar.Evacuation, logical shielding gas, more than 3 times repeatedly.With 400 turns per minute of 2 hours backward ball millings of speed ball milling
Add the Se powder with equal in quality during dry grinding in tank, and add dehydrated alcohol to all pellets of submergence, evacuation is simultaneously passed through high-purity
Ar gas continues ball milling 30 minutes, and rotating speed is 300 revs/min.After wet grinding, collect the sample in ball grinder, subsequently to through wet
Product after mill is dried process, and under vacuum condition, 60 degree of dryings 4 hours, vapor away whole dehydrated alcohol, obtains drying
Powdered precursor.
Powdered precursor is put in steel die and using tablet machine, predecessor is pressed into block.Block sample is put into
In boron nitride insulation tube, then it is loaded in pyrophillite synthetic cavity, use graphite as heating tube in synthetic cavity, pyrophillite is made
For insulation and pressure transmission material.Synthesis pressure is 4GPa, and temperature is 600 degree, 40 minutes heat-insulation pressure keeping time, stops heating nature cold
But release after 2 minutes.The Tetragonal PbSe of this condition preparation2Containing a small amount of Se, specific X-ray diffraction structure is shown in Fig. 2.
Embodiment 3：
With lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:1 is mixed, and is placed on not
In rust steel ball grinding jar.Evacuation, logical shielding gas, more than 3 times repeatedly.With 400 turns per minute of 2 hours backward ball millings of speed ball milling
Add the Se powder with equal in quality during dry grinding in tank, and add dehydrated alcohol to all pellets of submergence, evacuation is simultaneously passed through high-purity
Ar gas continues ball milling 30 minutes, and rotating speed is 300 revs/min.After wet grinding, collect the sample in ball grinder, subsequently to through wet
Product after mill is dried process, and under vacuum condition, 60 degree of dryings 4 hours, vapor away whole dehydrated alcohol, obtains drying
Powdered precursor.
Powdered precursor is put in steel die and using tablet machine, predecessor is pressed into block.Block sample is put into
In boron nitride insulation tube, then it is loaded in pyrophillite synthetic cavity, use graphite as heating tube in synthetic cavity, pyrophillite is made
For insulation and pressure transmission material.Synthesis pressure is 4GPa, and temperature is 800 degree, 40 minutes heat-insulation pressure keeping time, stops heating nature cold
But release after 2 minutes.The Tetragonal PbSe of this condition preparation2PbSe containing Emission in Cubic and simple substance Se, specific X-ray diffraction
Structure is shown in Fig. 3.
Embodiment 4：
With lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:1 is mixed, and is placed on not
In rust steel ball grinding jar.Evacuation, logical shielding gas, more than 3 times repeatedly.With 400 turns per minute of 2 hours backward ball millings of speed ball milling
Add the Se powder with equal in quality during dry grinding in tank, and add dehydrated alcohol to all pellets of submergence, evacuation is simultaneously passed through high-purity
Ar gas continues ball milling 30 minutes, and rotating speed is 300 revs/min.After wet grinding, collect the sample in ball grinder, subsequently to through wet
Product after mill is dried process, and under vacuum condition, 60 degree of dryings 4 hours, vapor away whole dehydrated alcohol, obtains drying
Powdered precursor.
Powdered precursor is put in steel die and using tablet machine, predecessor is pressed into block.Block sample is put into
In boron nitride insulation tube, then it is loaded in pyrophillite synthetic cavity, use graphite as heating tube in synthetic cavity, pyrophillite is made
For insulation and pressure transmission material.Synthesis pressure is 3GPa, and temperature is 700 degree, 40 minutes heat-insulation pressure keeping time, stops heating nature
Release after cooling down 2 minutes.The Tetragonal PbSe of this condition preparation2PbSe containing Emission in Cubic and simple substance Se, specific X-ray is spread out
Penetrate structure and see Fig. 4.
The present embodiment, as comparative example, illustrates that synthesis pressure will increase less than 3.8GPa impurity.
Embodiment 5：
With lead (Pb) powder and selenium (Se) powder as primary raw material, by Pb powder and Se powder with mol ratio 1:1 is mixed, and is placed on not
In rust steel ball grinding jar.Evacuation, logical shielding gas, more than 3 times repeatedly.With 400 turns per minute of 2 hours backward ball millings of speed ball milling
Add ratio 2.5%Se powder (by mass) excessive when dry grinding in tank, and add dehydrated alcohol to all pellets of submergence, evacuation is simultaneously
It is passed through high-purity Ar gas and continues ball milling 30 minutes, rotating speed is 300 revs/min.After wet grinding, collect the sample in ball grinder, with
Afterwards process is dried to the product after wet grinding, under vacuum condition, 60 degree of dryings 4 hours, vapor away whole dehydrated alcohol, obtain
To dry powdered precursor.
Powdered precursor is put in steel die and using tablet machine, predecessor is pressed into block.Block sample is put into
In boron nitride insulation tube, then it is loaded in pyrophillite synthetic cavity, use graphite as heating tube in synthetic cavity, pyrophillite is made
For insulation and pressure transmission material.Synthesis pressure is 4GPa, and temperature is 700 degree, 40 minutes heat-insulation pressure keeping time, stops heating nature cold
But release after 2 minutes.The Tetragonal PbSe of this condition preparation2Containing a small amount of Se, specific X-ray diffraction structure is shown in Fig. 5.
Last it should be noted that above example is only in order to illustrate technical scheme and unrestricted, this area
Other modifications or equivalent 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 in the middle of scope of the presently claimed invention.
Claims (7)
1. one kind directly prepares Tetragonal PbSe2The method of compound, have dry ball milling, wet ball grinding, be obtained powdered precursor,
The process of high-pressure synthesis；
Described dry ball milling, is that 1: 1 mixing is placed in the ball grinder filling protective gas in molar ratio by Se powder and Pb powder, ball material
Mass ratio is 20: 1, with 350～450 revs/min of rotating speed ball millings 1～2.5 hour, obtains a cube phase structure PbSe compound；
Described wet ball grinding, is to add Se powder after dry ball milling in ball grinder, and addition is 1 with the mol ratio of Pb powder
～1.03: 1；Injection dehydrated alcohol, injection rate is to cover whole ball material in ball grinder；It is milled to Emission in Cubic knot after filling protective gas
Structure PbSe compound is mixed homogeneously with Se powder；
Described prepared powdered precursor, is to be dried process to the product after wet grinding, vapors away whole dehydrated alcohol, obtain
To dried powder predecessor；
Described high-pressure synthesis, are pressed into block to dried powder predecessor and carry out high-pressure synthesis, synthesis pressure be 3.8～
5GPa, synthesis temperature is 600～800 DEG C, heat-insulation pressure keeping 40～45min, and cooling release obtains Tetragonal PbSe2Compound.
2. according to claim 1 directly prepare Tetragonal PbSe2The method of compound is it is characterised in that in dry ball milling
With the process of wet ball grinding, described fill protective gas, be after ball grinder evacuation, to be passed through Ar, repeat evacuation, logical Ar operation 3
～6 times.
3. according to claim 1 directly prepare Tetragonal PbSe2The method of compound is it is characterised in that dry ball milling is fast
Spend for 400 revs/min, Ball-milling Time 2 hours.
4. according to claim 1 directly prepare Tetragonal PbSe2The method of compound is it is characterised in that described wet method
Ball milling, is 10～15: 1 using ratio of grinding media to material, and with 200～300 revs/min of rotating speed ball millings 0.5 hour.
5. according to claim 1 directly prepare Tetragonal PbSe2The method of compound is it is characterised in that described drying
Process, be the lower 60 DEG C of dryings of vacuum condition 4 hours.
6. according to claim 1 directly prepare Tetragonal PbSe2The method of compound is it is characterised in that synthesis pressure is
4GPa, synthesis temperature is 700 DEG C, and the heat-insulation pressure keeping time is 40 minutes；With the liter of 200～400 DEG C/min before heat-insulation pressure keeping
Warm ramp is to 700 DEG C.
7. directly prepare Tetragonal PbSe according to any one of claim 1～62The method of compound it is characterised in that
The quality purity of described Pb powder and Se powder is not less than 99.9%.
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| CN107265412A (en) * | 2017-06-22 | 2017-10-20 | 河南理工大学 | A kind of lower thermal conductivity PbSe2The preparation method of thermoelectric compound |
| CN110649147A (en) * | 2019-09-11 | 2020-01-03 | 大连理工大学 | Second-phase doped TiNiSn-based Half-Heusler thermoelectric material and preparation method thereof |
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