CN104998593B - A kind of Hydrothermal Synthesiss processing technology - Google Patents
A kind of Hydrothermal Synthesiss processing technology Download PDFInfo
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- CN104998593B CN104998593B CN201510366073.7A CN201510366073A CN104998593B CN 104998593 B CN104998593 B CN 104998593B CN 201510366073 A CN201510366073 A CN 201510366073A CN 104998593 B CN104998593 B CN 104998593B
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Abstract
The present invention provides a kind of Hydrothermal Synthesiss processing technology, and the Hydrothermal Synthesiss processing technology comprises the following steps：Step 1) metallic compound that takes the first scheduled volume to include the first metal；Step 2) take the first non-metal simple-substance of the second scheduled volume；Step 3) metallic compound is mixed with the non-metal simple-substance, it is placed in solvent being configured to solution；Step 4) solution is heated to the first predetermined temperature and maintained for first scheduled time；Step 5) take step 4) in gained reaction product, and the reaction product is dried processing, the corresponding solid matter of acquisition；Step 6) solid matter is made to the block of predetermined shape；Step 7) predetermined pressure is forced into the block；Step 8) block is heated up with predetermined heating rate, and after the second predetermined temperature is warming up to, maintained for second scheduled time.Technological operation of the invention is simple, preparation efficiency is high, quality of finished product good.
Description
Technical field
The invention belongs to synthesize manufacture field, specifically, a kind of new Hydrothermal Synthesiss processing technology of the present invention.
Background technology
Hydrothermal Synthesiss refer to temperature be 100~1000 DEG C, pressure be to utilize material in the aqueous solution under the conditions of 1MPa~1GPa
The carried out synthesis of chemical reaction.Under subcritical and supercritical water heat condition, because reaction is in molecular level, reactivity is carried
Height, thus hydro-thermal reaction can substitute some high temperature solid state reactions.Again due to the homogeneous nucleation and nonhomogen-ous nucleation of hydro-thermal reaction
Mechanism is different from the flooding mechanism of solid phase reaction, thus can create noval chemical compound and green wood that other methods can not be prepared
Material.A series of Hydrothermal Synthesiss routes opened up and its developed on this basis gently with HTHP hydro-thermal reaction,
As the current important channel for obtaining most inorganic functional materials and extraordinary composition and the inorganic compound of structure.In Hydrothermal Synthesiss
In system, a variety of new synthetic routes and new synthetic method, such as direct method, seed-grain method, directing agent method, template have been developed
Method, complexing agent method, organic solvent method and microwave method.
But, research direction is concentrated on into Hydrothermal Synthesiss there is presently no report and solid high-voltage synthesizes the combination side of the two
Face.Moreover, existing hydro-thermal synthesis process is not also very perfect, in addition it is also necessary to be improved in many-side.
The content of the invention
In view of the above-mentioned problems, the present invention is improved and optimized to hydro-thermal synthesis process, using elemental nonmetal and gold
Belong to the mode that compound phase is combined, first under solution state, low temperature (for common Hydrothermal Synthesiss) enters in utilization
Row reaction, and adjust the pH value of reaction.In addition, the present invention is after middle low-temperature hydrothermal reaction has been carried out, herein in connection with super-pressure
Prepared by sintering process, to carry out the preparation of compound, have the advantage of the two concurrently.It is characteristic of the invention that work prepares skill simply, system
Standby process is without any organic solvent, and sample granularity is uniform, purity is high, and block materials consistency is high, and carrier concentration is controllable.Hair
The preparation technology of a person of good sense is not concerned only with the microscopic appearance of compound, and the current-carrying that concern is closely related with compound thermoelectric performance
The regulation and control of sub- concentration.
Specifically, the invention provides a kind of Hydrothermal Synthesiss processing technology, it is characterised in that the Hydrothermal Synthesiss processing
Technique comprises the following steps：
Step 1) metallic compound that takes the first scheduled volume to include the first metal；
Step 2) take the first non-metal simple-substance of the second scheduled volume；
Step 3) metallic compound is mixed with the non-metal simple-substance, it is placed in solvent being configured to solution；
Step 4) solution is heated to the first predetermined temperature and maintained for first scheduled time；
Step 5) take step 4) in gained reaction product, and be dried processing to the reaction product, obtain accordingly
Solid matter；
Step 6) solid matter is made to the block of predetermined shape；
Step 7) predetermined pressure is forced into the block；
Step 8) block is heated up with predetermined heating rate, and after the second predetermined temperature is warming up to, dimension
Held for second scheduled time.
Preferably, first metal is the metal in the main group of the periodic table of elements the 4th or the 5th main group；Described first is non-
Metal simple-substance is the non-metal simple-substance in the main group of the periodic table of elements the 5th or the 6th main group.
Preferably, the relation between first scheduled volume and second scheduled volume is that the molar ratio of the two is 1:
1.02 to 1:1.1.
Preferably, the solvent is water, and first metal is Pb, Sb or Ag, and the compound of first metal is institute
State the nitrate, sulfate or chloride of the first metal.
Preferably, first non-metal simple-substance is phosphorus or sulphur.
Preferably, first predetermined temperature is 100-220 degree, and first scheduled time is 2-18 hours.
Preferably, the step 5) also include washing the reaction product of the solution, the drying process is used
Drying mode for vacuum drying 4-12 hour, drying temperature be 45-60 DEG C or 60-70 DEG C.
Preferably, the step 4) also include the pH value for adjusting the solution to >=10, it is preferably adjusted to 11-12.5.This
The inventor of application has found, after the pH value of hydro-thermal reaction is adjusted into 11-12.5, reacts more thorough, product property is more preferable.
In a kind of preferred implementation, compound uses Pb (NO3)2Non-metal simple-substance uses S powder, in addition, also in chemical combination
The chloride of doped chemical is added in thing.
In a kind of preferred implementation, in the step 7) in the predetermined pressure that is previously mentioned refer to 1.3-2.5GPa,
It is preferred that 2.1GPa.Step 8) in the second predetermined temperature be that sintering temperature is 400~700 DEG C, preferably 600 DEG C, second make a reservation for
Time is 15~50 minutes.
Preferably, 1 is additionally added in the solution:1.5 NaOH and NaBH4.Further, with SbCl also when configuring solution3
Or BiCl3To be used as dopant.The two total content is the 0.5%-1.2% of the metallic compound of the first metal.
In another implementation, it can also include mixing for Pb if raw metal is selected in Pb, compound
Miscellaneous Bi, Sb or Ag, doping is the 0~2% of S elements.
In addition, in another implementation, if raw metal selects Pb, the raw material also includes BiCl3、SbCl3
And/or AgNO3Powder, doping is the 0~4% of S elements.Preferably, the raw material is included for S elements, mol ratio 1
~2.5% Sb, the Bi of mol ratio 0.4~0.8%.It is further preferred that the raw material also includes relative to S elemental mole ratios
0.3-2% Sb.Inventors herein have recognized that, after addition above-mentioned substance, the thermoelectricity capability of material, which has, further to be carried
Rise.
Raw metal can also be from Sb, Sn etc., can be with pure Sb, Sn metallic compound when from these metals
Prepared, accordingly can also add Pb in doping.
Advantages of the present invention is as follows：
1) 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 large-scale industrial production.
2) the powder body material particle prepared is divided equally, reproducible, and block materials consistency is high, with higher thermoelectricity
Performance.Exemplified by preparing PbS, its dimensionless figure factor is up to 0.76, suitable with the PbTe materials of commercial applications, but
The latter contains expensive Te elements.Certainly the technique of the present invention be can be also used for preparing other thermoelectric compounds, and it is prepared
Effect is also better than common hydro-thermal synthesis process.
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 xrd collection of illustrative plates in embodiment one exemplified by synthesizing PbS using the product prepared by present invention process.
Fig. 2 is the stereoscan photograph of the sample prepared by embodiment one.
Fig. 3 is the scanned photograph of sample prepared by embodiment one.
PbSs and its doped samples of the Fig. 4 prepared by embodiment two xrd collection of illustrative plates.
PbSs and its doped samples of the Fig. 5 prepared by embodiment two resistivity variation with temperature.
PbSs and its doped samples of the Fig. 6 prepared by embodiment two ZT value variation with temperature.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the present invention is described in detail.
Embodiment one
In one embodiment of the invention, PbS thermoelectric materials are prepared using the method for the present invention, step is as follows：
Step 1) -2) take equimolar than the metallic compound comprising Pb and S simple substance；Metallic compound elects acetic acid as
Lead.
Step 3) taken metallic compound is placed in stirring container with the non-metal simple-substance mixed, it is placed in solvent
It is configured to solution.Here solvent elects water as.
Step 4) appropriate alkali is added in a reservoir, the pH value of solution is adjusted to more than 8.The solution is heated to
100-220 degree, and maintain 3-24 hours；
Step 5) take step 4) in gained reaction product, and be dried processing to the reaction product, obtain accordingly
Solid matter；In the present embodiment, the drying process process used for：Scrubbed rear product is positioned over vacuum drying chamber
In, 3-10 hour is dried in vacuo, drying temperature is 50-60 DEG C or 60-70 DEG C.Inventor is had found by testing, and works as hydro-thermal
Reaction time, temperature was more than 100 degree more than 3 hours, you can obtain single-phase PbS dusty materials (such as Fig. 1), and sample granularity compares
Uniformly (such as Fig. 2).
Step 6) gained solid matter is put into mould, the block of predetermined character is made；
Step 7) predetermined pressure is forced into the block；
Step 8) block is heated up with predetermined heating rate, and after the second predetermined temperature is warming up to, dimension
Held for second scheduled time.Preferably, the pressure used during temperature-pressure is 2-3GPa.Temperature is 400~700 DEG C, is risen
Warm speed is 10~80 DEG C/min, and the time is 15min to 80min.After sintering, densified sample (such as Fig. 3) will be obtained.
In order to verify the performance of obtained sample, by the sample after sintering by cutting, tested after polishing using LSR-3
The resistivity of PbS samples, Seebeck (Seebeck) coefficient, the thermal conductivity of sample is tested using LFA-457.
As shown in table 1, higher sintering temperature helps to reduce resistivity, and reason is mainly：First, the consistency of sample
Increase with the rise of sintering temperature, the relatively low resistivity of high-compactness sample correspondence, secondly, can be produced under hot conditions few
The lattice defect of amount, improves carrier concentration.But sintering temperature is too high to cause sample decomposition to cause resistivity to increase,
Seebeck coefficients reduce.So, when sintering temperature is at 600 DEG C, PbS samples correspond to highest power factor.
Obtained PbS electronic transport performance is sintered under the conditions of the different sintering temperatures of table 1
Embodiment 2
In the present embodiment, employ with the similar mode of embodiment one to prepare sample, be in the present embodiment simply
The performance of increase gained compound, is added for Pb adulterate Sb, Bi or Ag, dopant is BiCl in the feed3、SbCl3Or
AgNO3, doping is the molar percentage 0~3% of S elements.
In the preparation and application process of thermoelectric material, the regulation and control of carrier concentration influence heavy to closing for thermoelectricity capability
Will, inventor has found that PbS carrier concentration can effectively be modulated by substituting part Pb formation instead type doping using Sb or Bi,
And seldom concern prepares doping PbS and other system thermoelectric materials using hydrothermal synthesis method before technical staff, the present invention is excellent
Select SbCl3And BiCl3The continuously adjustabe of PbS carrier concentrations is realized as dopant, table 2 is different elements and the doping of adulterating
Measure the influence to PbS carrier concentrations.It can be seen that a small amount of Sb and Bi of doping can effectively improve PbS carrier concentration and current-carrying
Transport factor.
Influences of the doping of table 2 Sb and Bi to PbS carrier concentrations and 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 Synthesiss combination high-pressure sinter is obtainedxPb1-xThe X-ray of S (x=0,0.01,0.02) sample is spread out
Penetrate collection of illustrative plates.In the figure illustrated embodiment, the Hydrothermal Synthesiss temperature used for 180 DEG C, the time be 12 hours, sintering pressure and
Temperature is respectively 3GPa and 600 DEG C.With the increase of Sb contents, all diffraction peaks are offset to the right, illustrate that atomic radius is smaller
Sb instead of Pb position.
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 samples in Range of measuring temp, it is seen that Sb, which adulterates, effectively reduces PbS resistivity.
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 doping 2%Sb of sample sample has higher thermoelectricity capability, and its maximum dimensionless figure factor is up to 0.76, with having engaged in trade
The PbTe materials of industryization application are suitable, but the latter contains expensive Te elements.
Embodiment three
In the present embodiment, inventor has carried out the experiment for preparing PbSe, experiment card using the preparation technology of the present invention
It is bright, it can equally process PbSe compounds using the synthesis technique of the present invention.In addition, the method for the present invention can also be extrapolated to member
Metal in the plain main group of periodic table the 4th or the 5th main group and the nonmetallic list in the main group of the periodic table of elements the 5th or the 6th main group
The preparation of any compound formed between matter.
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 (2)
1. a kind of Hydrothermal Synthesiss processing technology, it is characterised in that the Hydrothermal Synthesiss processing technology comprises the following steps：
Step 1) metallic compound comprising Pb is taken, metallic compound is lead acetate；
Step 2) take with Pb metallic compounds equimolar than S simple substance；
Step 3) taken lead acetate is placed in stirring container with the S simple substance mixed, it is placed in water being configured to solution；
Step 4) appropriate alkali is added in a reservoir, the pH value of solution is adjusted to more than 8, the solution is heated to 100-
220 DEG C, and maintain 3-24 hours；
Step 5) take step 4) in gained reaction product, washed, and the scrubbed reaction product is dried
Processing, obtains corresponding solid matter, the drying process process used for：Reaction product after will be scrubbed is positioned over vacuum and done
In dry case, 3-10 hour is dried in vacuo, drying temperature is 50-60 DEG C or 60-70 DEG C；
Step 6) solid matter is made to the block of predetermined shape；
Step 7) predetermined pressure is forced into the block；
Step 8) block is heated up with predetermined heating rate, the pressure used during temperature-pressure is 2-
3GPa, temperature is 600 DEG C, and heating rate is 10~80 DEG C/min, and the time is 15min to 80min.
2. Hydrothermal Synthesiss processing technology according to claim 1, it is characterised in that the step 4) also include described in regulation
The pH value of solution extremely >=10.
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