CN105565284A - Preparation method for orientated flaky SnSe powder - Google Patents

Preparation method for orientated flaky SnSe powder Download PDF

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Publication number
CN105565284A
CN105565284A CN201610124648.9A CN201610124648A CN105565284A CN 105565284 A CN105565284 A CN 105565284A CN 201610124648 A CN201610124648 A CN 201610124648A CN 105565284 A CN105565284 A CN 105565284A
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powder
preparation
snse
sheet
solution
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CN105565284B (en
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刘洪权
楚志颖
宋强
苏强
袁存辉
王岩强
谷亦杰
崔洪芝
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Shandong University of Science and 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
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/22—Particle morphology extending in two dimensions, e.g. plate-like with a polygonal circumferential shape

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention discloses a preparation method for orientated flaky SnSe powder. The preparation method comprises the following steps: (1) mixing Se powder with a NaOH solution, and then, completely dissolving the Se powder under the action of heating and pressurizing, so as to obtain a mixture solution; (2) cooling the dark red solution obtained in the step (1), then, sequentially adding SnCl2.2H2O and NaBH4 into the cooled solution, and carrying out a heated reaction; (3) filtrating the reacted solution, flushing a reaction product by distilled water until flushing fluid is neutral, carrying out vacuum drying on the reaction product, and then, collecting the dried reaction product. The flaky SnSe powder prepared by the preparation method is obviously preferentially oriented. The preparation method disclosed by the invention is simple and pollution-free and facilitates industrialized popularization, the obtained flaky SnSe powder is of a pure phase, the degree of orientation reaches 60% to 90%, and the yield is 70% to 80%.

Description

A kind of orientation sheet SnSe raw powder's production technology
Technical field
The present invention is specifically related to a kind of orientation sheet SnSe raw powder's production technology.
Background technology
Along with global energy is day by day in short supply, heat energy utilization is insufficient and the active demand of the outer celestial body energy of exploitation, the green energy resource converting materials such as thermoelectric material worldwide start research boom.Thermoelectric material can make heat energy and electric energy intercouple and conversion, is the critical material manufacturing thermoelectric conversion element.It is a kind of static energy converting material, heat energy and electric energy can be transformed mutually without the need to movable part.Take thermoelectric material as the thermounit of core component, the advantage such as there is portable construction, long service life, non-environmental-pollution, can use under the envrionment conditions of very severe.
Monocrystalline SnSe block materials shows excessive heat electrical property (ZT reaches 2.6), becomes the block materials of the highest thermoelectricity capability of report at present; But polycrystalline SnS e block materials thermoelectricity capability ZT value is only at about 0.6-0.8.Single crystal preparation technology controlling and process difficulty, cost is high, and polycrystalline material thermoelectricity capability is low, and the research of texturing SnSe becomes the feasible way of dealing with problems.
Summary of the invention
For the technical problem existed in prior art, the invention provides a kind of orientation sheet SnSe raw powder's production technology.This preparation method utilizes solvent-thermal method, the sheet SnSe powder of preparation preferred orientation, and can reach orientationization and control, the method realizes whole technique under aqueous systems, do not relate to organic solvent, with low cost, and technological process is simple, environmental protection, is convenient to industrialization promotion.
In order to solve above technical problem, technical scheme of the present invention is:
A kind of orientation sheet SnSe raw powder's production technology, comprises the steps:
1) by after Se powder and NaOH solution mixing, make Se powder dissolve completely under heating and pressurizing effect, obtain dark red solution;
2) by step 1) in obtain solution cooling after, add SnCl successively 22H 2o and NaBH 4, reacting by heating;
3) after solution filters after reacting, use distilled water flushing reaction product, until washing fluid is in neutral, collect after reaction product vacuum-drying.
Preferably, step 1) in, in the dark red solution obtained, the concentration of Se and NaOH is respectively 0.05-0.5mol/L and 1-3mol/L.
Preferably, step 1) in, the temperature after heating is 140-160 DEG C, insulation 0.8-1.5h.
Heating and pressurizing promotes that reaction is carried out, and accelerates the dissolving of Se.
Preferably, step 1) in, the pressure that Se powder dissolves is 1-3MPa.
Preferably, step 2) in, Se, NaOH, SnCl 22H 2o and NaBH 4the ratio of amount of substance be 0.5-2:15-30:0.5-2:15-30.
Under the strong alkali environment that NaOH provides, Se is fully dissolved, in reaction process, NaOH is simultaneously as mineralizer, promotes the crystallization of SnSe; NaBH 4as reductive agent by reducing metal ions, generate with chemically active particle, and then reaction generates orientation sheet SnSe powder.
Preferably, step 2) in, the temperature of reacting by heating is 80-140 DEG C, and the time of reaction is 1-15h.
Preferably, step 3) in, by product at vacuum 70-90 DEG C of dry 5-7 hour.
Orientation sheet SnSe powder prepared by above-mentioned preparation method, in the XRD of this sheet SnSe powder, (400) crystal face is the strongest diffraction peak, and sheet is class tetragon, length of side 10-60 μm.
Described sheet SnSe powder can prepare texturing SnSe block materials through oversintering.
Described sheet SnSe powder can application in thermoelectric conversion or photoelectric conversion.
Beneficial effect of the present invention is:
1, the sheet SnSe powder of obvious preferred orientation prepared of the present invention, can confirm (as shown in Figure 1,2,3, 4) by the XRD diffraction patterns of respective samples, SEM photo also illustrates its sheet-like morphology (as shown in Figure 2) very well simultaneously.Simple, pollution-free, the easy industrialization promotion of preparation method of the present invention, obtaining sheet SnSe powder is pure phase, and orientation degree reaches about 90%, and output is about 80%.
2, orientation SnSe powder of the present invention can be applied in the field such as thermoelectric conversion, photoelectric conversion, apply in thermoelectricity field, micron film directly can be utilized to make micron thermoelectric converter, the direction of vertical plate builds thermo-electric device, high performance thermo-electric device will be obtained; Also can be prepared into texturing block materials by the Structure Inheritance principle of the orientation feature of flaky powder and sintering process, and then obtain anisotropic thermoelectric material, control set direction assembly device and can obtain high performance thermo-electric device.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of SnSe prepared by embodiment 1;
Fig. 2 is the XRD figure spectrum of SnSe prepared by embodiment 2;
Fig. 3 is the XRD figure spectrum of SnSe prepared by embodiment 3;
Fig. 4 is orientation sample, without preferred orientation sample and standard XRD pattern contrast figure;
Fig. 5 is the SEM photo of the SnSe flaky powder of preparation.
Embodiment
Embodiment 1
Orientation sheet SnSe raw powder's production technology, comprises the steps:
(1) take 0.1579gSe powder and 4gNaOH respectively, put into autoclave successively, add appropriate distilled water, make reactor compactedness 70%.
(2) reactor is put into Constant Temp. Oven 140 DEG C insulation 1h, the reactor being cooled to room temperature with baking oven is taken out.
(3) 0.4514gSnCl is taken respectively 22H 2o and 4gNaBH 4, add successively in reactor.
(4) reactor is put into Constant Temp. Oven 100 DEG C insulation 15h.Question response still takes out after being cooled to room temperature with baking oven.
(5) reaction solution is constantly filtered with distilled water flushing, until solution is in neutral.By reactant vacuum 80 DEG C of drying 6 h before harvest.
The sheet SnSe powder that the method obtains is orthogonal SnSe pure phase, by the XRD figure spectrum of Fig. 1 is confirmed, and can find out that (400) crystal face has obvious preferred orientation, by the preferred orientation sample of Fig. 4, without preferred orientation sample and standard XRD pattern contrast, orientationization is more remarkable, calculates according to orientation degree
F＝(P–P 0)/(1–P 0)(1)
P=I{00l}/I{hkl}.P 0the calculation result of standard test specimen, F represents orientation degree; About 0.9 is reached by calculating orientation degree to the XRD figure modal data of Fig. 1.The pattern of the sheet SnSe powder finding out high yield prepared by present method can be known according to Fig. 5.
Embodiment 2
(1) take 0.1579gSe powder and 4gNaOH respectively, put into autoclave successively, add appropriate distilled water, make reactor compactedness 70%.
(2) reactor is put into Constant Temp. Oven 140 DEG C insulation 1h, the reactor being cooled to room temperature with baking oven is taken out.
(3) 0.4538gSnCl is taken respectively 22H 2o and 5gNaBH 4, add successively in reactor.
(4) reactor is put into Constant Temp. Oven 120 DEG C insulation 15h.Question response still takes out after being cooled to room temperature.
(5) reaction solution is constantly filtered with distilled water flushing, until solution is in neutral.By reactant vacuum 80 DEG C of drying 6 h before harvest.
The sheet SnSe powder that the method obtains is orthogonal SnSe pure phase, by the XRD figure spectrum of Fig. 2 is confirmed, and can find out that (400) crystal face has obvious preferred orientation, by the preferred orientation sample of Fig. 4, without preferred orientation sample and standard XRD pattern contrast, orientationization is more remarkable, calculates according to orientation degree
F＝(P–P 0)/(1–P 0)(1)
P=I{00l}/I{hkl}.P 0the calculation result of standard test specimen, F represents orientation degree; About 0.8 is reached by calculating orientation degree to the XRD figure modal data of Fig. 2.The pattern of the sheet SnSe powder finding out high yield prepared by present method can be known according to Fig. 5.
Embodiment 3
(1) take 0.1579gSe powder and 4gNaOH respectively, put into autoclave successively, add appropriate distilled water, make reactor compactedness 60%.
(2) reactor is put into Constant Temp. Oven 160 DEG C insulation 1h, the reactor being cooled to room temperature with baking oven is taken out.
(3) 0.4526gSnCl is taken respectively 22H 2o and 5gNaBH 4, add successively in reactor.
(4) reactor is put into Constant Temp. Oven 140 DEG C insulation 1h.Question response still takes out after being cooled to room temperature.
(5) reaction solution is constantly filtered with distilled water flushing, until solution is in neutral.By reactant vacuum 90 DEG C of drying 5 h before harvest.
The sheet SnSe powder that the method obtains is orthogonal SnSe pure phase, by the XRD figure spectrum of Fig. 3 is confirmed, and can find out that (400) crystal face has obvious preferred orientation, by the preferred orientation sample of Fig. 4, without preferred orientation sample and standard XRD pattern contrast, orientationization is more remarkable, calculates according to orientation degree
F＝(P–P 0)/(1–P 0)(1)
P=I{00l}/I{hkl}.P 0the calculation result of standard test specimen, F represents orientation degree; About 0.6 is reached by calculating orientation degree to the XRD figure modal data of Fig. 3.The pattern of the sheet SnSe powder finding out high yield prepared by present method can be known according to Fig. 5.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but the restriction not to invention protection domain; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still in protection scope of the present invention.

Claims (10)

1. an orientation sheet SnSe raw powder's production technology, is characterized in that: comprise the steps:
1) by after Se powder and NaOH solution mixing, make Se powder dissolve completely under heating and pressurizing effect, obtain dark red solution;
2) by step 1) in obtain solution cooling after, add SnCl successively 22H 2o and NaBH 4, reacting by heating;
3) after solution filters after reacting, use distilled water flushing reaction product, until washing fluid is in neutral, collect after reaction product vacuum-drying.
2. preparation method according to claim 1, is characterized in that: step 1) in, in the mixing solutions obtained, the concentration of Se and NaOH is respectively 0.05-0.5mol/L and 1-3mol/L.
3. preparation method according to claim 1, is characterized in that: step 1) in, the temperature after heating is 140-160 DEG C, insulation 0.8-1.5h.
4. preparation method according to claim 1, is characterized in that: step 1) in, the pressure that Se powder dissolves is 1-3Mpa.
5. preparation method according to claim 1, is characterized in that: step 2) in, Se, NaOH, SnCl 22H 2o and NaBH 4the ratio of amount of substance be 0.5-2:15-30:0.5-2:15-30.
6. preparation method according to claim 1, is characterized in that: step 2) in, the temperature of reacting by heating is 80-140 DEG C, and the time of reaction is 1-15h.
7. preparation method according to claim 1, is characterized in that: step 3) in, by product at vacuum 70-90 DEG C of dry 5-7 hour.
8. the orientation sheet SnSe powder prepared of the arbitrary described preparation method of claim 1-7, is characterized in that: in the XRD of this sheet SnSe powder, (400) crystal face is the strongest diffraction peak, and sheet is class tetragon, length of side 10-60 μm.
9. the textured SnSe block materials prepared through oversintering of sheet SnSe powder according to claim 8.
10. the application of sheet SnSe powder according to claim 8 in thermoelectric conversion or photoelectric conversion.
CN201610124648.9A 2016-03-04 2016-03-04 A kind of orientationization sheet SnSe raw powder's production technologies Active CN105565284B (en)

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN106744727A (en) * 2016-11-28 2017-05-31 福建师范大学 Screw dislocation drives the preparation method of growth spiral type stratiform stannic selenide nanometer sheet
CN107171019A (en) * 2017-04-18 2017-09-15 陕西科技大学 A kind of method that microwave-hydrothermal method prepares SnSe nano particles
CN107352515A (en) * 2017-07-06 2017-11-17 陕西科技大学 A kind of brilliant method of hydro-thermal method synthesis stannic selenide micron
CN107934924A (en) * 2017-11-17 2018-04-20 陕西科技大学 A kind of Hydrothermal preparation method for controlling laminated structure stannic selenide thickness
CN108389956A (en) * 2018-03-09 2018-08-10 哈尔滨工业大学深圳研究生院 A kind of preparation method of N-shaped SnSe base Thermoelectric Nano-materials
CN110329997A (en) * 2019-04-29 2019-10-15 安徽大学 A kind of preparation method of lower thermal conductivity SnSe nano material
CN110702675A (en) * 2019-11-06 2020-01-17 苏州大学 Application of two-dimensional nano material as dehydrogenase
CN113113531A (en) * 2021-03-16 2021-07-13 西北工业大学 Preparation method of high ZT value pure SnSe polycrystalline block thermoelectric material
CN115015335A (en) * 2022-08-05 2022-09-06 山东乾能科技创新有限公司 SnSe/SnO 2 Preparation method of/Gr composite material, MEMS ammonia gas sensor and application thereof

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106744727A (en) * 2016-11-28 2017-05-31 福建师范大学 Screw dislocation drives the preparation method of growth spiral type stratiform stannic selenide nanometer sheet
CN107171019A (en) * 2017-04-18 2017-09-15 陕西科技大学 A kind of method that microwave-hydrothermal method prepares SnSe nano particles
CN107352515B (en) * 2017-07-06 2019-10-18 陕西科技大学 A kind of method of hydro-thermal method synthesis stannic selenide micron crystalline substance
CN107352515A (en) * 2017-07-06 2017-11-17 陕西科技大学 A kind of brilliant method of hydro-thermal method synthesis stannic selenide micron
CN107934924A (en) * 2017-11-17 2018-04-20 陕西科技大学 A kind of Hydrothermal preparation method for controlling laminated structure stannic selenide thickness
CN107934924B (en) * 2017-11-17 2020-06-05 陕西科技大学 Hydrothermal preparation method for controlling thickness of tin selenide with sheet structure
CN108389956A (en) * 2018-03-09 2018-08-10 哈尔滨工业大学深圳研究生院 A kind of preparation method of N-shaped SnSe base Thermoelectric Nano-materials
CN110329997A (en) * 2019-04-29 2019-10-15 安徽大学 A kind of preparation method of lower thermal conductivity SnSe nano material
CN110702675A (en) * 2019-11-06 2020-01-17 苏州大学 Application of two-dimensional nano material as dehydrogenase
CN113113531A (en) * 2021-03-16 2021-07-13 西北工业大学 Preparation method of high ZT value pure SnSe polycrystalline block thermoelectric material
CN113113531B (en) * 2021-03-16 2023-09-08 西北工业大学 Preparation method of high ZT value pure SnSe polycrystal block thermoelectric material
CN115015335A (en) * 2022-08-05 2022-09-06 山东乾能科技创新有限公司 SnSe/SnO 2 Preparation method of/Gr composite material, MEMS ammonia gas sensor and application thereof
CN115015335B (en) * 2022-08-05 2022-11-22 山东乾能科技创新有限公司 SnSe/SnO 2 Preparation method of/Gr composite material, MEMS ammonia gas sensor and application thereof

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