CN111690985B - Quantum dot doped cuprous sulfide polycrystalline material and preparation method thereof - Google Patents
Quantum dot doped cuprous sulfide polycrystalline material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 79
- 239000002096 quantum dot Substances 0.000 title claims abstract description 71
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 238000007731 hot pressing Methods 0.000 claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
- 230000006698 induction Effects 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910004613 CdTe Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 abstract description 11
- 238000005303 weighing Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/10—Single-crystal growth directly from the solid state by solid state reactions or multi-phase diffusion
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention provides a quantum dot doped cuprous sulfide polycrystalline material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) providing copper powder and sulfur powder as initial raw materials; 2) adding quantum dots into the initial raw materials to form a powder raw material; 3) adding a grinding aid, and carrying out mixed ball milling to form a powder synthesis raw material; 4) according to the scheme, the cuprous sulfide powder doped with quantum dots is synthesized by using a ball milling method, and the thermal conductivity of the cuprous sulfide polycrystalline material can be effectively reduced and the thermoelectric property of the cuprous sulfide polycrystalline material can be improved by combining a radio frequency induction hot-pressing sintering method.
Description
Technical Field
The invention belongs to the fields of chemistry and chemical engineering and material science, and particularly relates to a quantum dot doped cuprous sulfide polycrystalline material and a preparation method thereof.
Background
Thermoelectric materials are increasingly attracting the interest of researchers because of their unique advantage of being able to directly effect conversion between thermal and electrical energy. Especially, the energy problem faced in the world is becoming more and more serious, and the appearance of thermoelectric materials provides a solution for solving the problem. Among them, the Cu-S based thermoelectric material is an important branch, and the Cu-S element has advantages that other systems of thermoelectric materials do not have because it is abundant in the earth' S reserves and is non-toxic and harmless. This is also one of the important reasons why copper-sulfur based thermoelectric materials are attracting increasing attention.
Cu2S materials were first applied to solar cells. It exhibits the characteristics of a P-type semiconductor due to the presence of a large number of copper vacancies within the materialAnd (4) sex. It was then found to have good thermoelectric properties. Generally, ZT values are used as an important measure of thermoelectric material performance in thermoelectric materials. ZT ═ S2σ T/κ, S represents the Seebeck coefficient, σ represents the electrical conductivity, and κ represents the thermal conductivity of the material. Low thermal conductivity is critical to the thermoelectric performance of the material. Quantum Dots (QDs) are nanoparticles composed of a limited number of atoms, generally spherical or spheroidal, made of semiconductor materials (usually composed of IIB-VIA or IIIA-VA elements) and having a stable diameter of 2-20 nm. Quantum dots are semiconductor nanostructures that confine conduction band electrons, valence band holes, and excitons in three spatial directions. The quantum dots have wide application prospects in the fields of solar cells, thermoelectricity, optical biomarkers and the like. However, the thermoelectric performance of the conventional thermoelectric material is poor, the thermal conductivity is not ideal, and the improvement of the performance of the thermoelectric material becomes a problem to be solved by those skilled in the art.
Therefore, how to provide a quantum dot doped cuprous sulfide polycrystalline material and a preparation method thereof are necessary to solve the above problems in the prior art.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a quantum dot doped cuprous sulfide polycrystalline material and a preparation method thereof, which are used for solving the problems of poor thermoelectric performance, poor thermal conductivity and the like of thermoelectric materials in the prior art.
In order to achieve the above objects and other related objects, the present invention provides a method for preparing a quantum dot doped cuprous sulfide polycrystalline material, comprising the steps of:
1) providing copper powder and sulfur powder as initial raw materials;
2) adding quantum dots into the initial raw materials to form a powder raw material;
3) adding a grinding aid, and carrying out mixed ball milling to form a powder synthesis raw material;
4) and carrying out hot pressing on the powder synthesis raw material by using radio frequency induction hot pressing equipment to obtain the quantum dot doped cuprous sulfide polycrystalline material with a flaky block structure.
As an alternative of the invention, in step 1), the molar ratio of the copper powder to the sulfur powder is between 1.9:1 and 2.1: 1.
As an alternative of the present invention, in step 2), the quantum dots comprise at least one of CdSe/ZnS, InP/ZnS, PbS and CdTe.
As an alternative of the present invention, in step 3), the grinding aid comprises n-hexane; the ball-material mass ratio in the mixing and grinding process is between 15:1 and 25:1, the mixing and ball-milling are carried out at room temperature, the rotating speed is 300r/min to 700r/min, and the ball-milling time is 550min to 850 min.
As an alternative of the invention, in the step 3) of carrying out the mixing and grinding process, the ball mill is set to change the turning direction every 30 min.
As an alternative scheme of the invention, in the step 4), after the powder synthesis raw material is loaded into a high-pressure-resistant graphite mold, hot pressing is carried out for 5min to 20min under the conditions of inert gas protection, 800 ℃ to 880 ℃ and 60MPa to 75MPa pressure by utilizing radio frequency induction hot pressing equipment, and then a hot-pressed sample is annealed along with a furnace to obtain the quantum dot doped cuprous sulfide polycrystalline material with a sheet block structure.
As an alternative of the invention, the power supply frequency of the radio frequency induction hot-pressing device is not less than 100 kHz.
As an alternative of the invention, the inert gas in the radio frequency induction hot-pressing equipment is high-purity nitrogen or argon, and the pressure in the furnace is 0.05-6 atmospheric pressures.
As an alternative scheme of the invention, the mass fraction of the quantum dots in the powder raw material is between 1% and 4%.
The invention also provides a quantum dot doped cuprous sulfide polycrystalline material, which is at least based on the quantum dot doped cuprous sulfide polycrystalline material with a flaky block structure and obtained by forming the raw materials of copper powder, sulfur powder and quantum dots.
As mentioned above, the quantum dot doped cuprous sulfide polycrystalline material and the preparation method thereof of the invention synthesize the cuprous sulfide powder doped with quantum dots by using a ball milling method, and the high-density sheet block material synthesized by combining a radio frequency induction hot-pressing sintering method can effectively reduce the thermal conductivity of the cuprous sulfide polycrystalline material and improve the thermoelectric property of the cuprous sulfide polycrystalline material.
Drawings
FIG. 1 is a schematic diagram showing the process flow of the preparation of the quantum dot doped cuprous sulfide polycrystalline material of the present invention.
Fig. 2 is a graph showing the thermal conductivity of undoped and doped quantum dot samples as a function of temperature in an embodiment of the present invention.
Description of the element reference numerals
S1-S4
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Please refer to fig. 1-2. It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the form, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
As shown in fig. 1-2, the present invention provides a method for preparing a quantum dot doped cuprous sulfide polycrystalline material, comprising the steps of:
1) providing copper powder and sulfur powder as initial raw materials;
2) adding quantum dots into the initial raw materials to form a powder raw material;
3) adding a grinding aid, and carrying out mixed ball milling to form a powder synthesis raw material;
4) and carrying out hot pressing on the powder synthesis raw material by using radio frequency induction hot pressing equipment to obtain the quantum dot doped cuprous sulfide polycrystalline material with a flaky block structure.
First, as shown in S1 in fig. 1, copper powder and sulfur powder are supplied as starting materials;
as an example, in step 1), the molar ratio of the copper powder to the sulfur powder is between 1.9:1 and 2.1: 1. Preferably, the molar ratio of the copper powder to the sulfur powder is 2:1, thereby facilitating the formation of Cu2And the proportioning relation of S.
Subsequently, as shown in S2 in fig. 1, quantum dots are added to the starting material to form a powder raw material;
the quantum dots include, for example, at least one of CdSe/ZnS (i.e., CdSe and ZnS are added simultaneously, and are mixed materials of two substances, and are themselves mixed), InP/ZnS, PbS, and CdTe, and the added quantum dots may be any one of the above materials, but of course, may be a combination of two or more of the above materials.
By way of example, the quantum dots account for 1-4% of the powder raw material by mass.
Continuing, as shown in S3 in FIG. 1, adding a grinding aid, and carrying out mixing and ball milling to form a powder synthesis raw material;
as an example, in step 3), the grinding aid comprises n-hexane; the ball-material mass ratio in the mixing and grinding process is between 15:1 and 25:1, the mixing and ball-milling are carried out at room temperature, the rotating speed is 300r/min to 700r/min, and the ball-milling time is 550min to 850 min.
As an example, in the mixing and grinding process in step 3), the ball mill is set to change the turning direction every 30 min.
Specifically, in an example, the method further includes a step of removing the grinding aid to perform hot pressing after the mixing and ball milling is performed, and the method may further include a step of performing hot pressing on the cleaned and dried powder synthesis raw material by using a radio frequency induction hot pressing device.
And finally, as shown in S4 in fig. 1, hot-pressing the powder synthesis raw material by using a radio frequency induction hot-pressing device to obtain the quantum dot doped cuprous sulfide polycrystalline material with a flaky block structure.
As an example, in the step 4), after the powder synthesis raw material is loaded into a high pressure resistant graphite mold, hot pressing is carried out for 5min to 20min under the conditions of inert gas protection, 800 ℃ to 880 ℃ and 60Mpa to 75Mpa pressure by using a radio frequency induction hot pressing device, and then a hot-pressed sample is annealed with a furnace, so as to obtain the quantum dot doped cuprous sulfide polycrystalline material with a sheet block structure.
Specifically, in one example, copper powder and sulfur powder are used as raw materials, the ball-to-material mass ratio is 20:1 according to a molar ratio of 2:1, doped quantum dots (CdSe/ZnS) are added into the raw materials according to the mass ratio, n-hexane is used as an auxiliary grinding agent, and ball milling is carried out at room temperature for 600 min. Further, the ball mill is set to change the turning direction every 30 min. Finally, the obtained powder material is subjected to hot-pressing sintering for 12min at the temperature of 810-830 ℃ by utilizing a radio frequency induction hot-pressing technology, so as to obtain a block material. In addition, the sheet-like bulk structure is a macroscopic sheet structure, and further, the cross section of the hot-pressed bulk sample with the mass fraction of doped quantum dots of 1% is shown in fig. 3(a), and fig. 3(b) also shows an EDS analysis spectrum within a red circle in fig. 3 (a).
Specifically, the hot-pressed sample can be cooled to room temperature along with the furnace to realize annealing.
As an example, the power frequency of the rf induction hot press apparatus is not less than 100 kHz.
As an example, the inert gas in the radio frequency induction hot-pressing equipment is high-purity nitrogen or argon, and the pressure in the furnace is 0.05-6 atmospheres, such as 2-5 atmospheres.
Specifically, through the scheme, the ball-milling mechanical alloying process is adopted, the ball-milling parameters and the mass percentage of the doped quantum dots are reasonably set, the doping in the cuprous sulfide is realized, and the block sheet material is obtained after the block material is rapidly sintered at a proper temperature by using radio frequency induction hot pressing, so that the thermoelectric material with the structural components is obtained, and has lower thermal conductivity than a sample without the doped quantum dots, the powder synthesis raw material is prepared by using the ball-milling, and the block is prepared by using hot pressing.
The invention synthesizes quantum dot doped cuprous sulfide powder by using a ball milling method, and combines a radio frequency induction hot pressing sintering method to synthesize a high-density sheet block material, wherein the thermoelectric material with the nano structure has better thermoelectric performance, and the nano structure can greatly reduce the heat conductivity so as to improve the thermoelectric performance. In a comparative example, Bi was synthesized by a solution-based synthesis strategy2Te3The test result of the/graphene quantum dot composite material shows that the thermal conductivity of the material is obviously reduced, so that phonon scattering is increased, the lattice thermal conductivity is reduced, but the method is time-consuming and energy-consuming and has complex process. The preparation method of the ball milling method has the advantages of simple operation, mass production and preparation and the like, is widely applied to the field of material synthesis and preparation, can regulate and control the powder microstructure by changing the ball milling condition parameters so as to introduce the nano particles, and is widely applied to the field of nano material preparation. In addition, the radio frequency induction hot pressing sintering technology combines the advantages of rapid sintering reaction and hot pressing molding, and can effectively inhibit the crystal grains from growing in the sintering process.
In addition, the present invention also provides a quantum dot doped cuprous sulfide polycrystalline material, wherein the polycrystalline material is preferably prepared by the preparation method of the quantum dot doped cuprous sulfide polycrystalline material of the present invention, and the polycrystalline material is a quantum dot doped cuprous sulfide polycrystalline material with a sheet-like block structure obtained based on copper powder, sulfur powder and quantum dots as raw materials, wherein in one example, the polycrystalline material has a general formula of: cu2S + y% wt quantum dots, y 1,2,3,4 … …, e.g. Cu2S + y% wt CdSe/ZnS, preferably, y ═ 1,2,3, 4.
To further illustrate the beneficial effects of the present invention, specific examples are provided.
Example 1:
(1) respectively weighing copper powder and sulfur powder in a stoichiometric ratio of 2:1, weighing copper powder and sulfur powder in corresponding mass, using normal hexane as a grinding aid for reaction, and performing ultrasonic grinding to synthesize an undoped cuprous sulfide powder material by using ball milling. Setting the ball milling speed at 500r/min and the ball milling time at 600 min.
(2) And preparing the polycrystalline cuprous sulfide block material by adopting a radio frequency induction hot-pressing sintering process. And (2) putting the powder into a graphite die, putting the graphite die into a radio frequency induction hot-pressing furnace, sintering for 13 minutes under the conditions of argon protection, 820 ℃ and 75MPa of pressure, and annealing a hot-pressed sample along with the furnace to finally obtain the polycrystalline cuprous sulfide block.
(3) The heat-treated hot-pressed block was tested for thermal conductivity using a model LSR-3/1100 thermoelectric measurement system, manufactured by Linseis corporation.
Example 2:
(1) weighing copper powder and sulfur powder in a stoichiometric ratio of 2:1 respectively, weighing copper powder and sulfur powder in corresponding mass, weighing and adding 1% of quantum dots in mass fraction, adding n-hexane as a grinding aid, mixing uniformly, sealing a ball milling tank, setting the ball milling speed at 500r/min, and ball milling time at 600 min.
(2) The specific steps (3) are as in steps (2) to (3) of example 1, and the results of the thermal conductivity test were obtained.
Example 3:
(1) weighing copper powder and sulfur powder in a stoichiometric ratio of 2:1 respectively, weighing copper powder and sulfur powder in corresponding mass, weighing and adding quantum dots with mass fraction of 3%, adding n-hexane as a grinding aid, mixing uniformly, sealing a ball milling tank, setting the ball milling speed at 500r/min, and ball milling time at 600 min.
(2) The specific steps (3) are as in steps (2) to (3) of example 1, and the results of the thermal conductivity test were obtained.
As shown in fig. 2, a graph showing the relationship between the thermal conductivity (k) of the undoped quantum dot sample (example 1) and the doped quantum dot sample (example 2 and example 3) with the temperature (Tempreature) in the above three examples is shown, wherein CdSe/ZnS quantum dot doped cuprous sulfide polycrystalline material is prepared by a ball milling method, a bulk material obtained after radio frequency induction hot pressing sintering is obtained, a result showing that the thermal conductivity changes with the temperature is obtained by test analysis, and the result shows that the thermal conductivity of the sample is reduced along with the increase of the doped mass percentage of the quantum dot, which can be beneficial to the improvement of the thermoelectric property of the material.
In summary, the invention provides a quantum dot doped cuprous sulfide polycrystalline material and a preparation method thereof, and the preparation method comprises the following steps: 1) providing copper powder and sulfur powder as initial raw materials; 2) adding quantum dots into the initial raw materials to form a powder raw material; 3) adding a grinding aid, and carrying out mixed ball milling to form a powder synthesis raw material; 4) according to the scheme, the cuprous sulfide powder doped with quantum dots is synthesized by using a ball milling method, and the high-density flaky block material synthesized by combining a radio frequency induction hot-pressing sintering method can effectively reduce the thermal conductivity of the cuprous sulfide polycrystalline material and improve the thermoelectric property of the cuprous sulfide polycrystalline material. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A preparation method of a quantum dot doped cuprous sulfide polycrystalline material is characterized by comprising the following steps:
1) providing copper powder and sulfur powder as initial raw materials;
2) adding quantum dots into the initial raw material to form a powder raw material, wherein the quantum dots comprise at least one of CdSe/ZnS, InP/ZnS, PbS and CdTe;
3) adding a grinding aid, and carrying out mixed ball milling to form a powder synthesis raw material;
4) and the cuprous sulfide polycrystalline material is doped with quantum dots, and is prepared by hot-pressing the powder synthesis raw material by using radio frequency induction hot-pressing equipment.
2. The method for preparing a quantum dot doped cuprous sulfide polycrystalline material according to claim 1, wherein in step 1), the molar ratio of said copper powder to said sulfur powder is between 1.9:1 and 2.1: 1.
3. The method for preparing a quantum dot doped cuprous sulfide polycrystalline material according to claim 1, wherein in step 3), said grinding aid comprises n-hexane; the ball-material mass ratio in the process of carrying out the mixing ball milling is between 15:1 and 25:1, the mixing ball milling is carried out at room temperature, the rotating speed is 300r/min to 700r/min, and the ball milling time is 550min to 850 min.
4. The method for preparing the quantum dot doped cuprous sulfide polycrystalline material according to claim 1, wherein in the step 3), the ball mill is set to change the turning direction every 30min during the mixing and ball milling process.
5. The method for preparing the quantum dot doped cuprous sulfide polycrystalline material according to claim 1, wherein in the step 4), after the powder synthesis raw material is loaded into a high pressure resistant graphite mold, hot pressing is carried out for 5min to 20min under the conditions of inert gas protection, 800 ℃ to 880 ℃ and 60Mpa to 75Mpa pressure by using a radio frequency induction hot pressing device, and then a hot pressing sample is annealed in a furnace to obtain the quantum dot doped cuprous sulfide polycrystalline material with a sheet block structure.
6. The method for preparing the quantum dot doped cuprous sulfide polycrystalline material according to claim 5, wherein the power frequency of the radio frequency induction hot pressing device is not less than 100 kHz.
7. The method for preparing the quantum dot doped cuprous sulfide polycrystalline material according to claim 5, wherein the inert gas in the radio frequency induction hot pressing equipment is high-purity nitrogen or argon, and the pressure in the furnace is 0.05-6 atm.
8. The preparation method of the quantum dot doped cuprous sulfide polycrystalline material according to any one of claims 1 to 7, wherein the mass fraction of the quantum dots in the powder raw material is between 1% and 4%.
9. The quantum dot doped cuprous sulfide polycrystalline material is characterized by being at least based on quantum dot doped cuprous sulfide polycrystalline material which is obtained by forming raw materials of copper powder, sulfur powder and quantum dots and has a flaky block structure; the quantum dots include at least one of CdSe/ZnS, InP/ZnS, PbS, and CdTe.
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| CN102443848A (en) * | 2012-01-29 | 2012-05-09 | 北京科技大学 | Method for improving thermoelectric properties of bismuth sulfide polycrystal |
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| CN107673395A (en) * | 2016-08-02 | 2018-02-09 | 中国科学院大连化学物理研究所 | A kind of thermoelectric material for vulcanizing indium doping cuprous sulfide and preparation method thereof |
| CN108383526A (en) * | 2018-02-28 | 2018-08-10 | 昆明理工大学 | A kind of Cu1.8The Quito S crystalline substance block thermoelectric material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443848A (en) * | 2012-01-29 | 2012-05-09 | 北京科技大学 | Method for improving thermoelectric properties of bismuth sulfide polycrystal |
| CN106283173A (en) * | 2016-07-21 | 2017-01-04 | 昆明理工大学 | A kind of method reducing Tellurobismuthite. polycrystalline lattice thermal conductivity |
| CN107673395A (en) * | 2016-08-02 | 2018-02-09 | 中国科学院大连化学物理研究所 | A kind of thermoelectric material for vulcanizing indium doping cuprous sulfide and preparation method thereof |
| CN108383526A (en) * | 2018-02-28 | 2018-08-10 | 昆明理工大学 | A kind of Cu1.8The Quito S crystalline substance block thermoelectric material and preparation method thereof |
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