CN113782665B - WSe (Wireless sensor package) 2 /MoS 2 Preparation method of composite thermoelectric material - Google Patents
WSe (Wireless sensor package) 2 /MoS 2 Preparation method of composite thermoelectric material Download PDFInfo
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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Abstract
The invention relates to a WSe 2 /MoS 2 A method for preparing a composite thermoelectric material. The method comprises preparing WSe by Chemical Vapor Deposition (CVD) 2 Nanoparticle, and WSe prepared therefrom 2 Powder metallurgy method and MoS for nano particles 2 Compounding the matrix to obtain WSe 2 /MoS 2 A composite thermoelectric material. The invention does not reduce MoS 2 Under the condition of the Seebeck coefficient of the matrix, moS is improved 2 The conductivity of the matrix effectively improves the power factor.
Description
Technical Field
The invention relates to the field of thermoelectric materials, in particular to a WSe 2 /MoS 2 A method for preparing a composite thermoelectric material.
Background
A great deal of heat is wasted in the current social production activities, which is a great concern, and thus capturing this wasted energy has great economic and environmental benefits. The thermoelectric material can directly convert heat energy into electric energy, and waste heat is recycled, so that the green-friendly development is greatly promoted, and the energy crisis is relieved. The performance of thermoelectric materials is represented by thermoelectric figure of merit (ZT) expressed by zt=s 2 Sigma T/kappa, where S represents the Seebeck coefficient, sigma represents the electrical conductivity, T represents the absolute temperature, kappa represents the thermal conductivity, S 2 σ is called a Power Factor (Power Factor). The larger the ZT value, the higher the thermoelectric energy conversion efficiency. I.e. high S, high sigma, low kappa. Increasing ZT of a material requires increasing S and sigma of the material, i.e. increasing the power factor, while reducing the thermal conductance. However, the conventional high-performance thermoelectric materials generally contain expensive elements, and part of the materials contain toxic elements such as Te, pb and the like, so that the practical application of the materials is seriously hindered, and new alternative materials are required to be searched.
Two-dimensional transition metal chalcogenides (Transition Metal Dichalcogenides (TMDCs)) are graphene-like two-dimensional materials having excellent optical, electrical, etc. characteristics, and research interest has grown greatly since the discovery of graphene. MoS (MoS) 2 One of them has large intrinsic band gap and high carrier mobility, shows great application prospect in semiconductor electronic devices, and TMDCs have the advantages of low cost and no toxicity, and have great potential as novel thermoelectric materials. However, for MoS 2 There is still some lack of research into thermoelectric properties. So far, the research has been conducted mainly on theoretical calculation research, babaei et al calculation found single-layer MoS 2 The maximum power factor of (2) can reach 2.8x10 -4 μWm -1 K -1 The method comprises the steps of carrying out a first treatment on the surface of the Tang et al found MoS by calculation 2 The ZT value of the nano-belt is about 3.0, greatly promoting MoS 2 As thermoelectric materials.
However, in recent years much higher ZT values have been obtained in low dimensional or nanoscale thermoelectric materials, as nanoparticles can scatter phonons at medium and long wavelengths, reduce the lattice thermal conductance of the material, while increasing the state density of carriers near the fermi level, and the nanocrystallized interface barrier can effectively filter low energy carriers, increasing the seebeck coefficient. The advent of nanocomposite materials has become a new direction to improve thermoelectric properties of materials.
Disclosure of Invention
The invention aims to provide a WSe 2 /MoS 2 A method for preparing a composite thermoelectric material. Preparation of WSe by Chemical Vapor Deposition (CVD) 2 Nanoparticle prepared by powder metallurgy method 2 Nanoparticles and MoS 2 Matrix compounding, preparation of WSe 2 /MoS 2 Composite thermoelectric material without reducing MoS 2 Under the condition of the Seebeck coefficient of the matrix, moS is improved 2 The conductivity of the matrix effectively improves the power factor.
The technical scheme of the invention is as follows:
WSe (Wireless sensor package) 2 /MoS 2 A method of preparing a composite thermoelectric material, the method comprising the steps of:
the first step: preparation of WSe by chemical vapor deposition 2 Nanoparticles:
(1) In the chemical vapor deposition equipment, W (CO) 6 Placing the quartz boat into a bubbler, and placing Se powder into the quartz boat;
wherein the molar ratio is W (CO) 6 ：Se＝1：5.0-10.0；
(2) Placing the quartz boat in the step (1) in the front region of a quartz tube of a horizontal tube furnace, connecting a bubbler with the left end inlet of the quartz tube of the tube furnace, and placing the quartz boat in an oil bath pan; the right-hand member of tubular furnace quartz capsule connects the water-cooling, wherein: the diameter of the quartz tube is as follows: 40-60mm, length is: 1.2-1.5m;
(3) Under inert atmosphere, heating the tube furnace at 10-15 ℃/min, closing carrier gas flow when the temperature of the tube furnace is raised to 500-600 ℃, opening an oil bath heating bubbler to 110-130 ℃, and setting the temperature of a cooling area to 20-50 ℃; when the temperature of the tube furnace is raised to 700-1000 ℃, an inert carrier gas flow, W (CO), is opened 6 And Se powder are volatilized and react for 15-30min at high temperature to generate WSe 2 Nanoparticles are deposited in the cooling zone. Wherein the gas isThe volume flow rate is 800-1200sccm;
(4) Collecting powder at the right end of the quartz tube;
(5) Placing the powder collected in step (4) in a quartz boat, placing in another tube furnace, heating the tube furnace to 400-600deg.C at 10-15deg.C/min under reducing atmosphere, and maintaining the temperature for 15-30min to obtain pure WSe 2 A nanoparticle;
the WSe 2 The particle size of the nano particles is 35-55nm;
the chemical vapor deposition method equipment comprises a gas circuit system, a bubbler, an oil bath pot, a tube furnace and a cooling system, wherein the bubbler is arranged in the oil bath pot, the gas circuit system is connected with the upper port of the bubbler, and the side end of the gas circuit system is connected with the inlet of the quartz tube;
the quartz tube of the tube furnace is divided into a front zone, a high-temperature heating zone (the length is 35-70% of the total length of the quartz tube) and a cooling zone from front to back in sequence; the front area of the quartz tube is provided with a quartz boat, and the cooling area is a quartz tube wrapping cooling system.
The inert gas in the step (3) is helium, argon or nitrogen;
the reducing atmosphere in the step (5) is hydrogen or carbon monoxide;
and a second step of: preparation of WSe by powder metallurgy 2 /MoS 2 Composite thermoelectric material:
(1) WSe prepared in the first step (5) 2 Nanoparticles and MoS 2 Ball milling and mixing the powder to obtain mixed powder; wherein WSe 2 The mass of the powder is 1 to 10 percent of the total mass of the mixed powder;
(2) Sintering the powder obtained in the previous step under hot pressing, and mixing the WSe 2 /MoS 2 Filling the powder into a graphite mold, placing into a hot-pressing sintering furnace, vacuumizing, heating when the vacuum degree is less than 10Pa, pressurizing at the same time, preserving heat for 90-150min when the vacuum degree is up to 1100-1300 ℃, naturally cooling, and releasing pressure after cooling to obtain compact WSe 2 /MoS 2 A composite thermoelectric material;
wherein the pressure is 40-60MPa, and the temperature rising rate is 10-15 ℃/min.
The ball-milling mixing in the step (1) is carried out for 24-96 hours with the ball-material ratio of 10:1;
the graphite die used in the hot-pressing sintering process in the step (2) has an inner diameter of 12.5-20.0mm, an outer diameter of 45-60mm and a height of 50-70mm.
The invention has the beneficial effects that:
(1) The invention prepares WSe by chemical vapor deposition method 2 The nanometer particles are spherical particles with the particle diameter of about 45nm, the process is simple, the preparation is easy, and the WSe 2 The low thermal conductivity helps to reduce the thermal conductivity of the matrix material.
(2) Preparation of WSe by chemical vapor deposition 2 The equipment of the nano particles is assembled by itself, so that the cost is low;
(3) The invention is in MoS 2 Incorporating nanoscale WSe 2 Greatly improve MoS 2 The conductivity of (C) is 3 times that of uncomplexed MoS, which is reported in literature 2 More than 500 times of the total number of the components; and WSe 2 MoS after nano-particle compounding 2 The absolute value of the Seebeck coefficient of the matrix is not reduced and is within the range of-490+/-40 mu V/K; the power factor is obtained through calculation, and the compounded material is 3 times of the uncomplexed material, so that the power factor is greatly improved.
(4) The method for preparing the sample by adopting the powder metallurgy method is simple, safe and harmless, can prepare the sample in large quantities, and is used for developing thermoelectric devices.
Drawings
FIG. 1 is a flow chart of a method of making the present invention;
FIG. 2 is an X-ray diffraction (XRD) data pattern of example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) data of example 1;
fig. 4 is a graph of conductivity data for examples 3, 4, and 5;
fig. 5 is a graph of seebeck coefficient data of examples 3, 4, and 5;
FIG. 6 is a graph of Power Factor (Power Factor) data for example 3, example 4, and example 5;
FIG. 7 is an X-ray diffraction (XRD) data pattern for examples 3, 4, and 5;
fig. 8 is a Raman (Raman) data graph of example 3, example 4, example 5;
FIG. 9 is a Transmission Electron Microscope (TEM) data diagram of example 5;
FIG. 10 shows a Chemical Vapor Deposition (CVD) process for preparing WSe 2 Is a schematic diagram of the original equipment;
FIG. 11 shows a Chemical Vapor Deposition (CVD) process for preparing WSe 2 Is an improved apparatus schematic.
Detailed description of the preferred embodiments
The invention will now be described in detail with reference to the accompanying drawings and specific embodiments thereof. The following examples are merely illustrative of the invention and the scope of the invention is intended to include the full contents of the claims and is not limited to the examples alone.
The reaction scheme of the invention is shown in FIG. 1, and WSe is prepared by Chemical Vapor Deposition (CVD) 2 Nanoparticle, and WSe prepared therefrom 2 Nanoparticles and MoS 2 The powder is ball-milled and uniformly mixed in different mass ratios, and finally hot-pressed sintering is carried out at different temperatures to obtain a compact sample, and the sample is characterized and the performance is detected.
In the prior art, as shown in fig. 10, the chemical vapor deposition apparatus is composed of two heating furnaces, the heating furnace 1 evaporates Se, and the heating furnace 2 reacts at high temperature.
In the invention, as shown in the figure 11 of the related equipment, only one heating furnace is used, and the device comprises a gas circuit system, a bubbler, an oil bath pot, a tubular furnace and a cooling system, wherein the bubbler is arranged in the oil bath pot, the gas circuit system is connected with the upper port of the bubbler, and the right port of the bubbler is connected with the inlet of a quartz tube;
the quartz tube of the tube furnace is divided into a front zone, a high-temperature heating zone (the length is 60-85% of the total length of the quartz tube) and a cooling zone from front to back in sequence; the front area of the quartz tube is provided with a quartz boat, and the cooling area is a quartz tube wrapping cooling system.
The carrier gas acts to evaporate the W (CO) 6 The steam and Se steam are blown to a high-temperature reaction area of the quartz tube, and the air flow speed is 800-1200sccm; oil (oil)The set temperature of the bath pot is 110-130 ℃, the set temperature of the tube furnace is 700-1000 ℃, firstly, the tube furnace is heated to 500-600 ℃ at 10-15 ℃/min, the air flow is closed, the vaporized Se powder is prevented from being blown away, the temperature is continuously heated to 700-1000 ℃ at 10-15 ℃/min, meanwhile, the oil bath pot is opened for heating, the temperature is kept for 5-10min after reaching the set temperature, the air flow is opened, the water cooling is opened, the chemical vapor deposition is started, and the powder is deposited in a cooling area.
The purpose of the oil bath is to heat the bubbler for evaporating W (CO) 6 The method comprises the steps of carrying out a first treatment on the surface of the The tube furnace provides the temperature required for the reaction; the cooling system is to wind a hollow copper pipe outside the pipe and introduce water flow for cooling the pipe wall to reduce the deposition WSe 2 Particle size; wherein the tube furnace sets the reaction temperature, and the waste heat at the left end of the furnace is utilized to evaporate Se, so that one furnace is not used for evaporating Se. Therefore, the number of the tube furnaces can be reduced, the distance between the air inlet and the high-temperature reaction area is shortened, the adhesion of the left-end tube wall is reduced, the reaction is more complete, the yield is increased, meanwhile, the equipment is simpler, and the energy consumption is reduced.
Wherein, the diameter of the bubbler in the step (1) is 20-40mm, and the length is 80-120mm; the quartz boat has the following dimensions: 40X 20X 15mm. The container selected is only the evaporation of the powder at the temperature of use and does not react with the powder.
The diameter of the quartz tube in the step (2) is as follows: 40-60mm, length is: 1.2-1.5m; the designated position of the quartz boat means that the tube furnace is set to the reaction temperature, and the optimal position is 430 ℃ at the position of 410-450 ℃ at the left end of the quartz tube, so as to ensure the stable evaporation of Se powder; the water cooling at the right end of the quartz tube is to wind a hollow copper tube on the outer wall of the quartz tube and to introduce water flow.
Example 1
The first step: preparation of WSe by chemical vapor deposition 2 The specific preparation method of the nanoparticle comprises the following steps:
(1) 2.1112g (i.e., 0.0051 mol) of W (CO) was weighed out 6 Placing in a bubbler, weighing 2.1932g (namely 0.0278 mol) Se powder, and placing in a quartz boat;
(2) Selecting a quartz tube with the diameter of 50mm and the length of 1.4m, wherein the length of a heating zone is 0.65m, and placing a quartz boat at a position of 430 ℃ when the tube furnace is set at 850 ℃; the bubbler is placed in an oil bath pan, the right end of the bubbler is connected with a quartz tube, and the left end of the bubbler is connected with a gas circuit; the right end of the quartz tube is connected with a cooling system;
(3) Argon is introduced into the quartz tube for 10min, the air flow rate is 1000sccm, and air in the quartz tube is discharged; heating the tube furnace at 10 ℃/min, closing argon when the temperature of the tube furnace reaches 600 ℃, opening an oil bath heating bubbler to 120 ℃, and simultaneously opening a water cooling system to keep the temperature of a cooling area of the quartz tube at 45 ℃; the tube furnace was continued to warm to 850℃and was held stationary for 5min, and an argon flow was turned on at a rate of 1000sccm, W (CO) 6 And Se powder is volatilized and then reacts for 25min in a high temperature area to generate WSe 2 The nano particles are deposited in a cooling area, and after the reaction is finished, the air flow, the tube furnace, the oil bath and the cooling system are closed.
(4) Cooling the tube furnace to room temperature, and collecting 0.9918g of powder at the right end of the quartz tube;
(5) Placing the collected powder into a quartz boat, and loading into another tubular furnace;
(6) Introducing hydrogen into the quartz tube for 10min, discharging air in the quartz tube, heating the tube furnace to 570 ℃ at 10 ℃/min, preserving heat for 15min, removing impurities in the collected powder, naturally cooling, and collecting 0.9589g of the powder.
Because the powder collected in the step (5) has excessive Se powder impurities, the Se powder impurities are removed, and the condition is that the collected powder is put into a tube furnace and hydrogen is introduced; the reason is W (CO) 6 High-temperature decomposition into W and CO, and reaction of W and Se to generate WSe 2 And (5) CO is discharged. In order to ensure complete reaction of W and Se, an excess of Se which is easy to remove is set and removed after the reaction is finished.
(7) X-ray diffraction (XRD) testing was performed on the powder collected in steps (4) and (6), using Bruker D8-focus, as shown in FIG. 1, by passing through a PDF card (WSe) 2 -PDF#38-1388 and Se-PDF#73-0465), wherein the powder is directly prepared by chemical vapor deposition method and contains excessive Se, and after heat treatment in hydrogen atmosphere, the excessive Se is completely removed to obtain WSe 2 Pure phase;
(8) Scanning Electron Microscope (SEM) observation of the powder of step (6) was performed, and the test results were as shown in FIG. 2, in which WSe can be observed 2 Spherical particlesUniformly distributed, selecting 200 particles to count the particle size, and obtaining WSe 2 The average particle diameter of the particles is 35-55nm, the median particle diameter is 45nm, and the synthesis of WSe is proved 2 Is spherical nano-particles.
Example 2
Preparation of WSe by chemical vapor deposition 2 The specific preparation method of the nanoparticle comprises the following steps:
(1) 1.9112g (i.e., 0.0046 mol) W (CO) was weighed out 6 Placing the mixture in a bubbler, weighing 2.0242g (namely 0.0256 mol) Se powder, and placing the Se powder in a quartz boat;
(2) Selecting a quartz tube with the diameter of 50mm and the length of 1.4m, and placing a quartz boat at a position of 430 ℃ when the tube furnace is set to 850 ℃; the bubbler is placed in an oil bath pan, the right end of the bubbler is connected with a quartz tube, and the left end of the bubbler is connected with a gas circuit; the right end of the quartz tube is connected with a cooling system;
(3) Argon is introduced into the quartz tube for 10min, the air flow rate is 1000sccm, and air in the quartz tube is discharged; heating the tube furnace at 10 ℃/min, closing argon when the temperature of the tube furnace reaches 600 ℃, opening an oil bath heating bubbler to 120 ℃, and simultaneously opening a water cooling system to keep the temperature of a cooling area of the quartz tube at 45 ℃; the tube furnace was continued to warm to 850℃and was held stationary for 5min, and an argon flow was turned on at a rate of 1000sccm, W (CO) 6 And Se powder is volatilized and then reacts for 23min in a high temperature area to generate WSe 2 The nano particles are deposited in a cooling area, and after the reaction is finished, the air flow, the tube furnace, the oil bath and the cooling system are closed.
(4) Cooling the tube furnace to room temperature, and collecting 0.9756g of powder at the right end of the quartz tube;
(5) Placing the collected powder into a quartz boat, and loading into another tubular furnace;
(6) Introducing hydrogen into the quartz tube for 10min, discharging air in the quartz tube, heating the tube furnace to 570 ℃ at 10 ℃/min, preserving heat for 15min, removing impurities in the collected powder, naturally cooling, and collecting 0.9196g of the powder.
WSe used in the present invention 2 The nano particles are prepared repeatedly by the process.
Example 3
Preparation of WSe by powder metallurgy method 2 /MoS 2 Composite thermoelectric material, in particular preparationThe method comprises the following steps:
(1) Weigh 20.02g MoS 2 Placing the powder in a ball milling tank, setting the ball-material ratio to be 10:1, setting the rotating speed to be 500r, and ball milling for 48 hours;
(2) Weighing 12.16g of the powder obtained in the step (1), putting the powder into a graphite mold with the diameter of 13.0mm, putting the graphite mold into a hot-pressing sintering furnace, vacuumizing until the vacuum degree is less than 10Pa, starting to heat up, heating up to 1300 ℃ at the same time at 10 ℃/min, starting to pressurize to 50MPa, preserving heat for 120min, naturally cooling, and releasing pressure after cooling to room temperature;
(3) And (3) demolding, namely obtaining a sintered sample with the diameter of 13.0mm, wherein the density is 97.89% of the theoretical density through a density test, and the density is higher.
Example 4
Preparation of WSe by powder metallurgy method 2 /MoS 2 The preparation method of the composite material comprises the following steps:
(1) 1.02g of WSe obtained in the first portion was weighed out 2 Nanoparticles, 19.50g MoS 2 Placing the powder in a ball milling tank, setting the ball-material ratio to be 10:1, setting the rotating speed to be 500r, and ball milling for 48 hours;
(2) Weighing 12.18g of the powder obtained in the step (1), loading into a graphite mold with the diameter of 13mm, placing into a hot-pressing sintering furnace, vacuumizing until the vacuum degree is less than 10Pa, starting to heat up, heating up to 1300 ℃ at the same time at 10 ℃/min, starting to pressurize at 50MPa, preserving heat for 120min, naturally cooling, and releasing pressure after cooling to room temperature;
(3) And (3) demolding, namely obtaining a sintered sample with the diameter of 13.0mm, wherein the density is 97.59% of the theoretical density through a density test, and the density is higher.
Example 5
Preparation of WSe by powder metallurgy method 2 /MoS 2 The preparation method of the composite material comprises the following steps:
(1) Weighing 2.06g of WSe obtained in the first part 2 Nanoparticle, 18.12g MoS was weighed 2 Placing the powder in a ball milling tank, setting the ball-material ratio to be 10:1, setting the rotating speed to be 500r, and ball milling for 48 hours;
(2) Weighing 12.13g of the powder obtained in the step (1), putting the powder into a graphite mold with the diameter of 13.0mm, putting the graphite mold into a hot-pressing sintering furnace, vacuumizing until the vacuum degree is less than 10Pa, starting to heat up, heating up to 1300 ℃ at the same time at 10 ℃/min, starting to pressurize to 50MPa, preserving heat for 120min, naturally cooling, and releasing pressure after cooling to room temperature;
(3) And (3) demolding, namely obtaining a sintered sample with the diameter of 13.0mm, wherein the density is 98.16% of the theoretical density through a density test, and the density is higher.
Test case
(1) Conductivity and Seebeck coefficient test
The bulk WSe obtained by hot-press sintering of example 3, example 4 and example 5 2 /MoS 2 The composite thermoelectric material was cut into 4×4×10mm samples in the axial direction, and the electrical conductivity and seebeck coefficient were measured with a ZEM-3 test instrument. The temperature range was 100-700 c, and the conductivity and seebeck coefficient obtained are shown in fig. 4 and 5. Example 3, example 4 and example 5, the conductivities increased with increasing temperature and decreased last, were due to the purchase of MoS 2 The purity was 99.5%, and the impurity phase contained 0.5% exhibited the conductivity characteristics of the impurity semiconductor. Example 3 the conductivity had a maximum at 400 c with increasing temperature of 230.77S/m, then began to decrease, and a minimum at 500 c of 285.52S/m, and continued to increase above 500 c; the conductivities of examples 4 and 5 had maxima at 300℃of 672.66S/m and 728.25S/m, respectively, and then began to decrease, and had minima at 600℃of 495.078S/m and 499.91S/m, respectively, and continued to increase above 600 ℃. In general, there is WSe 2 The conductivity is improved and 10% WSe is obtained during compounding 2 The composition is improved by 3 times than the conductivity, and the MoS is greatly improved 2 Conductivity of the substrate. The Seebeck coefficients in the three examples are all negative values, indicating an n-type thermoelectric material, the absolute value of the Seebeck coefficient decreases with increasing temperature in example 3, the Seebeck coefficients in examples 4 and 5 are both in the range of-490.+ -.40. Mu.V/K with increasing temperature, and WSe 2 The greater the content, the greater the absolute value of the seebeck coefficient. In summary, it is concluded that: WSe (Wireless sensor set) 2 /MoS 2 The composite material improves the conductivity while the absolute value of the Seebeck coefficient is not reduced.
WSe is calculated according to the conductivity and the Seebeck coefficient 2 /MoS 2 Composite materialAs shown in figure 6, the conductivity takes the absolute role in the power factor, and the law of the power factor changing along with the temperature is basically consistent with the conductivity along with WSe 2 The larger the content, the larger the power factor; at 300 ℃, there is a maximum, the power factors for example 3, example 4 and example 5 are respectively: 61.81 mu W/m -1 K -1 、155.00μW/m -1 K -1 And 183.08. Mu.W/m -1 K -1 10% WSe was added 2 The power factor of the sample is that WSe is not added 2 3 times, explaining WSe 2 Is obviously improved in MoS 2 The power factor of the substrate.
(2) X-ray diffraction (XRD) characterization
The sintered samples of example 3, example 4 and example 5 were XRD characterized, and the test results were shown in the XRD data pattern of FIG. 7 (test plane is a plane perpendicular to the direction of pressure), and were compared with standard PDF cards (MoS) 2 -PDF#37-1492、WSe 2 PDF # 38-1388), diffraction peaks appear at 14.3 degrees, 39.5 degrees, 44.1 degrees and the like of the sintered sample, and the diffraction peaks are compared with a standard card, namely MoS 2 No WSe was found 2 Mainly due to the purchased MoS 2 High crystallinity, high diffraction intensity and WSe prepared by CVD 2 Is in nanometer order, and after quenching, has poor crystallinity, low diffraction intensity and only MoS 2 1/100 of the ratio, the phase difference is extremely large, moS 2 Is covered with WSe 2 So that WSe cannot be found in the XRD pattern 2 Is a diffraction peak of (2).
(3) Raman (Raman) characterization
To further verify WSe 2 And MoS 2 The Raman test was performed with an insia Reflex type laser microscopic Raman spectrometer from Renishaw. As shown in the Raman spectrum data diagram of FIG. 8, the spectrum is measured at 409cm -1 And 385cm -1 Peak in the vicinity, and MoS 2 Corresponding to characteristic peaks of A 1g And
a mode. At 250cm -1 A peak appears in the vicinity of the peak,with WSe 2 Corresponds to the characteristic peak of (2) and follows WSe 2 The content is increased and the peak intensity is increased. So WSe can be obtained from Raman spectra 2 And MoS 2 Is a successful composite of (a).
(4) Transmission Electron Microscope (TEM) characterization
The TEM image as in figure (9) shows WSe 2 And MoS 2 Microstructure of the composite material. The obvious lamellar structure is matched with the lamellar structure of TMDs material, obvious chromatic aberration exists at the edge, high-resolution transmission observation is carried out at the position with obvious chromatic aberration (as in a picture frame), the interplanar spacing is measured through lattice fringes, the interplanar spacing of a dark area is 0.65nm, and the color difference corresponds to WSe 2 (002) The interplanar spacing of the light-colored regions is 0.280nm, corresponding to MoS 2 (100) In the face, it can be concluded that the dark areas are WSe 2 The light area is MoS 2 . Selected area electron diffraction (SEDA) patterns exhibit a series of diffraction rings, respectively in MoS 2 (004) (102), (008), (116) and WSe 2 (103) The (006) faces. It can be concluded that WSe 2 In MoS 2 Is a composite of edges of the (c).
The above examples and test examples are provided for the purpose of illustration only and the claims are fully intended to be fully understood by those skilled in the art from the foregoing description, examples and methods.
In summary, the WSe provided by the invention 2 /MoS 2 The composite thermoelectric material and the preparation method can obtain compact WSe 2 /MoS 2 A composite thermoelectric material. By at WSe 2 And MoS 2 The absolute value of the Seebeck coefficient is not reduced, and the conductivity is improved at the same time, thereby effectively improving the MoS 2 Is a power factor of (a).
The invention is not a matter of the known technology.
Claims (7)
1. WSe (Wireless sensor package) 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized by comprising the following steps:
the first step: preparation of WSe by chemical vapor deposition 2 Nanoparticles:
(1) In the chemical vapor deposition equipment, W (CO) 6 Placing the quartz boat into a bubbler, and placing Se powder into the quartz boat;
wherein the molar ratio is W (CO) 6 ：Se＝1：5.0-10.0；
(2) Placing the quartz boat in the step (1) in the front region of a quartz tube of a horizontal tube furnace, connecting a bubbler with the left end inlet of the quartz tube of the tube furnace, and placing the quartz boat in an oil bath pan; the right end of the quartz tube of the tube furnace is connected with a water cooling device,
(3) Under inert atmosphere, heating the tube furnace at 10-15 ℃/min, closing carrier gas flow when the temperature of the tube furnace is raised to 500-600 ℃, opening an oil bath heating bubbler to 110-130 ℃, and setting the temperature of a cooling area to 20-50 ℃; when the temperature of the tube furnace is raised to 700-1000 ℃, an inert carrier gas flow, W (CO), is opened 6 And Se powder are volatilized and react for 15-30min in a high temperature area to generate WSe 2 Depositing nanoparticles in a cooling zone;
(4) Collecting powder at the right end of the quartz tube;
(5) Placing the powder collected in step (4) in a quartz boat, placing in another tube furnace, heating the tube furnace to 400-600deg.C at 10-15deg.C/min under reducing atmosphere, and maintaining the temperature for 15-30min to obtain pure WSe 2 A nanoparticle;
the WSe 2 The particle size of the nano particles is 35-55nm;
and a second step of: preparation of WSe by powder metallurgy 2 /MoS 2 Composite thermoelectric material:
(1) WSe prepared in the first step (5) 2 Nanoparticles and MoS 2 Ball milling and mixing the powder to obtain mixed powder; wherein WSe 2 The mass of the powder is 1 to 10 percent of the total mass of the mixed powder;
(2) Sintering the powder obtained in the previous step under hot pressing, and mixing the WSe 2 /MoS 2 Filling the powder into a graphite mold, placing into a hot-pressing sintering furnace, vacuumizing, heating when the vacuum degree is less than 10Pa, pressurizing at the same time, preserving heat for 90-150min when the vacuum degree is up to 1100-1300 ℃, naturally cooling, and releasing pressure after cooling to obtain compact WSe 2 /MoS 2 A composite thermoelectric material;
wherein the pressure is 40-60MPa, and the temperature rising rate is 10-15 ℃/min.
2. A WSe as claimed in claim 1 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized in that the chemical vapor deposition method equipment comprises an air circuit system, a bubbler, an oil bath pot, a tube furnace and a cooling system, wherein the bubbler is arranged in the oil bath pot, the air circuit system is connected with the upper port of the bubbler, and the side end of the air circuit system is connected with the inlet of a quartz tube;
the quartz tube of the tube furnace is divided into a front zone, a high-temperature heating zone and a cooling zone from front to back in sequence; the front area of the quartz tube is provided with a quartz boat, and the cooling area is a quartz tube wrapping cooling system.
3. A WSe as claimed in claim 2 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized in that the diameter of a quartz tube is as follows: 40-60mm, length is: 1.2-1.5m.
4. A WSe as claimed in claim 1 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized in that the inert gas in the step (3) in the first step is helium, argon or nitrogen; the gas flow rate is 800-1200sccm.
5. A WSe as claimed in claim 1 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized in that the reducing atmosphere in the step (5) in the first step is hydrogen or carbon monoxide.
6. A WSe as claimed in claim 1 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized in that the ball-to-material ratio in the ball milling and mixing in the step (1) in the second step is 10:1, and the time is 24-96h.
7. A WSe as claimed in claim 1 2 /MoS 2 The preparation method of the composite thermoelectric material is characterized in that the inner diameter of a graphite mold used in the hot-pressing sintering process in the step (2) in the second step12.5-20.0mm, 45-60mm in outer diameter and 50-70mm in height.
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