CN118159115A - Bismuth and indium double-doped lead telluride thermoelectric material and preparation method thereof - Google Patents
Bismuth and indium double-doped lead telluride thermoelectric material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 29
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 16
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 14
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- KQNKJJBFUFKYFX-UHFFFAOYSA-N acetic acid;trihydrate Chemical compound O.O.O.CC(O)=O KQNKJJBFUFKYFX-UHFFFAOYSA-N 0.000 claims description 12
- 229940046892 lead acetate Drugs 0.000 claims description 12
- VOADVZVYWFSHSM-UHFFFAOYSA-L sodium tellurite Chemical compound [Na+].[Na+].[O-][Te]([O-])=O VOADVZVYWFSHSM-UHFFFAOYSA-L 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 10
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
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- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000001670 anatto Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229910002665 PbTe Inorganic materials 0.000 description 9
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
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Abstract
The invention discloses a bismuth and indium double-doped lead telluride thermoelectric material and a preparation method thereof. The general formula of the bismuth and indium double-doped lead telluride thermoelectric material is Pb 0.993‑xBi0.007Inx Te, wherein x=0.003-0.007, pb 0.993‑xBi0.007Inx Te nanocrystalline powder is synthesized by a solvothermal method, and then the Pb 0.993‑xBi0.007Inx Te nanocrystalline block is obtained by rapidly sintering and compacting the powder by a twice spark plasma sintering technology. The invention increases the number of two-dimensional Te vacancies in the unit cell by double doping of bismuth and indium, thereby enhancing phonon scattering, reducing the lattice heat conductivity of the material and obviously improving the thermoelectric performance of the lead telluride-based thermoelectric material.
Description
Technical Field
The invention belongs to the field of thermoelectric materials, and relates to a bismuth and indium double-doped lead telluride thermoelectric material and a preparation method thereof.
Background
The thermoelectric material can realize direct conversion of heat energy and electric energy, and provides important support for renewable energy sources and energy-saving technology. The power generation efficiency of a thermoelectric material is determined by the thermoelectric figure of merit zT of the material, where zt=s 2σT/κt, where S is the seebeck coefficient, σ is the electrical conductivity, κ t is the total thermal conductivity, and T is the thermodynamic temperature. However, there is a complex coupling relationship between these parameters, which restricts the rise of zT value. Therefore, in the thermoelectric field, efforts are made to overcome the complex coupling relation between these parameters to improve the performance of thermoelectric materials, and development of thermoelectric materials in the fields of thermoelectric power generation, automobile exhaust gas recycling, electronic equipment heat dissipation and the like is promoted to be the key point of research.
The lead telluride (PbTe) thermoelectric material is a thermoelectric material which is excellent in high temperature performance, has a relatively low thermal conductivity while having a good seebeck coefficient and electrical conductivity, is relatively simple in production process, and is advantageous for mass production and application. The method for improving the thermoelectric performance of the PbTe thermoelectric material is more common at present: (1) The optimization of carrier concentration, Z. -Y.Huang et al demonstrate that Ag-introduced decorative dislocations can promote the dissolution of dopants into the PbTe matrix at high temperature, thereby optimizing carrier concentration in combination with the static doping effect of Sb, the low-order dislocation can scatter medium-low frequency phonons but has little influence on electron scattering, so that higher carrier mobility is maintained, finally, in Sb and Ag 2 Te co-doped n-type PbTe, the maximum zT of 1.5 is obtained when 750K, the average zT reaches the optimization of 1.1(Z.-Y.Huang,F.Wang,C.Jung,et al,Decorated dislocations lead to dynamically optimized thermoelectric performance in N-type PbTe,Materials Today Physics37(2023),101198.);(2) lattice thermal conductivity between 323K and 823K, for example, Z. -Z.Luo et al introduce ZnTe alloy into Ga-doped n-type PbTe, precipitated Ga 2Te3 nano grains effectively scatter carrier phonons, lattice thermal conductivity is obviously reduced, and finally, the average zT of a sample in 323-823K reaches 1.26(Z.-Z.Luo,S.Cai,S.Hao,T.P.Bailey,et al.Kanatzidis,Extraordinary role of Zn in enhancing thermoelectric performance of Ga-doped n-type PbTe,Energy Environ.Sci.15(2022),368-375.). but no document of bismuth and indium double-doped lead telluride thermoelectric materials is currently seen.
Disclosure of Invention
The invention aims to provide a bismuth and indium double-doped lead telluride thermoelectric material and a preparation method thereof.
The technical scheme for realizing the purpose of the invention is as follows:
Bismuth and indium double doped lead telluride thermoelectric material has the chemical general formula Pb 0.993-xBi0.007Inx Te, where x=0.003-0.007.
Preferably, x=0.005.
The preparation method of the bismuth and indium double-doped lead telluride thermoelectric material comprises the following specific steps:
Step 1, the molar ratio of lead acetate trihydrate, sodium tellurite, bismuth nitrate pentahydrate and indium chloride is 0.986-0.99: 1:0.007: 0.003-0.007, adding lead acetate trihydrate, sodium tellurite, bismuth nitrate pentahydrate and indium chloride into ethylene glycol solution of polyvinylpyrrolidone, then adding sodium hydroxide solution, mixing and stirring at 55+/-5 ℃ to completely dissolve the mixture to form a reaction solution;
Step 2, placing the reaction solution at 230+/-1 ℃ for heat preservation reaction for 4+/-0.5 h, cooling to room temperature after the reaction is finished, centrifugally washing to remove impurities, vacuum drying, and grinding to obtain Pb 0.993-xBi0.007Inx Te nanocrystalline powder;
And 3, performing twice spark plasma sintering on Pb 0.993-xBi0.007Inx Te nanocrystalline powder, wherein the sintering temperature is 550+/-50 ℃, the heat preservation time is 15+/-5 min, and the sintering pressure is 60+/-5 MPa, so as to obtain the Pb 0.993-xBi0.007Inx Te nanocrystalline block.
Preferably, in step 1, the concentration of polyvinylpyrrolidone in the ethylene glycol solution of polyvinylpyrrolidone is 0.056g/ml.
Preferably, in step 1, the molar ratio of lead acetate trihydrate, sodium tellurite, bismuth nitrate pentahydrate, indium chloride is 0.988:1:0.007:0.005.
Preferably, in the step 1, the concentration of the sodium hydroxide solution is 5mol/L, and the volume ratio of the ethylene glycol solution of polyvinylpyrrolidone to the sodium hydroxide solution is 9:1.
Preferably, in the step 2, the washing mode is to wash 3 times by adopting ultrapure water and then wash 3 times by adopting absolute ethyl alcohol.
Preferably, in step 2, the centrifugal speed is 11000r/min and the centrifugal time is 2min.
Preferably, in the step 2, the vacuum drying temperature is 50-60 ℃ and the drying time is 12-15 h.
Compared with the prior art, the invention has the following advantages:
(1) The Pb 0.993-xBi0.007Inx Te nanocrystalline is synthesized by adopting a solvothermal method, so that chemical components, grain size and synthesis are convenient and fast, and a spark plasma sintering technology is adopted, so that compared with technologies such as hot press forming, the Pb 0.993-xBi0.007Inx Te nanocrystalline has lower process temperature and simpler process flow, can obtain materials with more excellent mechanical properties, is suitable for industrial application, and is beneficial to improving the material performance and reducing the production cost;
(2) The invention increases the density of two-dimensional Te vacancies in the lead telluride unit cell by double doping of bismuth and indium, successfully reduces the lattice thermal conductivity of the material, and the doping ensures that the material obtains higher electrical property, wherein Pb 0.988Bi0.007In0.005 Te has a high power factor of 2.01mW m -1K-2 and a total thermal conductivity of 0.93W m -1K-1 at 723K, and zT reaches 1.55.
Drawings
Fig. 1 is a graph of the change in conductivity (σ) versus temperature (T) of Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005, and 0.007) samples prepared in each of the examples and the comparative examples.
Fig. 2 is a graph of the change in seebeck coefficient (S) with respect to temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared in each of examples and comparative examples.
Fig. 3 is a graph of the power factor (S 2 σ) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005, and 0.007) samples prepared in each of the examples and the comparative examples.
Fig. 4 is a graph of the total heat conductivity (κ t) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared in each of the examples and the comparative examples.
Fig. 5 is a graph of the change in lattice thermal conductivity (κ l) versus temperature (T) of Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared in each of the examples and the comparative examples.
Fig. 6 is a graph of thermoelectric figure of merit (zT) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005, and 0.007) samples prepared for each of the examples and the comparative examples.
Detailed Description
The invention is further described in detail below with reference to examples and figures.
Example 1
3.2G of polyvinylpyrrolidone was dissolved in a hydrothermal kettle liner containing 57.6ml of ethylene glycol, then 1.6mmol of sodium tellurite was added, and the mixture was heated on a stirring table to 55℃and stirred, then 0.0112mmol of bismuth nitrate pentahydrate, 0.0048mmol of indium chloride and 1.584mmol of lead acetate trihydrate were added in this order, and finally 6.4ml of sodium hydroxide solution with a concentration of 5mol/L was added. Stirring for 10min to fully dissolve the medicines, screwing the hydrothermal kettle, putting the hydrothermal kettle into a baking oven at 230 ℃ for reaction for 4h, taking out the hydrothermal kettle after the reaction is finished, naturally cooling the hydrothermal kettle to room temperature, separating out products, washing the products with ultrapure water and absolute ethyl alcohol for 3 times, centrifuging at 11000r/min each time for 2min, and then putting the products into a vacuum drying oven at 55 ℃ for drying for 12h. Taking out a sample, grinding the sample into powder, then placing the powder into a graphite mold with the inner diameter of 10mm, carrying out spark plasma sintering, wherein the sintering temperature is 550 ℃, the heat preservation time is 15min, the sintering pressure is 60MPa, taking out a block, grinding the block into powder, then placing the block into the graphite mold with the inner diameter of 10mm again, carrying out secondary spark plasma sintering, and obtaining the Pb 0.99Bi0.007In0.003 Te nanocrystalline block with the sintering temperature of 550 ℃, the heat preservation time is 15min and the sintering pressure of 60 MPa. The thermoelectric performance test was performed perpendicular to the sintering pressure direction.
Example 2
3.2G of polyvinylpyrrolidone was dissolved in a hydrothermal kettle liner containing 57.6ml of ethylene glycol, then 1.6mmol of sodium tellurite was added, and the mixture was heated on a stirring table to 55℃with stirring, then 0.0112mmol of bismuth nitrate pentahydrate, 0.008mmol of indium chloride and 1.5808mmol of lead acetate trihydrate were added in this order, and finally 6.4ml of sodium hydroxide solution with a concentration of 5mol/L was added. Stirring for 10min to fully dissolve the medicines, screwing the hydrothermal kettle, putting the hydrothermal kettle into a baking oven at 230 ℃ for reaction for 4h, taking out the hydrothermal kettle after the reaction is finished, naturally cooling the hydrothermal kettle to room temperature, separating out products, washing the products with ultrapure water and absolute ethyl alcohol for 3 times, centrifuging at 11000r/min each time for 2min, and then putting the products into a vacuum drying oven at 55 ℃ for drying for 12h. Taking out a sample, grinding the sample into powder, then placing the powder into a graphite mold with the inner diameter of 10mm, carrying out spark plasma sintering, wherein the sintering temperature is 550 ℃, the heat preservation time is 15min, the sintering pressure is 60MPa, taking out a block, grinding the block into powder, then placing the block into the graphite mold with the inner diameter of 10mm again, carrying out secondary spark plasma sintering, and obtaining the Pb 0.988Bi0.007In0.005 Te nanocrystalline block with the sintering temperature of 550 ℃, the heat preservation time is 15min and the sintering pressure of 60 MPa. The thermoelectric performance test was performed perpendicular to the sintering pressure direction.
Example 3
3.2G of polyvinylpyrrolidone was dissolved in a hydrothermal kettle liner containing 57.6ml of ethylene glycol, then 1.6mmol of sodium tellurite was added, and the mixture was heated to 55℃on a stirring table and stirred, then 0.0112mmol of bismuth nitrate pentahydrate, 0.0112mmol of indium chloride and 1.5776mmol of lead acetate trihydrate were added in this order, and finally 6.4ml of sodium hydroxide solution with a concentration of 5mol/L was added. Stirring for 10min to fully dissolve the medicines, screwing the hydrothermal kettle, putting the hydrothermal kettle into a baking oven at 230 ℃ for reaction for 4h, taking out the hydrothermal kettle after the reaction is finished, naturally cooling the hydrothermal kettle to room temperature, separating out products, washing the products with ultrapure water and absolute ethyl alcohol for 3 times, centrifuging at 11000r/min each time for 2min, and then putting the products into a vacuum drying oven at 55 ℃ for drying for 12h. Taking out a sample, grinding the sample into powder, then placing the powder into a graphite mold with the inner diameter of 10mm, carrying out spark plasma sintering, wherein the sintering temperature is 550 ℃, the heat preservation time is 15min, the sintering pressure is 60MPa, taking out a block, grinding the block into powder, then placing the block into the graphite mold with the inner diameter of 10mm again, carrying out secondary spark plasma sintering, and obtaining the Pb 0.986Bi0.007In0.007 Te nanocrystalline block with the sintering temperature of 550 ℃, the heat preservation time is 15min and the sintering pressure of 60 MPa. The thermoelectric performance test was performed perpendicular to the sintering pressure direction.
Comparative example 1
3.2G of polyvinylpyrrolidone was dissolved in a hydrothermal lining of a kettle containing 57.6ml of ethylene glycol, then 1.6mmol of sodium tellurite was added, and the kettle was heated to 55℃on a stirring table with stirring, then 1.6mmol of lead acetate trihydrate was added, and finally 6.4ml of sodium hydroxide solution with a concentration of 5mol/L was added. Stirring for 10min to fully dissolve the medicines, screwing the hydrothermal kettle, putting the hydrothermal kettle into a baking oven at 230 ℃ for reaction for 4h, taking out the hydrothermal kettle after the reaction is finished, naturally cooling the hydrothermal kettle to room temperature, separating out products, washing the products with ultrapure water and absolute ethyl alcohol for 3 times, centrifuging at 11000r/min each time for 2min, and then putting the products into a vacuum drying oven at 55 ℃ for drying for 12h. Taking out a sample, grinding the sample into powder, then placing the powder into a graphite mold with the inner diameter of 10mm, carrying out spark plasma sintering, wherein the sintering temperature is 550 ℃, the heat preservation time is 15min, the sintering pressure is 60MPa, taking out a block, grinding the block into powder, then placing the block into the graphite mold with the inner diameter of 10mm again, carrying out secondary spark plasma sintering, and obtaining the PbTe nanocrystalline block with the sintering temperature of 550 ℃, the heat preservation time is 15min and the sintering pressure is 60 MPa. The thermoelectric performance test was performed perpendicular to the sintering pressure direction.
Comparative example 2
3.2G of polyvinylpyrrolidone was dissolved in a hydrothermal kettle liner containing 57.6ml of ethylene glycol, then 1.6mmol of sodium tellurite was added, and the mixture was heated to 55℃on a stirring table and stirred, then 0.0112mmol of bismuth nitrate pentahydrate and 1.5888mmol of lead acetate trihydrate were added in this order, and finally 6.4ml of sodium hydroxide solution with a concentration of 5mol/L was added. Stirring for 10min to fully dissolve the medicines, screwing the hydrothermal kettle, putting the hydrothermal kettle into a baking oven at 230 ℃ for reaction for 4h, taking out the hydrothermal kettle after the reaction is finished, naturally cooling the hydrothermal kettle to room temperature, separating out products, washing the products with ultrapure water and absolute ethyl alcohol for 3 times, centrifuging at 11000r/min each time for 2min, and then putting the products into a vacuum drying oven at 55 ℃ for drying for 12h. Taking out a sample, grinding the sample into powder, then placing the powder into a graphite mold with the inner diameter of 10mm, carrying out spark plasma sintering, wherein the sintering temperature is 550 ℃, the heat preservation time is 15min, the sintering pressure is 60MPa, taking out a block, grinding the block into powder, then placing the block into the graphite mold with the inner diameter of 10mm again, carrying out secondary spark plasma sintering, and obtaining the Pb 0.993Bi0.007 Te nanocrystalline block with the sintering temperature of 550 ℃, the heat preservation time is 15min and the sintering pressure of 60 MPa. The thermoelectric performance test was performed perpendicular to the sintering pressure direction.
Comparative example 3
3.2G of polyvinylpyrrolidone are dissolved in a hydrothermal lining of a kettle containing 57.6ml of ethylene glycol, then 1.6mmol of sodium tellurite are added, the mixture is heated to 55℃on a stirring table and stirred, then 0.008mmol of indium chloride and 1.592mmol of lead acetate trihydrate are added in sequence, and finally 6.4ml of sodium hydroxide solution with a concentration of 5mol/L are added. Stirring for 10min to fully dissolve the medicines, screwing the hydrothermal kettle, putting the hydrothermal kettle into a baking oven at 230 ℃ for reaction for 4h, taking out the hydrothermal kettle after the reaction is finished, naturally cooling the hydrothermal kettle to room temperature, separating out products, washing the products with ultrapure water and absolute ethyl alcohol for 3 times, centrifuging at 11000r/min each time for 2min, and then putting the products into a vacuum drying oven at 55 ℃ for drying for 12h. Taking out a sample, grinding the sample into powder, then placing the powder into a graphite mold with the inner diameter of 10mm, carrying out spark plasma sintering, wherein the sintering temperature is 550 ℃, the heat preservation time is 15min, the sintering pressure is 60MPa, taking out a block, grinding the block into powder, then placing the block into the graphite mold with the inner diameter of 10mm again, carrying out secondary spark plasma sintering, and obtaining the Pb 0.995In0.005 Te nanocrystalline block with the sintering temperature of 550 ℃, the heat preservation time is 15min and the sintering pressure of 60 MPa. The thermoelectric performance test was performed perpendicular to the sintering pressure direction.
TABLE 1
Fig. 1 is a graph of conductivity (σ) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005, and 0.007) samples prepared in examples and comparative examples, and it can be seen that the conductivity decreases with increasing temperature, showing the characteristics of a degenerate semiconductor; the conductivity increases over the entire temperature range after bismuth doping, which is the result of the increase in carrier concentration, and reaches 2018S cm -1 at 323K when x=0.007 and y=0.005.
Fig. 2 is a graph of seebeck coefficient (S) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared in examples and comparative examples, and it can be seen that the seebeck coefficients are all negative, indicating that the materials are n-type, the absolute value of the seebeck coefficient increases with temperature and decreases with increasing conductivity for samples doped with bismuth, whereas the absolute value of the seebeck coefficient of the indium single doped sample does not change much, and the absolute value of the seebeck coefficient obtains the maximum value of 260 μ V K -1 at 773K when x=0.007, y=0.005.
Fig. 3 is a graph of power factor (S 2 σ) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared in examples and comparative examples, and it can be seen that there is a substantial increase in power factor over the entire temperature period after bismuth and indium doping, and the average power factor at 423-823K for samples with a maximum value exceeding 2mW m -1K-2,Pb0.988Bi0.007In0.005 Te is also increased from 0.98mW m -1K-2 to 2.17mW m -1K-2 in the PbTe sample, by 121%.
Fig. 4 is a graph of total thermal conductivity (κ t) versus temperature (T) for samples of Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) prepared for each of the examples and comparative examples, it can be seen that the total thermal conductivity decreases with increasing temperature and that the sample of x=0.007, y=0.005 has the lowest total thermal conductivity of 0.88Wm -1K-1 at 823K.
Fig. 5 is a graph of the variation of lattice thermal conductivity (κ l) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared in examples and comparative examples, and it can be seen that the trend of other doped samples except comparative example 1 is consistent with the variation of the total thermal conductivity, and that the Pb 0.988Bi0.007In0.005 Te sample has the lowest lattice thermal conductivity of 0.55W m -1K-1 at 823K.
Fig. 6 is a graph of thermoelectric figure of merit (zT) versus temperature (T) for Pb 1-x-yBixIny Te (x=0 and 0.007, y=0, 0.003, 0.005 and 0.007) samples prepared for each example and comparative example, and it can be seen that when x=0.007, y=0.005, a maximum zT value of 1.55 is reached at 723K, which is 142% higher than the maximum value of 0.64 for comparative example 1, and an average zT of 1.17 is reached.
Claims (9)
1. The bismuth and indium double-doped lead telluride thermoelectric material is characterized by having a chemical formula of Pb 0.993-xBi0.007Inx Te, wherein x=0.003-0.007.
2. The bismuth and indium double doped lead telluride thermoelectric material of claim 1 wherein x = 0.005.
3. The method for preparing the bismuth and indium double-doped lead telluride thermoelectric material as claimed in claim 1 or 2, wherein the method comprises the following specific steps:
Step 1, according to the mole ratio of lead acetate trihydrate, sodium tellurite, bismuth nitrate pentahydrate and indium chloride of 0.986-0.99: 1:0.007: 0.003-0.007, adding lead acetate trihydrate, sodium tellurite, bismuth nitrate pentahydrate and indium chloride into an ethylene glycol solution of polyvinylpyrrolidone, then adding a sodium hydroxide solution, mixing and stirring at 55+/-5 ℃ to completely dissolve the mixture to form a reaction solution;
Step 2, placing the reaction solution at 230+/-1 ℃ for heat preservation reaction for 4+/-0.5 h, cooling to room temperature after the reaction is finished, centrifugally washing to remove impurities, vacuum drying, and grinding to obtain Pb 0.993-xBi0.007Inx Te nanocrystalline powder;
And 3, performing twice spark plasma sintering on Pb 0.993-xBi0.007Inx Te nanocrystalline powder, wherein the sintering temperature is 550+/-50 ℃, the heat preservation time is 15+/-5 min, and the sintering pressure is 60+/-5 MPa, so as to obtain the Pb 0.993-xBi0.007Inx Te nanocrystalline block.
4. The process according to claim 3, wherein in step 1, the concentration of polyvinylpyrrolidone in the ethylene glycol solution of polyvinylpyrrolidone is 0.056g/ml.
5. A method according to claim 3, wherein in step 1, the molar ratio of lead acetate trihydrate, sodium tellurite, bismuth nitrate pentahydrate, indium chloride is 0.988:1:0.007:0.005.
6. A method according to claim 3, wherein in step 1, the concentration of the sodium hydroxide solution is 5mol/L, and the volume ratio of the ethylene glycol solution of polyvinylpyrrolidone to the sodium hydroxide solution is 9:1.
7. The method of claim 3, wherein in step 2, the washing is performed by washing 3 times with ultrapure water and then 3 times with absolute ethanol.
8. A method according to claim 3, wherein in step 2, the centrifugation speed is 11000r/min and the centrifugation time is 2min.
9. The method according to claim 3, wherein in the step 2, the vacuum drying temperature is 50-60 ℃ and the drying time is 12-15 h.
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