CN113611792A - Copper-based chalcogenide thermoelectric composite material and preparation method thereof - Google Patents
Copper-based chalcogenide thermoelectric composite material and preparation method thereof Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 150000004770 chalcogenides Chemical class 0.000 title claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 80
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- 229940116318 copper carbonate Drugs 0.000 claims abstract description 21
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 21
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- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
Abstract
The invention belongs to the technical field of thermoelectric materials, and discloses a copper-based chalcogenide thermoelectric composite material and a preparation method thereof. The chemical general formula of the material is Cu1.8S-CuO, the material comprising a main phase Cu1.8S and a second phase CuO uniformly distributed in the main phase Cu1.8S is carried out; also comprises air holes which are uniformly distributed in the main phase Cu1.8And (S) in the step (A). The preparation method comprises three steps of solid-phase sintering of Cu elemental powder and S elemental powder respectively to obtain Cu1.8S, casting ingots; cu1.8S, ball-milling and mixing the cast ingot and the basic copper carbonate; cu1.8S‑Cu2(OH)2CO3And (3) performing spark plasma sintering on the mixed powder. The material provided by the invention has strong service stability and excellent thermoelectric performance.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and particularly relates to a copper-based chalcogenide thermoelectric composite material and a preparation method thereof.
Background
The thermoelectric energy conversion technology is a clean energy technology capable of realizing direct and mutual conversion between heat energy and electric energy, is expected to improve the current lower comprehensive utilization rate (about 40 percent) of energy and relieve the energy crisis, and a thermoelectric device prepared from thermoelectric materials has the characteristics of no moving parts, no noise, long-term stability and the like. The high-performance thermoelectric device is formed by connecting high-performance p-type thermoelectric materials and high-performance n-type thermoelectric materials in series, has wider application, and can be applied to deep space detection power supply and automobile exhaust waste heat recovery in the field of pyroelectric; and in the aspect of generating temperature difference by electricity, the thermoelectric generator is mainly applied to electronic element refrigeration, small-size refrigeration refrigerators and the like.
The thermoelectric material with high performance at present is Bi2Te3PbTe, PbS, Si-Ge alloys, etc., but these materials involve rare and precious metals or toxic and harmful elements, are either expensive, or violate the development concept of green high-performance thermoelectric materials. Therefore, finding and researching a compound formed by elements which are non-toxic, harmless, cheap and abundant and can be applied to an industrial production method as a thermoelectric material is very important basic work in the industry.
Cu1.8The S material is an intrinsic p-type semiconductor, the forbidden band width of the material is about 1.2eV, the S material is suitable for photoelectric and thermoelectric material applications, and the S material has the characteristics of rich elements, low cost and environmental friendliness, and is well paid attention by thermoelectric researchers. Cu1.8The S material has the characteristic of super ion conductor at high temperature, namely Cu ions in anions S2-Has extremely high mobility in the crystal lattice framework and is compared with Cu2The S material has a higher hole carrier concentration and therefore has better conductivity. Meanwhile, the fast migration behavior of Cu ions can scatter the propagation of phonons, so that Cu1.8The S material also has a very low lattice thermal conductivity.
However, Cu1.8When the S material reaches the phase transition temperature (about 90 ℃) at the ambient temperature, the Cu ions can migrate at a high speed, so that the concentration of the Cu ions on partial positions is lower than that of the Cu ions for maintaining the crystal structureCritical value of (b), thereby resulting in Cu1.8S on the surface of S is easier to volatilize, the thermoelectric property is weakened, and the stability is poor. Researchers have proposed incorporating a carbon or metal ion barrier layer with Cu2-xS material is prepared into multi-section thermoelectric material to improve the stability, but the method is not beneficial to batch production, and the bonding strength between the barrier layer and the matrix material is lower than the mechanical strength of the whole section material. Therefore, the inventor and the research and development team thereof carry out related research, exploration, test and analysis, and finally obtain the scheme of the invention.
Disclosure of Invention
The invention aims to provide a copper-based chalcogenide thermoelectric composite material and a preparation method thereof, so as to solve the problem of Cu in the prior art1.8The S material has poor stability as a thermoelectric material.
In order to achieve the above object, the present invention provides a copper-based chalcogenide thermoelectric composite material having a chemical formula of Cu1.8S-CuO, the material comprising a main phase Cu1.8S and a second phase CuO uniformly distributed in the main phase Cu1.8S is carried out; also comprises air holes which are uniformly distributed in the main phase Cu1.8And (S) in the step (A).
The beneficial effects of the first basic scheme are as follows: the main phase of the thermoelectric composite material is Cu1.8S, thus having Cu1.8The S material has good thermoelectric performance due to the nature of the S material. Experiments show that the second phase CuO is uniformly distributed in the main phase Cu1.8In S, the long-range migration of Cu ions can be inhibited, thereby improving the stability of the copper sulfide material. Compared with the prior art in which the macroscopic barrier layer is added, the macroscopic barrier layer is introduced after the preparation of the block material, the mechanical strength is weak, and the method is not suitable for batch production.
And in the main phase Cu1.8The introduction of an additional phase interface in S can reduce the lattice thermal conductivity of the material by strongly scattering phonons, and finally contributes to the optimization of Cu1.8The thermoelectric property of the S material; the introduction of pores also helps to reduce the lattice of the materialThermal conductivity and thus higher ZT values.
In addition, the electrical conductivity and the seebeck coefficient are in a coupling relation, when the electrical conductivity is increased, the seebeck coefficient is inevitably reduced, and the thermoelectric figure of merit ZT ═ σ S, which is an important index for judging the performance of the thermoelectric material, is2T/κL+κeWherein S, sigma, T, kappaLAnd kappaeRespectively representing the seebeck coefficient, electrical conductivity, absolute temperature, lattice thermal conductivity and carrier thermal conductivity. Therefore, it is often difficult to improve the thermoelectric figure of merit of a material by changing the electrical conductivity or seebeck coefficient, since both are difficult to balance. However, the inventor finds that the introduction of the divalent copper ions introduces electrons, reduces the carrier concentration of the material, namely reduces the electrical conductivity of the material, thereby improving the Seebeck coefficient of the material, and more importantly, the thermoelectric figure of merit of the material is obviously improved after the two are combined.
In conclusion, the copper-based chalcogenide thermoelectric composite material provided by the basic scheme has good stability and better thermoelectric performance.
In order to achieve the above object, the present invention provides a second basic scheme, a method for preparing a copper-based chalcogenide thermoelectric composite material, comprising the following steps in sequence:
step 3, adding Cu1.8S-Cu2(OH)2CO3Sintering the mixed powder by adopting a spark plasma sintering method to obtain Cu with a porous structure1.8The S-CuO block thermoelectric composite material is prepared by sintering at 300-500 ℃ for 5-30 min under 10-50 Mpa.
Has the advantages that: the material prepared by the method is found to comprise main phase Cu through scanning electron microscope and X-ray diffraction test1.8S and a second phase CuO prove that after the method is adopted, the addition of the basic copper carbonate does not influence the phase structure of the matrix material. In addition, a large number of pores are found in the material, and the research shows that the introduced basic copper carbonate is decomposed into H with volatility in the sintering process2O and CO2Thereafter, CuO is formed in situ on the surface of the base material, and is left as an impurity precipitate phase. These pores can significantly reduce Cu1.8The thermal conductivity of the S material.
The scheme adopts an indirect mode to introduce a stable oxide second phase and also is the same element with different valence states, and the finally formed composite material has high stability and good thermoelectric property.
Particularly, the inventors have searched and studied the basic copper carbonate and Cu1.8The mass ratio of S is controlled within the range of 0.5-10%, a good effect can be achieved, the amount is too small, the effect of a pore-forming agent is difficult to achieve, and the number of formed pores is too low; too large an amount will in turn affect the mechanical strength of the material and may have a negative impact on the thermoelectric properties of the material. The proportion ensures that the finally prepared material has high stability and good thermoelectric property.
In addition, the scheme adopts a solid-phase sintering method to synthesize Cu1.8S material of Cu1.8S has large grains, which is beneficial to maintaining good thermal conductivity of the material. In the step 1, the quartz tube is used as a sintering container, so that the quartz tube can resist high temperature, and can be softened at high temperature, the tube is convenient to seal, and the vacuum environment of solid-phase sintering is ensured; and the sintering method and the process parameters in the step 3 are adopted, so that the shape of the powder can be maintained, and the finally sintered material not only has better stability, but also has better thermoelectric performance.
In conclusion, the copper-based chalcogenide thermoelectric composite material with high stability and high thermoelectric performance can be prepared only by the mutual cooperation of the steps and the process parameters.
Further, during solid phase sintering in the step 1, firstly, heating to 300-500 ℃ from room temperature for the first time, and then, preserving heat for 3-8 hours; continuing to heat to 900-1100 ℃ for the second time, and then preserving the heat for 5-8 hours; finally cooling to room temperature along with the furnace to obtain Cu1.8And S, ingot casting.
Has the advantages that: the scheme is favorable for Cu1.8The synthesis of S does not contain impurities, has large crystal grains, is beneficial to improving the thermal conductivity of the material, and finally obtains the thermoelectric composite material with excellent thermoelectric performance.
Further, the first temperature rise rate is controlled to be 45-80 ℃/h, and the second temperature rise rate is controlled to be 70-100 ℃/h.
Has the advantages that: cu thus synthesized1.8The S material has better performance.
Further, the cooling rate of the step 1 along with the furnace is controlled to be 45-55 ℃/h.
Has the advantages that: cu thus synthesized1.8The S material has better performance.
Further, in the step 2, basic copper carbonate and Cu are used1.8The mass ratio of S is 1%.
Has the advantages that: according to the research, research and test of the inventor, the mass ratio is controlled to be 1:100, and the stability, the thermoelectric property and the like are comprehensively optimal.
Further, the protective atmosphere in the step 2 is H with the mass fraction of 5%2And 95% by mass of Ar.
Has the advantages that: the combination of properties of the final material is facilitated by such a collocation.
Further, the ball milling speed of the step 2 is 500-800 rpm, and the ball milling time is 10 min-1 h.
Has the advantages that: a large number of experiments prove that the Cu is obtained at the rotating speed and the ball milling time1.8The S cast ingot can be completely crushed and uniformly mixed with the basic copper carbonate, so that the comprehensive performance of the final material is ensured.
Further, the ball milled in the step 2 is a ball with the diameter of 6mm or 15mm, and the weight ratio of the ball milled to the material is 20-50: 1.
Has the advantages that: it is proved by a large number of tests that, at this weight ratio, Cu1.8The S cast ingot can be completely crushed and uniformly mixed with the basic copper carbonate, so that the comprehensive performance of the final material is ensured.
Furthermore, the purity of the Cu elemental powder and the S elemental powder is more than 99.95 percent, and the basic copper carbonate is of analytical grade.
Has the advantages that: the scheme can reduce the generation of impure phases and ensure the comprehensive performance of the final material.
Drawings
FIG. 1 is a scanning electron microscope (FESEM) image of example 1 of the present invention;
FIG. 2 is a comparison XRD of example 1 of the present invention and a comparative example;
FIG. 3 is a graph of conductivity versus temperature for example 1 of the present invention and a comparative example;
FIG. 4 is a graph showing the Seebeck coefficient with temperature for example 1 of the present invention and a comparative example;
FIG. 5 is a graph of power factor versus temperature for example 1 of the present invention and a comparative example;
FIG. 6 is a graph of thermal conductivity as a function of temperature for example 1 of the present invention and a comparative example;
FIG. 7 is a graph of thermoelectric figure of merit (ZT value) as a function of temperature for example 1 of the present invention and a comparative example;
FIG. 8 is a ZT value obtained by repeating three tests of example 1 of the present invention and comparative example.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1:
the invention relates to a copper-based chalcogenide thermoelectric composite material, the chemical general formula of which is Cu1.8S-CuO, the material comprising a main phase Cu1.8S and a second phase CuO uniformly distributed in the main phase Cu1.8S is carried out; also comprises air holes which are uniformly distributed in the main phase Cu1.8And (S) in the step (A).
The preparation method of the material sequentially comprises the following steps:
Wherein, the ball-milled sphere is a sphere with a diameter of 6mm or 15mm (in this embodiment, a sphere with a diameter of 6mm is selected), and the weight ratio of the ball-milled sphere to the material is 20-50: 1 (in this embodiment, 20: 1). The rotation speed during ball milling is 500-800 rpm (800 rpm in this embodiment), the ball milling time is 10 min-1 h (10 min in this embodiment), according to Cu1.8Quality of S and basic copper carbonate, basic copper carbonate and Cu in this example1.8The mass ratio of S is 1: 100.
Step 3, adopting a discharge plasma sintering method to treat the Cu1.8S-Cu2(OH)2CO3Sintering the mixed powder by first sintering Cu1.8S-Cu2(OH)2CO3The mixed powder is poured into a graphite mold with the diameter of 20mm, and the temperature is 300-500 ℃ and 10 ℃ -Sintering at 50MPa for 5-30 min, wherein the specific sintering temperature is 500 ℃, the sintering pressure is 50MPa, and the sintering time is 5min, and finally the Cu with the porous structure is formed1.8An S-CuO bulk thermoelectric composite material.
Examples 2-5 differ from example 1 only in the quality of the basic copper carbonate added in step 2, as specified in table 1.
TABLE 1
Now existing Cu1.8S thermoelectric materials as comparative examples comparative experiments were conducted with examples. Existing Cu1.8The S thermoelectric material was prepared according to the method of example 1, except that no basic copper carbonate was added in step 2.
1. FESEM (field emission scanning Electron microscope) characterization
Scanning electron microscopy was used to test the Cu produced in the examples1.8Microscopic morphology observation is carried out on the S-CuO bulk thermoelectric composite material, taking example 1 as an example, and an electron microscope image of the S-CuO bulk thermoelectric composite material is shown in FIG. 1. Fig. 1 shows that pores are generated and uniformly distributed after basic copper carbonate is added.
2. XRD (X-ray diffraction) characterization
Cu obtained in example was separately subjected to X-ray diffractometry1.8The S-CuO bulk thermoelectric composite material and the thermoelectric material provided in the comparative example were tested, and the results of the tests are shown in fig. 2, taking example 1 and the comparative example as examples. FIG. 2 shows that Cu can be synthesized by the method of example1.8The S is a polycrystalline bulk material of a main phase, and the existence of second-phase CuO is detected, which indicates that basic copper carbonate is actually decomposed into CuO in the sintering process and distributed in the form of second phase in Cu1.8S matrix material.
3. Thermoelectric property characterization
The performance of thermoelectric materials is characterized by a dimensionless thermoelectric figure of merit ZT, where ZT is σ S2T/κ, wherein σ S2Represents the power factor (sigma is the conductivity, S is the Seebeck coefficient), and T is the absolute temperatureAnd κ is the thermal conductivity (the sum of the lattice thermal conductivity and the carrier thermal conductivity).
3.1 Electrical Transmission Performance
Taking example 1 as an example, the thermoelectric materials provided in example 1 and comparative example were cut into 3 × 10mm rectangular blocks for the electrical conductivity, seebeck coefficient, and power factor tests using the resistivity and seebeck coefficient test system.
The results of the conductivity test are shown in fig. 3, and fig. 3 shows that the conductivity of the material is reduced to some extent after the CuO is introduced.
The seebeck coefficient test results are shown in fig. 4, and fig. 4 shows that the seebeck coefficient of the material is increased after CuO is introduced.
The power factor test results are shown in fig. 5, and fig. 5 shows that the power factor of the material is increased after the CuO is introduced.
3.2 thermal conductivity
The bulk thermoelectric materials prepared in examples and the thermoelectric materials provided in comparative examples were cut into wafers of phi 6mm for measuring thermal conductivity, and tested using a laser thermal conductivity meter. The test results are shown in fig. 6, taking example 1 and comparative example as examples. Fig. 6 shows that the thermal conductivity of the material decreases after CuO is introduced.
3.3ZT value
According to the above formula ZT ═ σ S2The ZT values obtained by the T/κ calculation are shown in FIG. 7 for example 1 and comparative example, respectively. Fig. 7 shows that the thermoelectric figure of merit ZT of the material is significantly improved after CuO is introduced.
The ZT values at 773K for the thermoelectric materials prepared in examples 1 to 5 and the thermoelectric material provided in the comparative example are shown in table 2.
TABLE 2
4. Characterization of stability
The above tests were repeated three times for the bulk thermoelectric materials prepared in examples and comparative examples, and the stability of the materials was judged by ZT values of the three tests. Taking example 1 and comparative example as examples, the test results are shown in fig. 8, and fig. 8 shows that the ZT value of the same sample is not large after multiple times of continuous tests at high temperature, while the ZT value of the comparative example is large after multiple times of tests, which shows that the stability of the material is better after the second phase CuO is introduced.
In conclusion, the copper-based chalcogenide thermoelectric composite material provided by the invention has higher service stability and good thermoelectric performance. Wherein, when Cu is in step 22(OH)2CO3And Cu1.8When the mass ratio of S is 1%, the thermoelectric figure of merit is highest, and the comprehensive performance is best.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention, and these changes and modifications should not be construed as affecting the performance of the invention and its practical application.
Claims (10)
1. A copper-based chalcogenide thermoelectric composite material, characterized by: the chemical general formula of the material is Cu1.8S-CuO, the material comprising a main phase Cu1.8S and a second phase CuO uniformly distributed in the main phase Cu1.8S is carried out; also comprises air holes which are uniformly distributed in the main phase Cu1.8And (S) in the step (A).
2. The method for preparing a copper-based chalcogenide thermoelectric composite material according to claim 1, wherein: the method sequentially comprises the following steps:
step 1, pouring Cu elemental powder and S elemental powder into a quartz tube according to the molar ratio of 1.8:1, and performing solid phase sintering in a vacuum environment to obtain Cu1.8S, casting ingots;
step 2, adding Cu1.8Putting the S cast ingot and the basic copper carbonate into a ball mill, and carrying out ball milling mixing under protective atmosphere to obtain Cu1.8S-Cu2(OH)2CO3Mixing the powder of basic copper carbonate and Cu1.8The mass ratio of S is 0.5-10%;
step 3, adding Cu1.8S-Cu2(OH)2CO3Sintering the mixed powder by adopting a spark plasma sintering method to obtain Cu with a porous structure1.8The S-CuO block thermoelectric composite material is prepared by sintering at 300-500 ℃ for 5-30 min under 10-50 Mpa.
3. The method for preparing a copper-based chalcogenide thermoelectric composite material according to claim 2, wherein: during solid phase sintering in the step 1, firstly, the temperature is increased to 300-500 ℃ from room temperature for the first time, and then the temperature is kept for 3-8 hours; continuing to heat to 900-1100 ℃ for the second time, and then preserving the heat for 5-8 hours; finally cooling to room temperature along with the furnace to obtain Cu1.8And S, ingot casting.
4. The method for preparing a copper-based chalcogenide thermoelectric composite material according to claim 3, wherein: in the step 1, the first temperature rise rate is controlled to be 45-80 ℃/h, and the second temperature rise rate is controlled to be 70-100 ℃/h.
5. The method for preparing a copper-based chalcogenide thermoelectric composite material according to claim 3, wherein: and the cooling rate of the step 1 along with the furnace is controlled to be 45-55 ℃/h.
6. The method for preparing a copper-based chalcogenide thermoelectric composite material according to claim 2, wherein: in the step 2, basic copper carbonate and Cu1.8The mass ratio of S is 1%.
7. The method for producing a copper-based chalcogenide thermoelectric composite material according to any one of claims 2 to 6, wherein: the protective atmosphere in the step 2 is H with the mass fraction of 5%2And 95% by mass of Ar.
8. The method for producing a copper-based chalcogenide thermoelectric composite material according to any one of claims 2 to 6, wherein: the ball milling speed of the step 2 is 500-800 rpm, and the ball milling time is 10 min-1 h.
9. The method for producing a copper-based chalcogenide thermoelectric composite material according to any one of claims 2 to 6, wherein: the ball milled in the step 2 is a ball with the diameter of 6mm or 15mm, and the weight ratio of the ball to the material during ball milling is 20-50: 1.
10. The method for producing a copper-based chalcogenide thermoelectric composite material according to any one of claims 2 to 6, wherein: the purities of the Cu elemental powder and the S elemental powder are more than 99.95 percent, and the basic copper carbonate is of analytical grade.
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