CN113488578A - Low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency and preparation method thereof - Google Patents
Low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency and a preparation method thereof3The composition of the SbBi/Fe/Ni p-type thermoelectric element is Ni/Sb/CdSb/Sb/Ni. The thermoelectric material selected by the thermoelectric device belongs to antimonide, and the composition elements of the thermoelectric device have the characteristics of high abundance and low price, and simultaneously have commercial Bi2Te3The base material may have comparable thermoelectric properties. And the thermoelectric device is comparable to conventional commercial Bi2Te3The base thermoelectric device has the characteristics of high conversion efficiency, wide application temperature range, high power-price ratio and the like, and is the highest value of the thermoelectric efficiency of the low-grade waste heat recovery temperature range at present. In addition, the thermoelectric module has high thermal stability and heatThe electric element has high processability and is a necessary condition for realizing large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of thermoelectric materials, and relates to a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency and a preparation method thereof.
Background
The modern industrial energy consumption is serious, and more than 60 percent of the energy consumption is consumed in various factoriesIs dissipated as waste heat. High-grade high-temperature waste heat is easy to reuse in industry, but low-temperature waste heat accounting for more than 50% of the total waste heat cannot be recycled by using a traditional method due to the characteristics of low quality, low energy density and the like. Thermoelectric power generation, as a clean and silent energy conversion technology, can directly convert waste heat into useful electric energy, reduce the consumption of fossil fuels and release the environmental crisis caused by the consumption of fossil fuels. The thermoelectric conversion efficiency is usually determined by a dimensionless thermoelectric figure of merit zT, zT ═ S2T/ρ κ, (T is absolute temperature, S is Zeebeck coefficient, ρ is resistivity, κ is thermal conductivity). Since thermoelectric figure of merit is closely related to temperature, achieving high thermoelectric performance at low temperatures is extremely challenging.
Although the development history in the field of thermoelectricity is long, the thermoelectric material used in the low-temperature waste heat temperature region (<600K) still only uses bismuth telluride alloy. Due to the small forbidden band width of bismuth telluride, severe bipolar effect can occur at the temperature of more than 450K, so that the thermoelectric performance is reduced, and on the other hand, due to the poor self-compatibility, the finally obtained typical conversion efficiency is usually below 7%. More importantly, the important component element tellurium of the bismuth telluride alloy has low earth reserves and low annual output, so that the large-scale use of bismuth telluride devices is limited. Due to the high material cost, the power price ratio of the bismuth telluride device is usually below 20W/$, which is only the case of considering the material cost, so that the development of thermoelectric devices with higher efficiency and richer and cheaper element compositions for low-grade waste heat recovery is a continuous research direction in the thermoelectric field.
Disclosure of Invention
The invention aims to provide a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency, which comprises an insulating heat-conducting ceramic plate and n-p thermoelectric units which are fixed on the insulating heat-conducting ceramic plate and are connected in series by a metal diversion layer, wherein the n-p thermoelectric units are connected with each other through a heat conduction layerThe n-p thermoelectric unit consists of an n-type thermoelectric element and a p-type thermoelectric element which are connected in series by adopting metal current conducting layers, wherein the n-type thermoelectric element is formed by Ni/Fe/Mg3SbBi/Fe/Ni (Mg herein)3SbBi represents only such a material, and does not mean that the composition of the thermoelectric semiconductor material is Mg3SbBi) with Mg3An SbBi material as a thermoelectric semiconductor material, Fe as a diffusion barrier layer, and Ni as an electrode; the p-type thermoelectric element has a composition of Ni/Sb/CdSb/Sb/Ni (CdSb represents only a material such as C and does not mean that the composition of the thermoelectric semiconductor material is CdSb), and uses a CdSb-based material as the thermoelectric semiconductor material, Sb as the diffusion barrier, and Ni as the electrode.
Further, said Mg3The composition of SbBi material is Mg3.1Y0.01SbBi, the composition of the CdSb material is Cd0.99Ag0.01And (5) Sb. The composition has higher thermoelectric performance, and the thermoelectric material can realize high thermoelectric figure of merit (zT) and higher 300-600K average zT.
Thermoelectric semiconductor material Cd used in the invention0.99Ag0.01Sb and Mg3.1Y0.01The SbBi has high processability and rich reserves of constituent elements, and is suitable for large-scale use. The Sb and Fe are used as diffusion shielding layers between the electrode materials Ni and the thermoelectric material, so that the diffusion of the electrode into the thermoelectric material can be effectively prevented, and the low interfacial resistivity is also an important factor for realizing high output power and thermoelectric conversion efficiency.
Further, the metal current carrier is pure metal such as Ni, Cu, Ag, Fe, Co, Mo, or an alloy thereof, and preferably is a copper sheet or a silver sheet.
Further, the insulating and heat conducting ceramic sheet may be aluminum oxide or aluminum nitride.
Further, the thickness of the metal flow guide body is 0.1-0.5 mm; the thickness of the insulating heat-conducting ceramic sheet is 0.1-1 mm.
Furthermore, in the n-type thermoelectric element and the p-type thermoelectric element, the thickness of the electrode Ni is 0.5 to 1.0mm, the thickness of the diffusion shielding layer Sb or Fe is 0.05 to 0.3mm, and the thermoelectric semiconductor material Mg3SbBi systemThe thickness of the material or the CdSb material is 2-6 mm.
Further, the thermoelectric element has a size of (1-3) mm X (5-7) mm, preferably 1.5mm X6 mm.
The invention discovers that antimonide (CdSb, Mg) through research3Sb2) Has excellent thermoelectric performance in a low-temperature region and an average zT in a 300-600K temperature region>1, the earth reserves of the components are abundant, the price is low, and the thermoelectric material system is a potential thermoelectric material system for replacing a bismuth telluride device. Thus, p-type Cd has been studied from the material to the device level0.99Ag0.1Sb and n-Mg3.1Y0.01Material properties and device properties of SbBi. The thermoelectric elements (p-type Ni/Sb/CdSb/Sb/Ni and n-type Ni/Fe/Mg) are successfully prepared by one-step hot-press forming3SbBi/Fe/Ni), the sandwich composition successfully prevents the diffusion between the material and the electrode, and has lower interfacial resistivity, thereby laying a foundation for realizing high conversion efficiency. Finally, the temperature at the hot end in 8 pairs of antimonide modules<The conversion efficiency of 10% is obtained at 600K, and the power price ratio under the temperature difference reaches 360W/$, so that the power price ratio of the traditional bismuth telluride device is more than 20 times. The antimonide thermoelectric module disclosed by the invention has great potential, has the characteristics of economy, sustainability, high efficiency and the like, and is a substitute for low-grade waste heat recovery of the traditional bismuth telluride device.
The second technical scheme of the invention provides a preparation method of a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency, which comprises the following steps:
(1) and (3) sample loading of a hot-pressing mold:
weighing electrode powder, diffusion shielding layer powder and thermoelectric semiconductor material powder, respectively loading the electrode powder, the diffusion shielding layer powder and the thermoelectric semiconductor material powder into a graphite die according to the composition layers of an n-type thermoelectric element and a p-type thermoelectric element, and compacting (namely, the upper side and the lower side of the thermoelectric semiconductor material respectively contain a layer of diffusion shielding layer powder and a layer of electrode powder in sequence);
(2) one-step hot pressing sample preparation:
placing the graphite mold after sample loading in a vacuum hot-pressing device, carrying out one-step hot pressing, cutting and sample preparation to obtain an n-type thermoelectric element and a p-type thermoelectric element with target sizes, and connecting the n-type thermoelectric element and the p-type thermoelectric element in series to form an n-p thermoelectric unit;
(3) module assembling:
connecting the n-p thermoelectric units through the metal guide layer, and fixing the n-p thermoelectric units on the insulating heat-conducting ceramic plate in sequence, namely assembling to obtain a target product.
Further, in the step (1), the particle size of the powder used may be selected to be 200 mesh.
Further, in the step (2), the hot-pressing process conditions of the n-type thermoelectric element are specifically as follows: raising the temperature to 550-650 ℃ at a rate of 100-150 ℃ per minute under a pressure of 80-100MPa, and preserving the temperature for 60-90 minutes. Optionally, the temperature is raised to 550 ℃ at a rate of 150 ℃ per minute under a pressure of 90MPa and held for 90 minutes.
Further, in the step (2), the hot-pressing process conditions of the p-type thermoelectric element are specifically as follows: heating to 350-400 ℃ at the rate of 100-150 ℃ per minute under the pressure of 50-80MPa, and keeping the temperature for 60-90 minutes. Optionally, the temperature is raised to 400 ℃ at a rate of 150 ℃ per minute under a pressure of 60MPa and held for 90 minutes.
Further, in the step (2), the absolute vacuum degree in the vacuum hot-pressing equipment is not more than 10-1Pa。
Further, in the step (3), the process conditions for cutting and sample preparation are as follows: cutting a cylindrical sample by using a diamond cutting line with the line diameter of 0.35-0.45mm, cutting at the speed of 200-260 revolutions per minute, adjusting the lifting speed of a sample table to be 0.1-0.5 mm/min, cooling by using cutting oil, and cutting the cylindrical sample. Optionally, a diamond cutting line with the line diameter of 0.35mm is used for cutting the cylindrical sample, the rotating speed of linear cutting is 260r/min, and the rising speed of the sample table is 0.1 mm/min.
Furthermore, the n-type thermoelectric element or the p-type thermoelectric element is welded with the metal flow guiding layer (i.e. the flow guiding sheet) by using soldering tin at a low temperature end, and is welded with the metal flow guiding layer by using Sn-Sb-Pb (i.e. ternary alloy representing Sn, Sb and Pb, and only adopting products which are conventionally sold in the field) at a high temperature end.
The invention selects the temperature zone of 300-600K with the average zT>Antimonide (p-type Cd) of 10.99Ag0.01Sb, n type Mg3.1Y0.01SbBi) is a thermoelectric material, and is a choice which has thermoelectric properties comparable to those of the traditional bismuth telluride matrix at low temperature. The p-type thermoelectric element was a cylindrical thermoelectric element obtained by using Sb as a diffusion barrier layer, Ni as an electrode, the n-type thermoelectric element was Fe as a diffusion barrier layer, and Ni as an electrode, and the one-step hot pressing method was used. The n-p thermoelectric element has good electrical and thermal stability and low interfacial resistivity by using the Sb and Fe as diffusion shielding layers through the sandwich structure, and can ensure that high output power and conversion efficiency are obtained by using the copper sheet as a flow guide body and the aluminum oxide ceramic sheet as an insulating and heat conducting effect. The structure of the design enables the antimonide module to achieve 10% conversion efficiency and 12kW/m when the heat source is 600K2The power density of (a) is the optimal value of the current low-grade waste heat temperature region. Meanwhile, the composition elements of the antimonide module have the characteristics of rich earth reserves, low price, high annual output and the like, so that the material cost is extremely low, the power-price ratio reaches 360W/$, and is 20 times that of the current commercial bismuth telluride module. The polycrystalline antimonide has isotropy in thermoelectric property and better processability, and brings convenience for realizing large-scale application of industrial production.
Compared with the prior art, the invention has the following advantages:
(1) the existing low-grade waste heat recovery thermoelectric device mainly comprises a bismuth telluride material, and the bismuth telluride has small modern width and is at temperature>The bipolar effect at 450K is serious, so that the thermoelectric performance is deteriorated, the power factor is reduced along with the increase of temperature, and the self-compatibility is poor. Although the research history of the bismuth telluride module is long and the bismuth telluride module has a mature process in the aspects of electrode preparation and the like, the thermoelectric conversion efficiency of low-grade waste heat recovery is lower than 7 percent due to the defect of the material performance. The invention selects antimonide as thermoelectric material of the module, the average power factor and the average zT of the module in a temperature zone of 300-600K are comparable to those of bismuth telluride material, the self-compatibility is good, the conversion efficiency is up to 10 percent when the heat source is 600K and the cold end is 280K, and the power density reaches 12kW/m2Is the optimal value realized by the temperature zone at present. In addition, for p-type thermoelectric elements, through a great deal of experimental study,the Sb is determined to have better effect when being used as a diffusion shielding layer, and the interface structures related by the invention are reported for the first time.
(2) The cost of the existing low-grade waste heat recovery thermoelectric device material is too high. The bismuth telluride material has the important constituent element of tellurium, the earth reserves are low, the annual output is also low, the thermoelectric property anisotropy is strong, the raw material processing waste is more, the batch production and the large-scale application of the bismuth telluride module are seriously limited, the power factor is reduced along with the temperature rise, and in fact, the power price ratio of the bismuth telluride module is only 20W/$. The n-p thermoelectric materials used in the present invention are all antimonides (p-type Cd)0.99Ag0.01Sb, n type Mg3.1Y0.01SbBi), the earth reserves of the constituent elements are rich, the annual output is high, meanwhile, the thermoelectric performance of the polycrystalline antimonide has isotropy, the processing is simpler, the average power factor in a low-grade waste heat temperature region is comparable to that of a bismuth telluride material, and the power cost ratio reaches 360W/$whenthe heat source is 600K, which is 20 times that of the bismuth telluride material. The advantages from materials to devices to cost are achieved, so that the antimonide module can replace the bismuth telluride module, and low-grade waste heat recovery is realized on a large scale.
Drawings
FIG. 1 is an XRD diffraction pattern and SEM and EDS scan pattern of an n-p thermoelectric material;
FIG. 2 is a graph of Seebeck coefficient (S), resistivity (ρ), thermal conductivity (κ), and thermoelectric figure of merit (zT) versus temperature for an n-p thermoelectric material;
FIG. 3 is a line scan of the resistance and SEM images and EDS scan and line scan of the thermoelectric elements of a thermoelectric module at an interface;
FIG. 4 is a scan of the interfacial resistivity of different interface structures of a p-type thermoelectric element;
the relationship among the load voltage (V), the output power (P), the conversion efficiency (eta) and the loop current (I) of the thermoelectric module under different temperature differences of 5;
FIG. 6 is the internal resistance (R) of the thermoelectric modulein) And open circuit voltage (V)oc) A relationship diagram with the temperature difference opinion;
FIG. 7 shows the power density (P) at different temperature differencesd) And loop current(I) The relationship between;
FIG. 8 shows life tests of a thermoelectric module at a hot side temperature of 555K, a cold side temperature of 308K for load voltage (V), output power (P), heat flow (Q), and conversion efficiency (η);
FIG. 9 is a graph of the cost performance (W/$) of a thermoelectric module versus different heat source temperatures;
FIG. 10 is a comparative view of various aspects of the raw materials of the elements.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, a p-type thermoelectric semiconductor material Cd was used0.99Ag0.01The preparation process of the Sb and p-type thermoelectric element is as follows:
firstly, elementary substance element raw materials Cd, Ag and Sb with the purity of more than 99.99 percent are adopted according to Cd0.99Ag0.01Weighing the Sb alloy according to the stoichiometric ratio, mixing, and carrying out vacuum packaging in a quartz tube;
and secondly, suspending the quartz tube containing the raw materials in a vertical high-temperature furnace, slowly heating to 600-800 ℃ at the rate of 150-200 ℃ per hour, preserving heat for 5-8 hours, then rapidly quenching and cooling to obtain a first ingot (namely a molten ingot), slowly heating to 800 ℃ at the rate of 200 ℃ per hour, and preserving heat for 8 hours at 800 ℃.
And (III) carrying out heat treatment on the first ingot after the high-temperature melting quenching obtained in the step (II), slowly heating to 350-450 ℃ at the speed of 150-200 ℃ per hour, preserving the heat for 2-4 days, then rapidly quenching and cooling to obtain a second ingot (namely an annealing ingot), wherein the temperature is slowly heated to 427 ℃ at the speed of 200 ℃ per hour, and preserving the heat for 2 days.
And (IV) grinding the annealed ingot obtained in the step (III) into powder to obtain the required p-type thermoelectric semiconductor material.
Thermoelectric semiconductor material Mg3.1Y0.01Preparation of SbBiThe process is as follows: firstly, elementary substance element raw materials Mg, Y, Sb and Bi with the purity of more than 99.99 percent are used as Mg3.1Y0.01Weighing the stoichiometric ratio in the SbBi alloy for proportioning, and vacuum packaging in a quartz tube;
secondly, suspending the quartz tube in which the raw materials are placed in a vertical high-temperature furnace, slowly heating to 1000-1100 ℃ at the rate of 150-200 ℃ per hour, preserving the heat for 5-8 hours, and then rapidly quenching and cooling to obtain a first ingot (namely a molten ingot); here, a slow temperature increase to 1050 ℃ at a rate of 200 ℃ per hour was chosen and the incubation at 1050 ℃ was carried out for 8 hours.
Thirdly, carrying out heat treatment on the first ingot after the high-temperature melting quenching obtained in the second step, slowly heating to 600-700 ℃ at the speed of 150-200 ℃ per hour, preserving the heat for 2-4 days, and then rapidly quenching and cooling to obtain a second ingot (namely an annealed ingot); here, the temperature was slowly raised to 650 ℃ at a rate of 200 ℃ per hour and held for 2 days.
And (IV) grinding the annealed ingot obtained in the step (III) into powder to obtain the required n-type thermoelectric material.
In addition, load voltage (V), output power (P), heat flow (Q)out) Conversion efficiency (. eta.), Power Density (P)d) Loop current (I), internal resistance (R)in) Interfacial contact resistivity (p)c) And the like can be obtained by using a measurement method which is conventional in the field.
And the rest of the raw materials or treatment techniques which are not specifically described indicate that the raw materials or the treatment techniques are all conventional commercial raw materials or conventional treatment techniques in the field.
Example 1:
a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency is composed of n-p thermoelectric elements, and the n-type thermoelectric elements are Mg3.1Y0.01SbBi as a thermoelectric semiconductor material, the composition of which is expressed as Ni/Fe/Mg3SbBi/Fe/Ni, p-type thermoelectric element composed of Cd0.99Ag0.01Sb is taken as a thermoelectric semiconductor material, the composition of the thermoelectric semiconductor material is recorded as Ni/Sb/CdSb/Sb/Ni, wherein Fe and Sb are respectively Mg3.1Y0.01SbBi and Cd0.99Ag0.01Diffusion barrier layer of Sb, Ni as electrode, hNi(i.e. theThickness of electrode Ni) ═ 0.5 to 1.5mm (preferably 0.9mm in this example), hSb,Fe(i.e., the thickness of the diffusion barrier layer Sb, Fe) ═ 0.05 to 0.3mm (preferably 0.1mm in this embodiment), hCdSb,Mg3SbBi(i.e. the thickness of the thermoelectric semiconductor material) is 3-5mm (preferably 4mm in this embodiment), the n-p thermoelectric elements are connected in series by a metal current guiding layer, and the thermoelectric pair is fixed on the insulating ceramic sheet by ceramic packaging technology.
The preparation method of the thermoelectric module comprises the following steps:
(1) weighing Ni powder, Sb and Fe powder and thermoelectric material powder according to the mass calculated by the volume multiplied by the density, wherein the required powder mass is as follows: ni mass 0.67g (0.9mm), Sb diffusion barrier layer 0.075g (0.1mm), Fe diffusion barrier layer 0.088g (0.1mm), thermoelectric material CdSb mass 3.07g (4mm), thermoelectric material Mg3The mass of SbBi is 2.22g (4mm), and the SbBi is sequentially loaded into a graphite die and compacted;
(2) carrying out one-step hot pressing sample preparation on the graphite mold loaded in the step (1) by using vacuum hot pressing equipment, wherein Ni/Fe/Mg3The hot-pressing process conditions of the SbBi/Fe/Ni thermoelectric element are as follows: heating to 550 ℃ at the rate of 150 ℃ per minute under the pressure of 90MPa, and preserving the temperature for 90 minutes; under the hot-pressing process condition of the Ni/Sb/CdSb/Sb/Ni thermoelectric element: the temperature was raised to 400 ℃ at a rate of 150 ℃ per minute under a pressure of 60MPa and held for 90 minutes. The pressure is 40MPa, the heating rate is 150 ℃ to 450 ℃, and the temperature is kept for 90 minutes.
A cylindrical sample with a diameter of 12mm and a thickness of 6mm was finally obtained.
(3) Cutting the cylindrical sample obtained in the step (2) of hot pressing sample preparation by using a wire cutting machine, wherein the process conditions for cutting and sample preparation are as follows: cutting a cylindrical sample by using a diamond cutting line with the line diameter of 0.35mm, wherein the rotating speed of the linear cutting is 260r/min, the rising speed of a sample table is 0.1mm/min, and the temperature is reduced by using cutting oil to finally obtain the cylindrical sample with the size of 1.5 multiplied by 6mm3The thermoelectric elements are respectively a p-type thermoelectric element and an n-type thermoelectric element, and are connected in series to form an n-p thermoelectric unit.
(4) And (3) welding the n-p thermoelectric unit obtained by wire cutting in the step (3) with a flow deflector at a low-temperature end by using soldering tin, welding the high-temperature end with the flow deflector by using Sn-Sb-Pb, wherein the flow deflector is a copper sheet and has the thickness of 0.2mm, and then connecting the obtained n-p thermoelectric pair (namely the n-p thermoelectric unit) with a ceramic sheet by using a ceramic packaging technology, wherein the ceramic sheet is an aluminum oxide ceramic sheet and has the thickness of 0.2 mm.
Fig. 1 shows the microstructure characterization of the thermoelectric material obtained by the one-step hot press molding method, and an XRD diffraction pattern, an SEM picture and an EDS scan show that the thermoelectric material obtained by the preparation method is a single phase, which is a prerequisite for ensuring that the material has high thermoelectric performance. The temperature-dependent performance curve of the selected n-p thermoelectric material is shown in FIG. 2, which shows that the thermoelectric performance of the material obtained by the preparation method can be comparable to that reported in the literature. As shown in FIG. 3, the p-type thermoelectric element obtained by the four-probe method had an interface contact resistance of about 1.35 m.OMEGA.and an interface contact resistivity of about 30. mu. OMEGA.cm2The n-type thermoelectric element has an interface contact resistance of about 0.55 m.OMEGA.and an interface contact resistivity of about 12 μ OMEGA.cm2The SEM pictures show that the interfaces of the n-p thermoelectric elements have obvious interfaces, and further EDS maps also prove that no obvious diffusion phenomenon exists between the thermoelectric materials and the electrodes. FIG. 4 is a study of the interfacial resistivity of different interface designs of p-thermoelectric elements, and the results show that the interface Ni/Sb/CdSb/Sb/Ni is designed to have the lowest interfacial resistivity, so that the influence of the interfacial resistance on the output power and the conversion efficiency of the device can be reduced;
FIG. 5 is a performance test of a thermoelectric module, revealing the relationship between load voltage (V), output power (P), conversion efficiency (η) and loop current (I) for an antimonide thermoelectric module. As shown in fig. 5a, c, the load voltage gradually decreases with the increase of the loop current, mainly because the increase of the loop current is due to the decrease of the resistance of the load resistor under the condition of a certain temperature difference, so the load voltage decreases, and meanwhile, the voltage value increases with the increase of the temperature difference; fig. 5a and c show the relationship between the output power and the loop current, different from the load voltage, the output power will reach a peak value with the increase of the loop current, and then decrease, the peak value generally appears under the condition that the load resistance is equal to the module internal resistance, and meanwhile, the larger the temperature difference, the larger the output power; under the condition of constant temperature difference, the thermoelectric conversion efficiency of the single-leg device is firstly increased and reduced along with the increase of current, as shown in fig. 5b and d, but the peak value does not occur in the condition that the internal resistance and the external resistance are equal due to joule heat and the Peltier effect.
The internal resistance and open circuit voltage of the thermoelectric module at different temperature differences are shown in fig. 6, the internal resistance increases with increasing temperature difference, mainly because the average resistivity of the thermoelectric material increases with increasing temperature difference, and the internal resistance of the module is greater than the resistance of the constituent materials themselves, mainly because of the interface resistance during assembly. The open circuit voltage is compared with the Seebeck coefficient of the material and the voltage value calculated by the temperature difference, and the module structure relates to less heat loss.
The relationship between the power density of the thermoelectric module and the loop current under different temperature differences is shown in FIG. 7, the output power density of the module increases with the increase of the temperature difference, and when the heat source is 600K, the output power density can reach 12kW/m2. In addition, the thermoelectric module has good thermal stability, and the output power and the conversion efficiency of the thermoelectric module are basically unchanged when the thermal insulation test is performed at the hot end temperature of 555K and the cold end temperature of 308K, which indicates that the device has a long service life, as shown in fig. 8.
Fig. 10 shows that the thermoelectric material selected for the working thermoelectric module has advantages over the commercial bismuth telluride material in terms of element abundance, annual output, unit price, etc., and the antimonide thermoelectric module has higher conversion efficiency and lower manufacturing cost under the same temperature difference.
Further comparing the cost performance of the two thermoelectric modules, as shown in fig. 9, the power cost ratio of antimonide is as high as 360W/$, which is more than 20 times that of the commercial bismuth telluride module, and the antimonide thermoelectric module designed by the invention has the advantages of abundant storage, high annual output, high power cost ratio, and higher conversion efficiency, and is an effective competitor for realizing low-grade waste heat recovery through thermoelectric devices.
Example 2
Most of them were the same as in example 1 except that in step (1) of this example, the thickness of the electrode layer Ni was selected to be 0.5mm, the thicknesses of the diffusion barrier layers Sb and Fe were selected to be 0.05mm, and the thickness of the thermoelectric material was selected to be 5 mm.
Example 3
Compared with example 1, most of the components are the same except that Ni/Fe/Mg is added in step (2) of this example3The SbBi/Fe/Ni process conditions are as follows: the temperature was raised to 600 ℃ at a rate of 150 ℃ per minute under a pressure of 90MPa and held for 90 minutes.
Example 4
Compared with example 1, most of them are the same, except that silver plate is selected as the current carrier (i.e. metal current guiding layer) in step (4) of this example, and the thickness is 0.2 mm.
Example 5
Compared with the embodiment 1, most of the parts are the same, except that in the step (4) of the embodiment, the low-temperature end is welded with the current carrier by using soldering tin, and the high-temperature end is welded with the current carrier by using Ag-Zn brazing solder.
Example 6:
compared with the embodiment 1, most of the embodiments are the same, except that in the embodiment, the hot-pressing process conditions of the n-type thermoelectric element are as follows: the temperature was raised to 650 ℃ at a rate of 100 ℃ per minute under a pressure of 80MPa and held for 60 minutes.
Example 7:
compared with the embodiment 1, most of the embodiments are the same, except that in the embodiment, the hot-pressing process conditions of the n-type thermoelectric element are as follows: the temperature was raised to 550 ℃ at a rate of 150 ℃ per minute under a pressure of 100MPa and held for 90 minutes.
Example 8:
compared with the embodiment 1, most of the embodiments are the same, except that in the embodiment, the hot-pressing process conditions of the p-type thermoelectric element are as follows: the temperature was raised to 400 ℃ at a rate of 100 ℃ per minute under a pressure of 80MPa and held for 60 minutes.
Example 9:
compared with the embodiment 1, most of the embodiments are the same, except that in the embodiment, the hot-pressing process conditions of the p-type thermoelectric element are as follows: the temperature was raised to 350 ℃ at a rate of 150 ℃ per minute under a pressure of 80MPa and held for 90 minutes.
Example 10:
compared with the embodiment 1, the method is mostly the same, except that in the embodiment, the process conditions for cutting and preparing the sample are as follows: cutting a cylindrical sample by using a diamond cutting line with the line diameter of 0.35mm, cutting at the speed of 200 revolutions per minute, adjusting the rising speed of a sample table to be 0.1mm/min, cooling by using cutting oil, and cutting the cylindrical sample.
Example 11:
compared with the embodiment 1, the method is mostly the same, except that in the embodiment, the process conditions for cutting and preparing the sample are as follows: cutting a cylindrical sample by using a diamond cutting line with the line diameter of 0.45mm, cutting at the rate of 260 revolutions per minute, adjusting the rising speed of a sample table to be 0.5mm/min, cooling by using cutting oil, and cutting the cylindrical sample.
Example 12:
compared with example 1, most of them are the same except that in this example, in the n-type thermoelectric element and the p-type thermoelectric element, the thickness of the electrode Ni is 0.5mm, the thickness of the diffusion barrier Sb or Fe is 0.05mm, and the thermoelectric semiconductor material Mg3The thickness of the SbBi material or the CdSb material is 2 mm.
Example 13:
compared with example 1, most of them are the same except that in this example, the thickness of the electrode Ni is 1.0mm, the thickness of the diffusion barrier Sb or Fe is 0.3mm, and the thermoelectric semiconductor material Mg is used in the n-type thermoelectric element and the p-type thermoelectric element3The thickness of the SbBi material or the CdSb material is 6 mm.
In addition, in the above embodiments, the metal current carrier may be replaced with high-melting-point metal such as Ni, Cu, Ag, Fe, Co, Mo, or an alloy thereof, as needed.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency is characterized by comprising an insulating heat-conducting ceramic plate and an n-p thermoelectric unit which is fixed on the insulating heat-conducting ceramic plate and is connected in series by a metal diversion layer, wherein the n-p thermoelectric unit is composed of an n-type thermoelectric element and a p-type thermoelectric element which are connected in series by the metal diversion layer, and the n-type thermoelectric element is composed of Ni/Fe/Mg3SbBi/Fe/Ni in Mg3An SbBi material as a thermoelectric semiconductor material, Fe as a diffusion barrier layer, and Ni as an electrode; the p-type thermoelectric element has a composition of Ni/Sb/CdSb/Sb/Ni, and is formed by using a CdSb material as a thermoelectric semiconductor material, using Sb as a diffusion barrier layer and using Ni as an electrode.
2. The low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency of claim 1, wherein said Mg is selected from the group consisting of3The composition of SbBi material is Mg3.1Y0.01SbBi, the composition of the CdSb material is Cd0.99Ag0.01Sb。
3. The low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as claimed in claim 1, wherein said metal current carrier is a pure metal or alloy of Ni, Cu, Ag, Fe, Co, Mo.
4. The low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as claimed in claim 1, wherein the insulating and heat conducting ceramic sheet is alumina or aluminum nitride.
5. The low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as claimed in claim 1, wherein the metal current carrier has a thickness of 0.1-0.5 mm; the thickness of the insulating heat-conducting ceramic sheet is 0.1-1 mm;
in the n-type thermoelectric element and the p-type thermoelectric element, the thickness of the electrode Ni is 0.5 to 1.0mm, and the diffusion shieldThe thickness of the layer Sb or Fe is 0.05-0.3mm, and the thermoelectric semiconductor material Mg3The thickness of the SbBi material or the CdSb material is 2 to 6 mm.
6. The method of manufacturing a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as set forth in any one of claims 1 to 5, comprising the steps of:
(1) and (3) sample loading of a hot-pressing mold:
weighing electrode powder, diffusion shielding layer powder and thermoelectric semiconductor material powder, respectively filling the electrode powder, the diffusion shielding layer powder and the thermoelectric semiconductor material powder into a graphite die according to the composition layers of an n-type thermoelectric element and a p-type thermoelectric element, and compacting;
(2) one-step hot pressing sample preparation:
placing the graphite mold after sample loading in a vacuum hot-pressing device, carrying out one-step hot pressing, cutting and sample preparation to obtain an n-type thermoelectric element and a p-type thermoelectric element with target sizes, and connecting the n-type thermoelectric element and the p-type thermoelectric element in series to form a plurality of n-p thermoelectric units;
(3) module assembling:
connecting the n-p thermoelectric units through the metal guide layer, and fixing the n-p thermoelectric units on the insulating heat-conducting ceramic plate in sequence, namely assembling to obtain a target product.
7. The method for manufacturing a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as claimed in claim 6, wherein in step (2), the hot-pressing process conditions of the n-type thermoelectric element are as follows: raising the temperature to 550-650 ℃ at a rate of 100-150 ℃ per minute under a pressure of 80-100MPa, and preserving the temperature for 60-90 minutes.
8. The method for manufacturing a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as claimed in claim 6, wherein in the step (2), the hot-pressing process conditions of the p-type thermoelectric element are as follows: heating to 350-400 ℃ at the rate of 100-150 ℃ per minute under the pressure of 50-80MPa, and keeping the temperature for 60-90 minutes.
9. The method for manufacturing a low-grade waste heat recovery antimonide thermoelectric module with high conversion efficiency as claimed in claim 6, wherein in step (3), the process conditions for cutting and preparing the sample are as follows: cutting a cylindrical sample by using a diamond cutting line with the line diameter of 0.35-0.45mm, cutting at the speed of 200-260 revolutions per minute, adjusting the lifting speed of a sample table to be 0.1-0.5 mm/min, cooling by using cutting oil, and cutting the cylindrical sample.
10. The method of claim 6, wherein the n-type thermoelectric element or the p-type thermoelectric element is soldered to the metal current guiding layer at a low temperature end using solder, and the n-type thermoelectric element or the p-type thermoelectric element is soldered to the metal current guiding layer at a high temperature end using Sn-Sb-Pb.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB903731A (en) * | 1959-06-15 | 1962-08-15 | Westinghouse Electric Corp | Thermoelectric members |
| GB912571A (en) * | 1959-03-21 | 1962-12-12 | Siemens Ag | A process for the production of a system zn cd sb |
| JP2003092435A (en) * | 2001-09-17 | 2003-03-28 | Komatsu Ltd | Thermoelectric module and its manufacturing method |
| CN101345284A (en) * | 2008-08-29 | 2009-01-14 | 中国科学院上海硅酸盐研究所 | P type europium cadmium stibium based pyroelectric material and preparation method thereof |
| US20090211619A1 (en) * | 2008-02-26 | 2009-08-27 | Marlow Industries, Inc. | Thermoelectric Material and Device Incorporating Same |
| WO2016013366A1 (en) * | 2014-07-25 | 2016-01-28 | 日立化成株式会社 | Thermoelectric conversion module and method for making same |
| US20180175270A1 (en) * | 2016-12-15 | 2018-06-21 | Hyundai Motor Company | Thermoelectric material and method for preparing the same |
| CN109616568A (en) * | 2018-11-27 | 2019-04-12 | 同济大学 | Three magnesiumization of N-type, two antimony alloy thermoelectric material with high mobility and preparation method thereof |
| WO2019169970A1 (en) * | 2018-03-07 | 2019-09-12 | 南方科技大学 | N-type mg-sb-based room temperature thermoelectric material and preparation method therefor |
| CN110257667A (en) * | 2019-05-30 | 2019-09-20 | 同济大学 | A kind of three magnesiumization of N-type, two antimony alloy thermoelectric material and its preparation |
| JP2020167265A (en) * | 2019-03-29 | 2020-10-08 | 国立研究開発法人産業技術総合研究所 | Thermoelectric conversion material and manufacturing method thereof |
| CN112670395A (en) * | 2020-12-27 | 2021-04-16 | 同济大学 | Germanium telluride based thermoelectric single-leg device with high conversion efficiency and power density and preparation thereof |
| CN112921205A (en) * | 2021-01-26 | 2021-06-08 | 广西大学 | Rapid preparation of high thermoelectric property n-type Mg3Sb2Method for producing base material |
-
2021
- 2021-06-29 CN CN202110723991.6A patent/CN113488578B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB912571A (en) * | 1959-03-21 | 1962-12-12 | Siemens Ag | A process for the production of a system zn cd sb |
| GB903731A (en) * | 1959-06-15 | 1962-08-15 | Westinghouse Electric Corp | Thermoelectric members |
| JP2003092435A (en) * | 2001-09-17 | 2003-03-28 | Komatsu Ltd | Thermoelectric module and its manufacturing method |
| US20090211619A1 (en) * | 2008-02-26 | 2009-08-27 | Marlow Industries, Inc. | Thermoelectric Material and Device Incorporating Same |
| CN101345284A (en) * | 2008-08-29 | 2009-01-14 | 中国科学院上海硅酸盐研究所 | P type europium cadmium stibium based pyroelectric material and preparation method thereof |
| WO2016013366A1 (en) * | 2014-07-25 | 2016-01-28 | 日立化成株式会社 | Thermoelectric conversion module and method for making same |
| US20180175270A1 (en) * | 2016-12-15 | 2018-06-21 | Hyundai Motor Company | Thermoelectric material and method for preparing the same |
| WO2019169970A1 (en) * | 2018-03-07 | 2019-09-12 | 南方科技大学 | N-type mg-sb-based room temperature thermoelectric material and preparation method therefor |
| CN109616568A (en) * | 2018-11-27 | 2019-04-12 | 同济大学 | Three magnesiumization of N-type, two antimony alloy thermoelectric material with high mobility and preparation method thereof |
| JP2020167265A (en) * | 2019-03-29 | 2020-10-08 | 国立研究開発法人産業技術総合研究所 | Thermoelectric conversion material and manufacturing method thereof |
| CN110257667A (en) * | 2019-05-30 | 2019-09-20 | 同济大学 | A kind of three magnesiumization of N-type, two antimony alloy thermoelectric material and its preparation |
| CN112670395A (en) * | 2020-12-27 | 2021-04-16 | 同济大学 | Germanium telluride based thermoelectric single-leg device with high conversion efficiency and power density and preparation thereof |
| CN112921205A (en) * | 2021-01-26 | 2021-06-08 | 广西大学 | Rapid preparation of high thermoelectric property n-type Mg3Sb2Method for producing base material |
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