CN101409324A - Bismuth-telluride-based thermoelectric electrification device and manufacturing method thereof - Google Patents
Bismuth-telluride-based thermoelectric electrification device and manufacturing method thereof Download PDFInfo
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- CN101409324A CN101409324A CN200810040956.9A CN200810040956A CN101409324A CN 101409324 A CN101409324 A CN 101409324A CN 200810040956 A CN200810040956 A CN 200810040956A CN 101409324 A CN101409324 A CN 101409324A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 50
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 50
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005476 soldering Methods 0.000 claims abstract description 44
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000919 ceramic Substances 0.000 claims abstract description 36
- 238000005507 spraying Methods 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 239000000565 sealant Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000010248 power generation Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000003466 welding Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010285 flame spraying Methods 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 238000007747 plating Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010891 electric arc Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 238000009713 electroplating Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910000679 solder Inorganic materials 0.000 claims description 3
- 238000004857 zone melting Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 2
- 238000002360 preparation method Methods 0.000 claims 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000007750 plasma spraying Methods 0.000 abstract description 13
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000005678 Seebeck effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Abstract
The invention relates to a bismuth telluride-based thermoelectric generating device and a manufacturing method thereof. The bismuth telluride-based thermoelectric generating device is characterized by consisting of a perforated bracing frame, P/N-type elements, a barrier layer, a soldering tin layer, a low-temperature terminal electrode, a ceramic substrate, a sealant, a high-temperature terminal spraying electrode and the ceramic substrate; the pattern of the low-temperature terminal electrode corresponds to holes of the perforated bracing frame. The manufacturing method comprises the steps of preparing the perforated bracing frame, preparing the elements, mounting the elements, soldering the cold terminal electrode with tin, spaying a hot terminal electrode, grinding the sprayed surface and the like; the perforated bracing frame is put on the ceramic substrate covered by the low-temperature terminal electrode, the low-temperature terminal electrode is arranged in a hole of the bracing frame, the bismuth telluride-based P/N-type elements are put in the holes of the bracing frame, the soldering tin layers of the elements contact with a tin layer on the low-temperature terminal electrode, the elements are soldered on the low-temperature terminal electrode by heating; the high-temperature terminal of the device is sprayed with aluminum or aluminum alloy and taken as the high-temperature terminal electrode, and the P/N-type elements are connected in series. The device and the method overcome the problem that the existing tin soldering devices are restricted by operating environment and temperature, and the rejection rate and the manufacturing cost are far less than these of plasma spraying devices.
Description
Technical Field
The invention relates to a thermoelectric device and a manufacturing method thereof, in particular to a sealed bismuth telluride-based low-temperature thermoelectric power generation device and a manufacturing method thereof, belonging to the technical field of thermoelectric conversion.
Background
Thermoelectric power generation is a technology for realizing direct conversion of heat energy and electric energy by utilizing the Seebeck effect of a semiconductor material, and has wide application prospect and potential social and economic benefits in the aspects of solar photoelectric-thermoelectric composite power generation, industrial waste heat thermoelectric power generation and the like.
The thermoelectric power generation device is the key of the thermoelectric power generation technology, mainly comprises thermoelectric elements made of two semiconductor materials, namely a P-type semiconductor material and an N-type semiconductor material, the voltage of a single thermoelectric element is very low, and a large number of P-type thermoelectric elements and N-type thermoelectric elements are generally required to be connected in a conductive series connection and a heat conduction parallel connection mode to form the thermoelectric device so as to obtain higher voltage and be convenient to use.
FIG. 1 shows a typical bismuth telluride-based low-temperature thermoelectric device, which is composed of a P/N type element, an electrode and a ceramic substrate. The manufacturing steps are as follows: 1) cutting P/N type elements with designed size; 2) preparing an electrode on a ceramic substrate; 3) soldering tin P/N type elements on the electrodes in series and parallel connection. Such a thermoelectric power generation device has the following problems in practical use: 1) in a humid environment, moisture is gathered in gaps inside the device, and the device is easy to generate thermal short circuit, so that the output power is greatly reduced; 2) in the using process, the device loses efficacy due to the falling of soldering tin at high temperature, the using temperature range of the device is limited by the melting point of the soldering tin, and the potential of the bismuth telluride-based material cannot be fully exerted.
In view of the above problems, US patent (US5875098) provides a bismuth telluride-based thermoelectric power generating device as shown in fig. 2, which is composed of a P/N type element, a molybdenum barrier layer, an aluminum electrode, a porous grid basket of a high temperature organic material, and an electrically insulating thin film. US patent (US5856210) discloses a method of manufacturing such a device, comprising the steps of: 1) manufacturing a high-temperature organic material porous grid basket; 2) cutting P/N type elements and loading into a grid basket; 3) plasma spraying molybdenum metal as a barrier layer and spraying aluminum metal as an electrode; 4) grinding until the grids are exposed; 5) an electrically insulating film is applied. The grid eliminates the gaps between the elements, and the melting point of the aluminum is far higher than the use temperature of the device, so that the limitation of the use of the device in a humid environment and the limitation of the melting point of soldering tin are well overcome. However, the manufacturing cost of such devices is high, much higher than the cost of soldering devices, because: 1) the metal molybdenum barrier layer and the aluminum electrode are sprayed by plasma, the spraying temperature is high, heat is gathered on the grid basket, the temperature of the grid basket is increased and the grid basket is deformed, the workload of the subsequent process, namely grinding is increased, devices are scrapped due to serious deformation, and the rate of finished products of the devices is reduced; 2) plasma spraying equipment is expensive in manufacturing cost and high in operating cost, and electrodes with certain thicknesses are sprayed for dozens of times, so that the cost is quite high.
The use temperature of the bismuth telluride-based power generation device prepared by the soldering method is limited, and the yield of the device prepared by plasma spraying is low, and the cost is high, so that the large-scale application of the device is limited by high cost. Therefore, a method is urgently needed to be provided, which can not only improve the use temperature of the bismuth telluride-based power generation device, but also reduce the cost.
Disclosure of Invention
Aiming at the problems, the invention provides a bismuth telluride-based thermoelectric power generation device different from the existing structure and a manufacturing method thereof, so as to overcome the limitation of a soldering device on the use environment and temperature, and the rejection rate and the cost of the manufacturing of the bismuth telluride-based thermoelectric power generation device are far lower than those of the existing plasma spraying device.
The bismuth telluride-based thermoelectric power generation device provided by the invention is composed of a porous support frame, a P/N type bismuth telluride element, a barrier layer, a soldering tin layer, a low-temperature terminal electrode, a ceramic substrate, a sealant, a high-temperature terminal spraying electrode and a ceramic substrate. It is characterized in that: (1) the low-temperature terminal electrode is sintered on the ceramic substrate, the pattern of the low-temperature terminal electrode is matched with the holes of the porous support frame, and when the porous support frame is placed on the ceramic substrate, the low-temperature terminal electrode is completely positioned in the holes of the matched porous support frame; (2) the porous support frame is positioned on the ceramic substrate, and the low-temperature terminal electrode and the P/N type element are positioned in the holes of the support frame; (3) a soldering tin layer and a barrier layer are sequentially arranged between the low-temperature terminal electrode and the P/N type element, the soldering tin layer combines the P/N type element and the low-temperature terminal electrode together, and the barrier layer prevents soldering tin atoms from diffusing to the bismuth telluride base material so as to avoid deteriorating the performance of the bismuth telluride base material; (4) the sealant is positioned between the porous support frame and the ceramic substrate to seal the gap; (5) the other end of the P/N type element is sequentially provided with a barrier layer, a high-temperature end spraying electrode and a ceramic substrate. Thus, the bismuth telluride-based thermoelectric power generation device with electric conduction series connection and heat conduction parallel connection is formed.
The porous support frame eliminates the gap between the P/N type elements, overcomes the limitation of the device to the use environment, and overcomes the limitation of the device to the use temperature by the high-temperature end electrode. The barrier layer is prepared by adopting an electroplating or flame spraying method, the high-temperature terminal electrode is prepared by adopting flame spraying or electric arc spraying, the cost is greatly lower than that of plasma spraying, the thermal deformation in the device spraying process is far smaller than that of plasma spraying, the workload and the rejection rate of subsequent processes are reduced, and the cost is reduced.
The manufacturing method of the bismuth telluride-based thermoelectric power generation device comprises the following steps: preparing a porous support frame, preparing elements, loading the elements, soldering cold-end electrodes, spraying hot-end electrodes, grinding a sprayed surface and the like.
The manufacturing method is described in detail below with reference to the accompanying drawings:
1) and (4) preparing a porous support frame. Selecting high temperature resistant resin (trade name: PBB) as material of porous support frame, heating the material to liquid state, injecting into preheated mould, maintaining pressure, forming, introducing water to cool mould to room temperature, and taking out the support frame. The porous support frame is provided with straight holes without steps for inclination and element positioning. The size of the porous support is determined by the requirements of the device. Due to the structural characteristics of the device, an element positioning step does not need to be arranged in the porous support frame, so that the structure of a forming die of the porous support frame is simplified, and the manufacturing cost of the die is reduced.
2) And (5) preparing the element. Zone-melting or sintering bismuth telluride-based materials are adopted. Slicing a bismuth telluride base material, plating nickel on the sliced material to form a barrier layer, plating tin on one end of the nickel plated material to form a tin welding layer on the bismuth telluride base element, and then cutting to obtain a P-type element and an N-type element with specified sizes. The barrier layer is prepared by adopting an electroplating method, Al or Al alloy can be directly sprayed, and because the melting point of Al and the alloy thereof is low, the barrier layer adopts flame spraying or electric arc spraying, and the cost can be greatly reduced compared with plasma spraying. The thickness of the nickel layer as the barrier layer is 5 to 50 μm.
3) And (6) loading the element. The low-temperature terminal electrode is a 0.2-0.4mm copper sheet, the low-temperature terminal electrode is sintered on an alumina (or aluminum nitride) ceramic substrate, and soldering tin is carried out on the low-temperature terminal electrode to form a soldering tin layer on the low-temperature terminal electrode, wherein the thickness of the soldering tin layer is not more than 150 microns. The porous support frame is placed on the ceramic substrate, the low-temperature end electrode is positioned in the hole of the porous support frame, the P-type element and the N-type element are sequentially arranged, and the soldering tin layer of the element is in contact with the soldering tin layer on the low-temperature end electrode. And covering a positioning plate at the other end of the porous support frame, and clamping to obtain the assembled modular device.
4) And soldering the cold-end electrode. And (3) putting the assembled and clamped modular device into welding equipment, and heating to 200 ℃ to realize cold end electrode welding to obtain the cold end welded modular device. The cold end electrode welding equipment is an insulation box with a conveyor belt, the manufacturing cost is not as high as one tenth of that of plasma spraying equipment, the operation is simple, and the operation cost is low, so that the cold end electrode welding cost is greatly lower than that of the plasma spraying method in the prior art.
5) Hot end (high temperature end) electrode spraying. And mounting the modularized devices with the welded cold-end electrodes on a fixture with a circulating water cooling device, and horizontally mounting the modularized devices on a workbench of spraying equipment together. During spraying, the workbench is fixed, and the spray head moves. And spraying 200-800 micron aluminum or aluminum alloy as a hot end electrode by adopting flame spraying or electric arc spraying equipment. So that the P/N type elements form a serial structure, and sealant is coated between the porous support frame and the low-temperature end ceramic substrate. Compared with the prior art, the invention adopts the circulating water cooling device, thereby effectively reducing the heat accumulation on the device and avoiding the deformation of the device caused by the temperature rise, thereby reducing the rejection rate of the device and lowering the cost.
6) And grinding the spraying surface. The spray face must be ground until the edges of the porous support frame are exposed, for which purpose the spray module is mounted in a surface grinder for grinding, the height of the module being controlled within a suitable range during grinding.
Drawings
FIG. 1 is a prior art bismuth telluride based thermoelectric power generation device made by a tin soldering method;
FIGS. 2 a-c are schematic diagrams of a bismuth telluride-based thermoelectric power generation device prepared by a metal spraying method in the prior art, wherein a is a top view of the device, b is a 1-1 section view of the device, and c is a 2-2 section view of the device;
FIGS. 3 a-C are schematic views of the porous scaffold of the present invention, wherein a is a front view, B is a sectional view taken along line B-B, and C is a sectional view taken along line C-C;
FIG. 4 is a schematic view of a bismuth telluride base element;
fig. 5a to d are schematic assembly diagrams of the bismuth telluride-based thermoelectric power generation device provided by the present invention, wherein a is a bottom view, b is a cross-sectional view, c is a partial enlarged sectional view in b, and d is a top view;
fig. 6 a-b are schematic diagrams of hot end spraying of the bismuth telluride-based thermoelectric power generation device provided by the invention, wherein a is a cross-sectional view and b is a top view;
fig. 7 a-b are schematic diagrams of a bismuth telluride-based thermoelectric power generation device provided by the invention, wherein a is a perspective view of the device, and b is a cross-sectional view of the device;
in the figure, 10 is a porous support frame, 20 is a P-type element, 21 is an N-type element, 22 is a barrier layer, 23 is a soldering tin layer on the element, 30 is a ceramic substrate, 31 is a low-temperature end electrode, 32 is a soldering tin layer on the low-temperature end electrode, 33 is a positioning plate, 34 is a soldering tin layer after low-temperature end welding, 41 is a device after cold end electrode welding and before hot end electrode spraying, 51 is a circulating water cooling device in a clamp, 52 is a clamp, 53 is a spray head, 54 is a thermal spraying workbench, 55 is a high-temperature end electrode, and 56 is sealant.
Detailed Description
The essential features and the remarkable advantages of the present invention will be further clarified below with reference to the accompanying drawings.
The manufacturing method of the bismuth telluride-based thermoelectric power generation device comprises the following steps: preparing a porous support frame, preparing elements, loading the elements, soldering cold-end electrodes, spraying hot-end electrodes, grinding a sprayed surface and the like. Now, the following is explained in detail:
1) and (4) preparing a porous support frame. A high-temperature resistant resin (trade name: PBB) is selected as a material of the porous support frame 10, the material is heated to a liquid state, injected into a preheated mold, kept under pressure, molded, cooled to room temperature by introducing water, and taken out. Porous support frame 10 as shown in fig. 3, the pores of the porous support frame are straight and have no slope or element positioning step. The size of the porous support is determined by the requirements of the device. Because of the structural characteristics of the device, the porous support frame does not need to be provided with element positioning steps, so that the structure of the forming die of the porous support frame is simplified, and the manufacturing cost of the die is reduced.
2) And (5) preparing the element. Zone-melting or sintering bismuth telluride-based materials are adopted. Slicing a bismuth telluride base material, plating nickel on the sliced piece to form a barrier layer 22, plating tin on one end of the nickel-plated piece to form a tin welding layer 23 on the bismuth telluride base element, and then cutting to obtain a P-type element 20 and an N-type element 21 (see figure 4) with specified sizes. The barrier layer is prepared by adopting an electroplating method, Al or Al alloy can be directly sprayed, and because the melting point of Al and the alloy thereof is low, the barrier layer adopts flame spraying or electric arc spraying, and the cost can be greatly reduced compared with plasma spraying.
3) And (6) loading the element. The low-temperature terminal electrode 31 is a 0.2-0.4mm copper sheet, the low-temperature terminal electrode 31 is sintered on an alumina (or aluminum nitride) ceramic substrate 30, soldering tin is carried out on the low-temperature terminal electrode 31, and a soldering tin layer 32 on the low-temperature terminal electrode 31 is formed, wherein the thickness of the soldering tin layer is not more than 150 microns. The porous support 10 is placed on the ceramic substrate 30, the low-temperature terminal electrode 31 is positioned in the hole of the porous support 10, and the P-type component 20 or the N-type component 21 is sequentially loaded, taking care that the solder layer 23 of the component is in contact with the solder layer 32 on the low-temperature terminal electrode 31. And covering the other end of the porous support frame 10 with a positioning plate 33, and clamping to obtain the assembled modular device, which is shown in fig. 5.
4) And soldering the cold-end electrode. And (3) putting the assembled and clamped modular device into welding equipment, and heating to 200 ℃ to realize cold end electrode welding to obtain a cold end welded modular device 41. The cold end electrode welding equipment is an insulation box with a conveyor belt, the manufacturing cost is not as high as one tenth of that of plasma spraying equipment, the operation is simple, and the operation cost is low, so that the cold end electrode welding cost is greatly lower than that of the plasma spraying method in the prior art.
5) Hot end (high temperature end) electrode spraying. The cold-side electrode welded modular device 41 is mounted on a fixture 52 with a circulating water cooling means 51 and then mounted horizontally together on a work table 54 of the painting equipment. During spraying, the table 54 is stationary and the head 53 is moved. And spraying 200-800 micron aluminum or aluminum alloy as the hot end electrode 55 by adopting flame spraying or electric arc spraying equipment. The P/N type elements are connected in series, and a sealant 56 is coated between the porous support frame and the low temperature end ceramic substrate. Compared with the prior art, the invention adopts the circulating water cooling device, thereby effectively reducing the heat accumulation on the device and avoiding the deformation of the device caused by the temperature rise, thereby reducing the rejection rate of the device and lowering the cost. (FIG. 6)
6) And grinding the spraying surface.
A cross-sectional view of the structure fabricated into a device is shown in fig. 7.
The bismuth telluride-based thermoelectric power generation device provided by the invention comprises a porous support frame, a P/N type bismuth telluride element, a barrier layer, a soldering tin layer, a low-temperature terminal electrode, a ceramic substrate, a sealant, a high-temperature terminal electrode and a ceramic substrate; wherein,
(1) the low-temperature terminal electrode 31 is sintered on the ceramic substrate 30, and the pattern of the low-temperature terminal electrode 31 is matched with the holes of the porous support frame 10;
(2) the porous support frame 4 is positioned between the upper ceramic substrate and the lower ceramic substrate, and the low-temperature terminal electrode 31 and the P/ N type elements 21 and 20 are positioned in the holes of the porous support frame 10; the holes of the porous support frame are straight holes;
(3) a soldering tin layer 32 (not shown) and a barrier layer 22 are sequentially arranged between the low-temperature terminal electrode 31 and the P/N type element, and the P/N type element and the low-temperature terminal electrode are combined together through the soldering tin layer 34 welded at the low-temperature terminal;
(4) the sealant 56 is positioned between the porous support frame 10 and the ceramic substrate 30;
(5) the other end of the P/N type element is sequentially provided with a barrier layer 22 and a high-temperature end electrode 55, so that the bismuth telluride-based thermoelectric power generation device with electric conduction series connection and heat conduction parallel connection is formed.
Claims (10)
1. A bismuth telluride-based thermoelectric power generation device is composed of a porous support frame, a P/N type bismuth telluride element, a barrier layer, a soldering tin layer, a low-temperature end electrode, a ceramic substrate, a sealant, a high-temperature end spraying electrode and a ceramic substrate; the method is characterized in that: (1) the low-temperature terminal electrode is sintered on the ceramic substrate, the pattern of the low-temperature terminal electrode is matched with the holes of the porous support frame, and when the porous support frame is placed on the ceramic substrate, the low-temperature terminal electrode is completely positioned in the holes of the matched porous support frame; (2) the porous support frame is positioned on the ceramic substrate, and the low-temperature terminal electrode and the P/N type element are positioned in the holes of the support frame; (3) a soldering tin layer and a barrier layer are sequentially arranged between the low-temperature terminal electrode and the P/N type element, and the soldering tin layer combines the P/N type element and the low-temperature terminal electrode together; (4) the sealant is positioned between the porous support frame and the ceramic substrate; (5) the other end of the P/N type element is sequentially provided with a barrier layer, a high-temperature end spraying electrode and a ceramic substrate; the bismuth telluride-based thermoelectric power generation device with electric conduction series connection and heat conduction parallel connection is formed.
2. The bismuth telluride based thermoelectric power generating device as in claim 1 wherein the pores of the porous support are straight and have no steps for pitch and component positioning.
3. The bismuth telluride based thermoelectric power generation device as in claim 1, wherein the barrier layer is a metallic nickel layer having a thickness of 5 to 50 μm.
4. The bismuth telluride based thermoelectric power generating device as defined in claim 1 wherein said ceramic substrate is aluminum oxide or aluminum nitride.
5. The bismuth telluride based thermoelectric power generation device as in claim 1 wherein the low temperature terminal electrode is a 0.2-0.4mm copper sheet and the thickness of the solder layer on the low temperature terminal electrode is no more than 150 microns.
6. The bismuth telluride based thermoelectric power generating device as defined in claim 1 wherein the high temperature terminal electrode is aluminum or aluminum alloy and has a thickness of 200-800 μm.
7. The method for preparing the bismuth telluride-based thermoelectric power generation device as in any one of claims 1 to 6, which is characterized by comprising six steps of porous support frame preparation, element loading, cold end electrode soldering, high-temperature end electrode spraying and spraying surface grinding, and specifically comprises the following steps of:
1) preparing a porous support frame: selecting high temperature resistant resin as the material of the porous support frame, heating the material to liquid state, injecting the material into a preheated mold, keeping the pressure, forming, introducing water to cool the mold to room temperature, and taking out the support frame. The hole of the porous support frame is a straight hole, and the size of the porous support frame is determined according to the requirements of the device;
2) element preparation: adopting a zone-melting or sintered bismuth telluride base material, slicing the bismuth telluride base material, plating nickel on the slices to form a barrier layer, plating tin on one end of the nickel plating to form a tin welding layer on the bismuth telluride base element, and then cutting to obtain a P-type element and an N-type element with specified sizes;
3) loading the element: sintering the copper sheet of the low-temperature terminal electrode on a ceramic substrate of aluminum oxide or aluminum nitride, and soldering tin on the low-temperature terminal electrode to form a soldering tin layer on the low-temperature terminal electrode; placing a porous support frame on a ceramic substrate, positioning a low-temperature end electrode in a hole of the porous support frame, sequentially loading a P-type element or an N-type element, contacting a soldering tin layer of the element with a soldering tin layer on the low-temperature end electrode, covering a positioning plate at the other end of the porous support frame, and clamping to obtain an assembled modular device;
4) soldering a cold end electrode: putting the assembled and clamped modular device into welding equipment, and heating to 200 ℃ to realize cold end electrode welding to obtain a cold end welded modular device;
5) high-temperature end electrode spraying: spraying aluminum or aluminum alloy on the modular device welded with the cold end electrode prepared in the step 4 by adopting flame spraying or electric arc spraying equipment to serve as a high-temperature end electrode; forming a series structure of the P/N type elements, and coating a sealant between the porous support frame and the low-temperature end ceramic substrate;
6) grinding the spraying surface: and 5, grinding the prepared spraying module on a grinding machine to control the height of the module.
8. The method for producing a bismuth telluride-based thermoelectric power generating device as claimed in claim 7, wherein the cold-end electrode soldering in step 4 is carried out in a heat-insulating box with a conveyor belt.
9. The method for preparing a bismuth telluride based thermoelectric power generation device as claimed in claim 7, wherein the high temperature end electrode spraying is carried out by installing a modular device welded with a cold end electrode on a jig provided with a circulating water cooling device, and then horizontally installing the modular device on a worktable, and keeping the worktable still, and moving a nozzle for flame spraying or arc spraying.
10. The method for manufacturing a bismuth telluride based thermoelectric power generating device as claimed in claim 7, wherein the nickel barrier layer of the P-type or N-type bismuth telluride element is manufactured by an electroplating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810040956.9A CN101409324B (en) | 2008-07-24 | 2008-07-24 | Manufacturing method of bismuth-telluride-based thermoelectric electrification device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810040956.9A CN101409324B (en) | 2008-07-24 | 2008-07-24 | Manufacturing method of bismuth-telluride-based thermoelectric electrification device |
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| Publication Number | Publication Date |
|---|---|
| CN101409324A true CN101409324A (en) | 2009-04-15 |
| CN101409324B CN101409324B (en) | 2013-10-16 |
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