CN107706296B - Thermoelectric device with integrated packaging structure and preparation method thereof - Google Patents
Thermoelectric device with integrated packaging structure and preparation method thereof Download PDFInfo
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- CN107706296B CN107706296B CN201710848199.7A CN201710848199A CN107706296B CN 107706296 B CN107706296 B CN 107706296B CN 201710848199 A CN201710848199 A CN 201710848199A CN 107706296 B CN107706296 B CN 107706296B
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- H01L23/3107—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
- H01L23/3121—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed a substrate forming part of the encapsulation
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Abstract
the integrated packaging structure thermoelectric device and the preparation method thereof of the invention comprise the following steps: a thermoelectric module including at least a pair of P-type and N-type thermoelectric materials and having a high temperature end and a low temperature end; insulation layers provided on a high temperature end side and a low temperature end side of the thermoelectric module; a buffer layer provided on a high-temperature end side of the thermoelectric module; an upper cover integrally covering the thermoelectric module, the insulating layer and the buffer layer; a bottom plate for placing the thermoelectric module and forming a closed housing space with the upper cover; and a plurality of output sensors respectively assembled and connected with the thermoelectric module and the bottom plate. According to the invention, the thermoelectric material and the high-temperature metal electrode can be prevented from being oxidized, and can be directly used for a long time in a high-temperature and atmospheric environment, so that the service life and the reliability of the thermoelectric device are improved.
Description
Technical Field
The invention relates to a thermoelectric device, in particular to a thermoelectric device with an integrated packaging structure and a preparation method thereof.
background
The thermoelectric conversion technology is a technology for directly converting heat energy and electric energy by using a semiconductor material, is an environment-friendly energy conversion technology, has obvious advantages in the aspects of recycling industrial waste heat and automobile exhaust waste heat, and plays an important role in improving the utilization rate of the waste heat, improving the comprehensive utilization efficiency of energy, reducing fossil fuel consumption, improving the environment, improving the climate and the like.
The wide application of the thermoelectric conversion technology is limited by two factors, namely, the intrinsic thermoelectric property of the thermoelectric material determines the theoretical highest conversion efficiency of the thermoelectric material; the second is the device preparation integration technology, which directly affects the device reliability and the device conversion efficiency.
With the development of a new material preparation technology, the performance of thermoelectric materials of multiple systems is greatly improved. Meanwhile, the thermoelectric component integration technology is optimized, and the technology of a multi-section cascade device is broken through, so that the efficiency of the thermoelectric device is continuously improved. However, for thermoelectric devices, especially high temperature thermoelectric devices, the operating temperature is typically 300 ℃ to 1000 ℃. In the high-temperature service process of the thermoelectric device, the performance of the thermoelectric device is reduced or even fails due to volatilization of partial component elements or oxidation of materials, so that the thermoelectric device without the packaging structure cannot be used at high temperature and in an air environment for a long time, and the practical application of the thermoelectric device is seriously hindered.
To avoid this problem, a coating is usually formed on the surface of the thermoelectric material for protection. Chen et al [ Lidong Chen, Takashi Goto, Rong Tu and Toshio Hirai, High-temperature oxidation catalyst of PbTe and oxidation-responsive glass coating [ J ].1997 PROCEEDINGS, Sixteenth International Conference on Thermoelectrics (ICT): 251-254, a 30-50 μm glass coating is applied to the surface of PbTe to prevent it from being oxidized. Chinese patent publication CN 103146301A discloses a preparation method of a skutterudite-based inorganic protective coating, MITSURU KAMBE et al [ MITSURU KAMBE, TAKAHIRO JINUSHI, and ZENZO ISIJIMA, Encapsulated Thermoelectric Modules and compatible pads for Advanced Thermoelectric Systems [ J ], Journal of Electronic Materials,39(9), 2010: 1418-.
Reference 1, filed by the same applicant, discloses a multilayer protective coating combining a transition layer and a barrier layer, for CoSb3The volatilization of the middle Sb and the oxidation of the thermoelectric material from outside to inside have certain effects, however, in the actual preparation, the condition for preparing the protective coating on the thermoelectric material is harsh, and the coating usually cracks or falls off due to high and low temperature thermal shock of the thermoelectric device in the actual use process. In addition, it is difficult to ensure the continuity, uniformity and compactness of the coating for the thermoelectric element having a structure of a special shape such as a right angle, a sharp point, etc. The problem of oxidation of the electrode material of the thermoelectric device cannot be completely solved by the coating.
prior art documents:
Patent documents:
Patent document 1: chinese patent publication CN 104465976 a.
disclosure of Invention
The problems to be solved by the invention are as follows:
In view of the above problems, an object of the present invention is to provide a thermoelectric device with an integrated package structure, which has a long lifetime and high reliability, and a method for manufacturing the same, so that the thermoelectric device can stably operate for a long time in an operating temperature range, and overcome many technical problems such as coating protection only on thermoelectric materials.
as mentioned above, the preparation of the high-temperature protective coating of the thermoelectric material by the conventional high-temperature protection technology for thermoelectric materials not only has great technical difficulty, but also can cause cracking or falling off of the prepared coating due to high-temperature and low-temperature thermal shock in the actual service process of thermoelectric devices. In addition, it is difficult to obtain a continuous, uniform and dense coating for thermoelectric elements having special portions such as right angles and sharp points or special-shaped structures, and high-temperature metal electrode materials also face the technical problems of oxidation, mechanical matching and difficult coating of the coating.
Based on the current technical situation, the inventor researches and aims at the existing method for protecting the thermoelectric device by using coatings, and mainly introduces an integrated packaging technology to integrally package the thermoelectric component in a sealed and high-temperature-resistant shell so as to ensure that the thermoelectric material is in an anaerobic environment, thereby prolonging the service life, improving the reliability and the like of the thermoelectric device.
Means for solving the problems:
In order to solve the above-described problems, a thermoelectric device having an integrated package structure according to the present invention includes: a thermoelectric module including at least a pair of P-type and N-type thermoelectric materials and having a high temperature end and a low temperature end; insulation layers provided on a high temperature end side and a low temperature end side of the thermoelectric module; a buffer layer provided on a high-temperature end side of the thermoelectric module; an upper cover integrally covering the thermoelectric module, the insulating layer and the buffer layer; a bottom plate for placing the thermoelectric module and forming a closed housing space with the upper cover; and a plurality of output sensors respectively assembled and connected with the thermoelectric module and the bottom plate.
According to the thermoelectric device with the integrated packaging structure, the thermoelectric material and the high-temperature metal electrode can be prevented from being oxidized, the thermoelectric device can be directly used for a long time in a high-temperature and atmospheric environment, and the service life and the reliability of the thermoelectric device are improved.
In the present invention, the housing space defined by the upper cover and the bottom plate may further include: thermal insulation material disposed in the inner space and the periphery of the plurality of thermoelectric modules; a volatilization suppressing material provided on a high-temperature end side of the thermoelectric module; and an oxygen-absorbing material disposed near a high-temperature end of the thermoelectric module.
according to the invention, in the integrated packaging process, the volatile element in the thermoelectric material is introduced at the high-temperature end, so that the volatilization process of the thermoelectric material under the high-temperature condition can be inhibited, and the performance attenuation speed of the thermoelectric device is further reduced. And a heat insulating material is embedded in the packaging device structure, so that heat leakage of the thermoelectric device can be reduced, and the output performance of the thermoelectric device is improved. Oxygen absorption material is introduced into the packaging device, so that residual oxygen can be removed, and the service life and reliability of the thermoelectric device are improved.
In the present invention, the heat insulating material may be one or more selected from alumina ceramic fiber, zirconia ceramic fiber, nano silica composite, aerogel, and aerogel composite.
In the present invention, the thermoelectric element may be selected from a Bi-Te based alloy, a Pb-Te based alloy, and CoSb3A single-stage component, a multi-stage component or a cascade component composed of one or more thermoelectric materials selected from the group consisting of skutterudite, Mg-Si-based alloys, diamond-like compounds, Half-Heusler alloys, SiGe-based alloys, and Ziegler phase compounds.
In the present invention, the insulation resistance of the insulation layer may be equal to or greater than 1 M.OMEGA., wherein the thickness of the insulation layer on the high temperature end side is equal to or less than 0.2mm, and the thickness of the insulation layer on the low temperature end side is equal to or less than 0.5 mm.
In the present invention, the buffer layer may be one or more selected from Ni foam, Ti foam, Cu foam, and graphite paper, and the thickness of the buffer layer is less than or equal to 0.3 mm.
In the present invention, the upper cover and the bottom plate may be made of a material selected from the group consisting of Fe-based alloy, Ni-based alloy, and Co-based alloy; the thickness of the upper cover is 0.05 mm-0.5 mm, and the thickness of the bottom plate is 0.05 mm-0.5 mm.
In the present invention, the output sensor may include: the thermoelectric module comprises a base used for being assembled and fixed with the bottom plate, an output electrode used for being electrically connected with the thermoelectric module, and an insulating sleeve arranged between the base and the output electrode.
The preparation method of the thermoelectric device with the integrated packaging structure comprises the following steps: preparing insulating layers arranged on the high-temperature end side and the low-temperature end side of the thermoelectric module; placing a buffer layer on the high-temperature end side; connecting the positive and negative terminals of the thermoelectric assembly with the output electrode of the output sensor; and assembling the thermoelectric assembly and the output sensor on a bottom plate, covering an upper cover, and welding and sealing the upper cover and the bottom plate and the output sensor and the bottom plate in a vacuum or inert gas environment. According to the invention, the thermoelectric component can be integrally packaged through a simple and easy process, and the thermoelectric device with an integrated packaging structure is obtained.
In the present invention, before the sealing, a heat insulating material may be filled in the inner gap and the vicinity of the outer periphery of the thermoelectric module.
The invention has the following effects:
According to the invention, the thermoelectric component can be integrally packaged through a simple and easy process to obtain the thermoelectric device with an integrated packaging structure, so that the thermoelectric material and the high-temperature metal electrode are prevented from being oxidized, and the service life and the reliability of the thermoelectric device are improved.
The foregoing and other objects, features and advantages of the invention will be better understood from the following detailed description taken in conjunction with the accompanying drawings.
drawings
FIG. 1 is a schematic structural diagram of a terrace-structured packaged flat thermoelectric device D according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a circular truncated cone structure packaged flat plate type thermoelectric device D according to an embodiment of the invention;
FIG. 3 is a schematic diagram of the structure of a packaged Y-configuration thermoelectric device D according to an embodiment of the present invention;
Fig. 4 is a schematic structural view of the output sensor 6;
FIG. 5 is a graph showing the change in performance of the fabricated thermoelectric device D of the integrated package structure in air;
FIG. 6 is a graph comparing the performance of the encapsulated assembly filled with insulating material 7 and without insulating material 7;
Description of the symbols:
1 a thermoelectric module;
2 an insulating layer;
3 a buffer layer;
4, covering the cover;
5, a bottom plate;
6 an output sensor;
7 heat insulating material;
8 suppressing volatile materials;
9 oxygen absorbing material.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting. The same or corresponding reference numerals denote the same components in the respective drawings, and redundant description is omitted.
In order to solve the above problem, the thermoelectric device D having an integrated package structure (hereinafter, simply referred to as thermoelectric device D) according to the present invention is hermetically welded by a case, and has a high temperature end and a low temperature end. The thermoelectric device D includes: thermoelectric module 1, insulating layer 2, buffer layer 3, shell, output sensor 6. The housing may be made of, for example, a high temperature resistant alloy and may include a top cover 4 and a bottom plate 5.
In the present embodiment, the thermoelectric module 1 is selected from Bi-Te based alloys, Pb-Te based alloys, and CoSb3A single-stage or multi-stage or cascade module of one or more thermoelectric materials selected from the group consisting of skutterudite, Mg-Si based alloys, diamond-like compounds, Half-Heusler alloys, SiGe based alloys, and Ziegler phase compounds. The thermoelectric module 1 comprises at least one pair of P-type and N-type thermoelectric materials.
Specifically, the thermoelectric module 1 may be, for example, a flat plate structure type thermoelectric module or a Y structure type thermoelectric module, but is not limited thereto. The parallelism of the parallel surfaces of the high-temperature end and the low-temperature end in the flat-plate structure type thermoelectric module is less than or equal to 0.1 mm; the parallelism of the parallel surfaces of the high-temperature end electrode and the low-temperature end electrode of the Y-shaped structural component is less than or equal to 0.1 mm. When the thermoelectric module is a flat-plate structure type thermoelectric module, the flatness of the parallel surface of the electrode between the high-temperature end and the low-temperature end is less than or equal to 0.1mm/100mm, and the roughness Ra is less than or equal to 3.2; when the thermoelectric module is a Y-structure type thermoelectric module, the flatness of the parallel surface of the electrode between the high-temperature end and the low-temperature end is less than or equal to 0.1mm/100mm, and the roughness Ra is less than or equal to 3.2. In the present embodiment, the thermoelectric module 1 may be produced directly without a coating layer, or may be produced on the thermoelectric module 1 with a protective coating layer produced, and the latter protective effect is more excellent.
the insulating layer 2 includes an insulating layer 2 located at a high temperature end side and an insulating layer 2 located at a low temperature end side, and covers the high temperature end and the low temperature end of the thermoelectric device D, respectively, and may be one or a combination of several selected from oxides, nitrides, carbides, and mica sheets containing Al, Si, B, and Cr, or may be Al2O3AlN or Si3N4A multilayer structure formed by sintering integrally with the electrode material, wherein the insulating layer 2 on the low temperature end side may be the same as the insulating layer 2 on the high temperature end side, andmay be a polyimide copper clad structure. In the present embodiment, the insulation resistance of the insulating layer 2 is preferably 1 M.OMEGA.. Preferably, the thickness of the insulating layer 2 at the high-temperature end side is less than or equal to 0.2 mm; the thickness of the insulating layer 2 at the low-temperature end side is less than or equal to 0.5 mm.
the buffer layer 3 may be provided on the high-temperature end side of the thermoelectric module 1, and the buffer layer 3 may be one or more selected from Ni foam, Ti foam, Cu foam, and graphite paper, but is not limited thereto, and in the present embodiment, the thickness of the buffer layer 3 on the high-temperature end side is preferably 0.3mm or less in order to release thermal expansion of the thermoelectric module 1 under high-temperature conditions.
The upper cover 4 and the base plate 5 are formed together as a case for covering the thermoelectric module 1, and the material is selected from Fe-based (stainless steel) alloy, high-temperature Ni-based alloy, or high-temperature Co-based alloy material. In the present embodiment, the thickness of the upper cover 4 is preferably 0.05mm to 0.5mm, and the thickness of the bottom plate 5 is preferably 0.05mm to 0.5 mm. The shape of the upper cover 4 is freely optimized according to the structure of the thermoelectric module 1, and may be, for example, a truncated pyramid with a rounded edge and a truncated cone, or a non-standard shaped special structure. The bottom plate 5 is formed with a through hole for mounting an output sensor 6 described later.
As shown in fig. 4, the output sensor 6 is composed of a base 62, an insulating sheath 63, and an output electrode 61, and one end to which the base 62 is attached is connected to the thermoelectric module 1 and assembled to the bottom plate 5. An insulating sleeve 63 is arranged between the base 62 and the output electrode 61. The insulating sleeve 63 is preferably made of high-temperature resin, glass, ceramic or the like, the insulation resistance between the insulating sleeve 63 and the base 62 and between the insulating sleeve 63 and the output electrode 61 is not less than 1M omega, and the leakage rate is 10-6less than or equal to Pa.L/s. In the present embodiment, the base 62 is preferably made of the same material as the upper cover 4 and the bottom plate 5.
further, the thermoelectric device D may further include: a heat insulating material 7, a volatilization suppressing material 8, and an oxygen absorbing material 9. In the space surrounded by the upper cover 4 and the base plate 5, a heat insulating material 7 is disposed in the inner space of the thermoelectric module 1 and the periphery thereof for reducing heat radiation and heat exchange between the high temperature side and the low temperature side of the thermoelectric device D. In this embodiment, the heat insulating material 7 is preferably one or more of alumina ceramic fiber, zirconia ceramic fiber, nano silica composite, aerogel, and aerogel composite.
The volatilization suppressing material 8 and the oxygen absorbing material 9 are placed on the high temperature end side in the space surrounded by the upper cover 4 and the bottom plate 5, and are wrapped with a high temperature insulating material. In the present embodiment, the volatilization suppressing material 8 is a volatile element block for suppressing the loss of the material element, and the oxygen absorbing material 9 is foam Ti for removing the residual oxygen amount.
next, a specific mounting step of the package-in-package structure thermoelectric device D according to the present invention is explained.
the preparation method of the thermoelectric device with the integrated packaging structure mainly comprises the following steps: preparing the insulating layers disposed on the high-temperature end side and the low-temperature end side of the thermoelectric module; placing a buffer layer on the high-temperature end side; connecting the positive and negative terminals of the thermoelectric module with the output electrode of the output sensor; and assembling the thermoelectric module and the output sensor on the bottom plate, covering the upper cover, and welding and sealing the upper cover and the bottom plate and the output sensor and the bottom plate in a vacuum or inert gas environment. Before the sealing step, a filling step of filling the heat insulating material into the gap and the vicinity of the periphery of the thermoelectric module may be further included.
specifically, an insulating layer 2 covering the high temperature end and the low temperature end of the thermoelectric module 1 is prepared, and a buffer layer 3 is disposed on the high temperature end side of the thermoelectric module 1. a bottom plate 5 is formed as the bottom of the case of the thermoelectric device D, on which the thermoelectric module 1 and a plurality of output sensors 6 (two as shown in fig. 1 and 2) are mounted, and it is ensured that output electrodes 61 of the output sensors 6 are fixedly connected to the positive and negative terminals of the thermoelectric module 1, respectively, for example, the output electrodes 61 of the output sensors 6 are soldered to the positive and negative terminals of the thermoelectric module 1. a space between the output electrodes 61 and a base 62 in the output sensors 6 is sealed by an insulating sleeve 63. in the space surrounded by the upper cover 4 and the bottom plate 5, an insulating material 7 is disposed in the inner gap of the thermoelectric module 1 and the periphery thereof. then, hermetic welding of the upper cover 4 and the bottom plate 5, and the base 62 and the bottom plate 5 of the output sensors 6 is performed in a vacuum or inert gas atmosphere, respectively, thereby obtaining an integrally packaged structure thermoelectric device D. if the inside of the packaged device is a vacuum environment, the vacuum degree is <10 Pa. if the inside of the packaged device is an inert gas environment, the inert gas may be argon.
meanwhile, in order to obtain a better protection effect, a volatilization suppressing material 8 for suppressing loss of volatile elements to affect material performance and an oxygen absorbing material 9 for removing residual oxygen are respectively placed near the high-temperature end side inside the space surrounded by the upper cover 4 and the bottom plate 5.
According to the invention, the thermoelectric component can be integrally packaged through a simple and easy process to obtain the thermoelectric device with an integrated packaging structure, so that the thermoelectric material and the high-temperature metal electrode are prevented from being oxidized, and the service life and the reliability of the thermoelectric device are improved. Meanwhile, in the integrated packaging process, the volatile element in the thermoelectric material is introduced into the high-temperature end, the high-temperature volatilization process is inhibited, the performance attenuation speed of the thermoelectric device is reduced, the heat insulation material is embedded into the structure of the packaging device, the heat leakage of the thermoelectric device is reduced, and the output performance of the thermoelectric device is improved.
Hereinafter, the present invention will be described in further detail with reference to specific examples.
(example 1)
Referring to FIG. 1, example 1 shows a terrace-edge structure packaged flat plate type thermoelectric device D, which is formed by magnetron sputtering on CoSb3Preparation of SiO with thickness of 20 μm on the surface of a high-temperature electrode2The coating is used as an insulating layer 2 on the high temperature end side, and Si is used on the low temperature end side3N4the copper-clad substrate was used as an insulating layer 2 on the low-temperature end side, and further, foamed Ni having a thickness of 0.2mm was placed as a buffer layer 3.
design processing is carried out to upper cover 4 and bottom plate 5 of encapsulation usefulness, and the material chooses for use in this embodiment is Fe base 304 stainless steel, and wherein upper cover 4 is the positive four-sided terrace with edges of the skirt border fillet of taking of fretwork, and the thickness of bottom plate 5 is 0.5mm, and it has two diameters of 6 mm's through-hole with output sensor 6 complex to process on it.
Firstly, the base 62 of the bottom plate 5 and the output sensor 6 are assembled and combined, and then CoSb is put3the thermoelectric module 1 is assembled with the base plate 5 and the output sensor 6, and then the output electrode 61 is fixed by soldering to the positive and negative terminals of the thermoelectric module 1, and the solder is Sn95Sb5. In the space surrounded by the upper cover 4 and the bottom plate 5, aerogel, that is, an insulating material 7 is prepared in the inner space and the periphery of the thermoelectric module 1. And insulating coated Sb blocks, namely, volatilization inhibiting materials 8 and foam Ti, namely, oxygen absorbing materials 9 are put at the side close to the high-temperature end.
then, the upper cover 4 is covered, and the precise matching of the upper cover 4 and the bottom plate 5 is realized. And putting the whole shell into a sealed box, vacuumizing, filling 1.0MPa of argon, welding the joint of the base 62 of the output sensor 6 and the bottom plate 5 by using laser welding at a welding current of 120A and a welding speed of 150 mu m/s, and continuously and annularly welding the joint of the upper cover 4 and the bottom plate 5 by using laser welding at a welding current of 150A and a welding speed of 150 mu m/s, so that the sealed packaging of the thermoelectric component 1 is realized, and the thermoelectric device D with an integrated packaging structure is obtained.
Fig. 5 shows a performance change diagram of the thermoelectric device D in the air, i.e., a performance service condition, and it can be seen from fig. 5 that the thermoelectric device D operates in the air at 526 ℃ for about 30 days at the high temperature end, and the open-circuit voltage, the internal resistance and the output power are stable, which indicates that the thermoelectric device D achieves the expected sealing protection effect.
(example 2)
Referring to fig. 2, embodiment 2 shows a terrace structure encapsulating a flat plate type thermoelectric device D. Specifically, in CoSb3base/Bi2Te3In the base segmented thermoelectric module 1, mica having a thickness of 0.04mm was placed as the insulating layer 2 on the high-temperature end side, and Al was used on the low-temperature end side2O3The copper-clad substrate is used as an insulating layer 2, and foam Cu with the thickness of 0.2mm is put in the copper-clad substrate to be used as a buffer layer 3.
then, the upper cover 4 and the bottom plate 5 for packaging are designed and processed, in this embodiment, the material is Ni-based alloy Inconel600 (73 Ni-15Cr-Ti, Al), wherein the upper cover 4 is a hollow round table with a skirt edge and a rounded corner, the thickness of the round table is 0.1mm, the thickness of the bottom plate 5 is 0.3mm, and two through holes with the diameter of 6mm, which are matched with the output sensor 6, are processed on the round table.
Firstly, the base 62 of the bottom plate 5 and the output sensor 6 are assembled and combined, and then CoSb is put3base/Bi2Te3assembling the segmented thermoelectric module 1 with the bottom plate 5 and the output sensor 6, then connecting the output electrode 61 with the positive and negative ends of the thermoelectric module 1 in a matching way, and then welding and fixing, wherein the solder is Sn95Sb5. In the space surrounded by the upper cover 4 and the bottom plate 5, in CoSb3base/Bi2Te3The inner gap and the periphery of the base segmented thermoelectric module 1 are filled with zirconia ceramic fiber, i.e., heat insulating material 7. And an insulating treated Sb block, namely, a volatilization inhibiting material 8 and foamed Ti, namely, an oxygen absorbing material 9 are put in the high-temperature end.
Then, the upper cover 4 is covered, and the precise matching of the upper cover 4 and the bottom plate 5 is realized. And putting the whole shell into a sealed box, vacuumizing, filling 1.0MPa of argon, welding the joint of the base 62 of the output sensor 6 and the bottom plate 5 by using laser welding at a welding current of 120A and a welding speed of 150 mu m/s, and continuously and annularly welding the joint of the upper cover 4 and the bottom plate 5 by using laser welding at a welding current of 160A and a welding speed of 150 mu m/s, so that the sealed packaging of the thermoelectric component 1 is realized, and the thermoelectric device D with an integrated packaging structure is obtained.
(example 3)
Referring to fig. 3, embodiment 3 is a packaged thermoelectric device D of a Y-shaped structure. Firstly, an AlN insulating layer 2 having a thickness of 20 μm was formed on the high temperature side of a thermoelectric module 1 of Y-type Half-Heusler alloy, and a BN coated insulating layer 2 having a thickness of 25 μm was formed on the low temperature side. Then, graphite paper having a thickness of 0.2mm was put in the high temperature end side as the cushion layer 3.
the upper cover 4 and the bottom plate 5 for packaging are designed and processed, and in the embodiment, the material is Co-based alloy Co70Cr28Fe21Si, wherein the upper cover 4 is a hollowed rectangular prismoid with a rounded corner at the skirt edge, the thickness is 0.1mm, the thickness of the bottom plate 5 is 0.3mm, and two through holes with the diameter of 6mm matched with the output sensor 6 are processed on the bottom plate.
Firstly assembling and combining the base plate 5 and the base 62 of the output sensor 6, then assembling the thermoelectric component 1 of the Half-Heusler alloy with the base plate 5 and the output sensor 6, then matching and connecting the output electrode 61 with the positive and negative ends of the thermoelectric component 1 and then welding and fixing, wherein the welding flux is Sn95Sb5. In the space surrounded by the upper cover 4 and the base plate 5, a nano silica composite material, i.e., a heat insulating material 7 is filled in the inner space and the outer periphery of the thermoelectric module 1.
Then, the upper cover 4 is covered, and the precise matching of the upper cover 4 and the bottom plate 5 is realized. The whole shell is placed into a sealed box and is vacuumized to 10Pa, the joint of the base 62 and the bottom plate 5 of the output sensor 6 is welded by laser welding at the welding current of 120A and the welding speed of 150 mu m/s, and then the joint of the upper cover 4 and the bottom plate 5 is welded by resistance welding at the welding current of 5000A and the welding pressure of 2.0KN, so that the thermoelectric component 1 is sealed and packaged, and the thermoelectric device D with the integrated packaging structure is obtained.
The above embodiments are intended to illustrate and not to limit the scope of the invention, which is defined by the claims, but rather by the claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (8)
1. A thermoelectric device having an integrated package structure, comprising:
A thermoelectric module including at least a pair of P-type and N-type thermoelectric materials and having a high temperature end and a low temperature end;
insulation layers provided on a high temperature end side and a low temperature end side of the thermoelectric module;
a buffer layer provided on a high-temperature end side of the thermoelectric module;
an upper cover integrally covering the thermoelectric module, the insulating layer and the buffer layer;
a bottom plate for placing the thermoelectric module and forming a closed housing space with the upper cover; and
a plurality of output sensors respectively connected with the thermoelectric module and the bottom plate in an assembling way;
The shell space enclosed by the upper cover and the bottom plate also comprises:
Thermal insulation materials placed in the inner gap and the periphery of the thermoelectric component;
A volatilization suppressing material provided on a high-temperature end side of the thermoelectric module; and
And the oxygen absorbing material is arranged near the high-temperature end of the thermoelectric module.
2. The one-piece package structure thermoelectric device of claim 1,
The heat insulating material is one or more of alumina ceramic fiber, zirconia ceramic fiber, nano silicon dioxide composite material, aerogel and aerogel composite material.
3. the one-piece package structure thermoelectric device of claim 1,
the thermoelectric component is selected from Bi-Te based alloy, Pb-Te based alloy, CoSb3A single-stage component, a multi-stage component or a cascade component composed of one or more thermoelectric materials selected from the group consisting of skutterudite, Mg-Si-based alloys, diamond-like compounds, Half-Heusler alloys, SiGe-based alloys, and Ziegler phase compounds.
4. The one-piece package structure thermoelectric device of claim 1,
the insulation resistance of the insulation layer is more than or equal to 1M omega, wherein the thickness of the insulation layer at the high-temperature end side is less than or equal to 0.2mm, and the thickness of the insulation layer at the low-temperature end side is less than or equal to 0.5 mm.
5. The one-piece package structure thermoelectric device of claim 1,
the buffer layer is one or more selected from foamed Ni, foamed Ti, foamed Cu and graphite paper, and the thickness is less than or equal to 0.3 mm.
6. the one-piece package structure thermoelectric device of claim 1,
The upper cover and the bottom plate are both made of Fe-based alloy, Ni-based alloy or Co-based alloy materials;
The thickness of the upper cover is 0.05 mm-0.5 mm, and the thickness of the bottom plate is 0.05 mm-0.5 mm.
7. The one-piece package structure thermoelectric device of claim 1,
the output sensor includes: the thermoelectric module comprises a base used for being assembled and fixed with the bottom plate, an output electrode used for being electrically connected with the thermoelectric module, and an insulating sleeve arranged between the base and the output electrode.
8. A method for preparing the integrally packaged structure thermoelectric device according to any one of claims 1 to 7, comprising:
preparing insulating layers arranged on the high-temperature end side and the low-temperature end side of the thermoelectric module;
placing a buffer layer on the high-temperature end side;
Connecting the positive and negative terminals of the thermoelectric assembly with the output electrode of the output sensor; and
assembling the thermoelectric assembly and the output sensor on a bottom plate, covering an upper cover, and welding and sealing the upper cover and the bottom plate, and the output sensor and the bottom plate in a vacuum or inert gas environment,
Before the sealing, a heat insulating material is filled in the inner gap and the vicinity of the periphery of the thermoelectric module.
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| RU209979U1 (en) * | 2021-05-19 | 2022-03-24 | Общество с ограниченной ответственностью "Завод "Кристалл" | THERMOELECTRIC MODULE |
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| CN110061123A (en) * | 2019-05-24 | 2019-07-26 | 航天特种材料及工艺技术研究所 | A kind of lower thermal conductivity thermo-electric device and preparation method thereof |
| CN111261793B (en) * | 2020-01-20 | 2021-11-02 | Tcl华星光电技术有限公司 | Display panel, preparation method thereof and display device |
| CN113161473B (en) * | 2021-04-19 | 2023-02-17 | 武汉理工大学 | Method for improving performance of p-type polycrystalline bismuth telluride material and preparation method |
| CN113257758B (en) * | 2021-05-11 | 2022-06-28 | 上海空间电源研究所 | Novel thermoelectric device integrated module for high temperature area |
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| CN101217177A (en) * | 2004-08-31 | 2008-07-09 | 株式会社东芝 | Thermoelectric conversion device |
| CN104890325A (en) * | 2014-03-03 | 2015-09-09 | 中国科学院上海硅酸盐研究所 | Protective coating for thermoelectric material or thermoelectric device |
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| CN101217177A (en) * | 2004-08-31 | 2008-07-09 | 株式会社东芝 | Thermoelectric conversion device |
| CN104890325A (en) * | 2014-03-03 | 2015-09-09 | 中国科学院上海硅酸盐研究所 | Protective coating for thermoelectric material or thermoelectric device |
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| RU209979U1 (en) * | 2021-05-19 | 2022-03-24 | Общество с ограниченной ответственностью "Завод "Кристалл" | THERMOELECTRIC MODULE |
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