CN105742470A - Thermoelectric module structure and method of manufacturing the same - Google Patents
Thermoelectric module structure and method of manufacturing the same Download PDFInfo
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- CN105742470A CN105742470A CN201410753318.7A CN201410753318A CN105742470A CN 105742470 A CN105742470 A CN 105742470A CN 201410753318 A CN201410753318 A CN 201410753318A CN 105742470 A CN105742470 A CN 105742470A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 305
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- 238000009792 diffusion process Methods 0.000 claims abstract description 66
- 238000009413 insulation Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
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- 239000004332 silver Substances 0.000 claims description 17
- 229910002665 PbTe Inorganic materials 0.000 claims description 15
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 15
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- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
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- 238000009434 installation Methods 0.000 claims description 11
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000679 solder Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- 229910018985 CoSb3 Inorganic materials 0.000 claims description 2
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- 229910052759 nickel Inorganic materials 0.000 description 10
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- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
The invention discloses a thermoelectric module structure and a manufacturing method thereof. The thermoelectric element is disposed on the substrate. The insulation protection structure is disposed around the thermoelectric element. The thermoelectric element includes at least three electrode plates, a first type thermoelectric material, a second type thermoelectric material and a diffusion barrier structure. A first electrode plate and a second electrode plate among the three electrode plates are disposed on the substrate. The first type thermoelectric material is disposed on the first electrode plate. The second type thermoelectric material is disposed on the second electrode plate. A third electrode plate among the three electrode plates is disposed on the first type thermoelectric material and the second type thermoelectric material. The diffusion barrier structure is disposed at both ends of the first type thermoelectric material and the second type thermoelectric material. In addition, a method of fabricating a thermoelectric module structure is also provided.
Description
Technical field
The present invention relates to a kind of modular structure and manufacture method thereof, and particularly relate to a kind of thermoelectric module architecture and manufacture method thereof.
Background technology
Electrothermal module is applied in Waste Heat Recovery utilization has become trend.For the application of temperature in response to used heat, middle high-temperature thermoelectric material and electrothermal module are developed in the recent period gradually.But, the operating temperature of warm thermoelectric material is 200～600 DEG C, and the fusing point of refrigerated module rich tin solder used is both less than 232 DEG C.When application of temperature is higher than 200 DEG C, most solders can melt, and causes the problems such as structure collapses.In now, temperature electrothermal module is for avoiding the problems referred to above, adopts two kinds of manufacture methods at present, and one is diffusion-bondingmethod (Diffusionbondingmethod), another kind of for hard solder method (Brazingmethod).Diffusion-bondingmethod is to apply pressure simultaneously and improve ambient temperature on material, and two kinds of solid-state materials are made directly a kind of mode of affixed conjunction.Atom is utilized to carry out diffusion mutually on joint interface to reach the purpose engaged.Ambient temperature during joint be generally two solid-state materials fusing point more than half to accelerate the diffusion of atom.The purpose pressurizeed is then eliminate the hole that two articles is formed because rough surface contacts with each other.Diffusion-bondingmethod can cause that extremely serious is problem of oxidation.That is, if the surface of grafting material forms stable oxide under high temperature, it will the quality that impact engages, for instance mechanical strength reduction, thermal resistance and resistance raise and makes the electrothermal module figure of merit and decrease in efficiency etc..Further, in pressure process, the plastic deformation of junction also can reduce material function.
If additionally, the temperature of module assembled is too high, except causing atom and spreading the deterioration accelerating thermoelectric material in a large number, thermal coefficient of expansion is still had not mate the reliability issues etc. that (CTEmismatch) causes.Low temperature electrothermal module often uses nickel as diffused barrier layer, it is possible to effectively stop the diffusion of stannum, copper and silver, but nickel is susceptible to diffusion reaction with the tellurium in thermoelectric material, generate nickel tellurium (NiTe) Jie's metal.Meanwhile, nickel also easily diffuses to the Bi of N-type2Te3In and affect the function of thermoelectric material.Above two situation all can deteriorate the performance of thermoelectric material.If it addition, correlational study is pointed out nickel as warm thermoelectric material Pb0.5Sn0.5The diffused barrier layer of Te, interface place after assembling can produce Jie's metallic compound one layer complicated, causes interface resistance to be substantially increased.This kind of behavior can reduce the effective figure of merits of module, and it is instant for therefore developing more suitable diffused barrier layer to replace the use of nickel.
Summary of the invention
It is an object of the invention to provide a kind of thermoelectric module architecture and manufacture method thereof, there is high temperature protection (hightemperatureprotection) and diffusion barrier (diffusionbarrier) function.
For reaching above-mentioned purpose, the structure of a kind of electrothermal module of the present invention includes at least one substrate, a thermoelement, at least three battery lead plate and an insulation protection structure.Thermoelement is arranged at least one substrate.Insulation protection structure is arranged at around thermoelement.Thermoelement includes at least three battery lead plate, one first type thermoelectric material, a Second-Type thermoelectric material and a diffusion barrier structure.One first battery lead plate in the middle of at least three battery lead plate and one second battery lead plate are arranged at least one substrate as one end of thermoelement.First type thermoelectric material is arranged on the first battery lead plate.One end of first type thermoelectric material electrically connects with the first battery lead plate.Second-Type thermoelectric material is arranged on the second battery lead plate.One end of Second-Type thermoelectric material electrically connects with the second battery lead plate.One the 3rd battery lead plate in the middle of at least three battery lead plate is arranged on the first type thermoelectric material and Second-Type thermoelectric material as the other end of thermoelement.The other end of the 3rd battery lead plate and the first type thermoelectric material and the other end electrical connection of Second-Type thermoelectric material.Diffusion barrier structure is arranged in the two ends of the first type thermoelectric material and Second-Type thermoelectric material.
The manufacture method of a kind of electrothermal module of the present invention comprises the steps.A diffusion barrier structure is formed at the two ends of one first type thermoelectric material and a Second-Type thermoelectric material.One second battery lead plate of one first battery lead plate sum in the middle of at least three battery lead plate is arranged at least one substrate as one end of a thermoelement.Respectively two ends are included the first type thermoelectric material of diffusion barrier structure and Second-Type thermoelectric material is arranged on the second battery lead plate of the first battery lead plate sum in the middle of at least three battery lead plate.One the 3rd battery lead plate in the middle of at least three battery lead plate is arranged in two ends as the other end of thermoelement and includes on the first type thermoelectric material and the Second-Type thermoelectric material of diffusion barrier structure, to form a thermoelement.Formation one insulation protection structure around thermoelement, to form an electrothermal module.One end of first type thermoelectric material electrically connects with the first battery lead plate.One end of Second-Type thermoelectric material electrically connects with the second battery lead plate.The other end of the 3rd battery lead plate and the first type thermoelectric material and the other end electrical connection of Second-Type thermoelectric material.
Based on above-mentioned, the electrothermal module of the present invention includes insulation protection structure, and it can be avoided the material at high temperature oxidation of each element and layer structure and deteriorate.The electrothermal module of the present invention includes the diffusion barrier structure of single or multiple lift to be had buffering and reduces the unmatched function of thermal coefficient of expansion.
For the features described above of the present invention and advantage can be become apparent, special embodiment below, and coordinate appended accompanying drawing to be described in detail below.
Accompanying drawing explanation
The schematic diagram of the structure of the electrothermal module of the multiple different exemplary embodiment of Fig. 1, Fig. 5, Fig. 7 to Fig. 8, Figure 10 to Figure 12, Figure 14 respectively present invention；
Fig. 2 is the schematic diagram of the manufacture method of the thermoelectricity bulk of the present invention one exemplary embodiment；
The upper schematic diagram of Fig. 3 a and insulation protection structure model that Fig. 3 b is Fig. 2 and schematic side view；
The schematic diagram of the manufacture method of the electrothermal module of the multiple different exemplary embodiment of Fig. 4, Fig. 6, Fig. 9, Figure 13 respectively present invention；
The schematic diagram of the structure of the thermoelectricity pin of the multiple different exemplary embodiment of Figure 15, Figure 16 respectively present invention；
The structure of the thermoelectricity pin of the multiple different exemplary embodiment of Figure 17, Figure 18 respectively present invention and the schematic diagram of connected structure；
The pyroelecthc properties figure of Figure 19 a～Figure 19 d respectively layer structure Ag/PbTe/Ag of the present invention one exemplary embodiment.
Symbol description
100,300,400,500,600,700,800,900: electrothermal module
110,310,410,510,610,710,810,910: first substrate
120,420,620,720,820,920: second substrate
130A, 330A, 430A, 530A, 630A, 730A, 830A, 930A: the first battery lead plate
130B, 330B, 430B, 530B, 630B, 730B, 830B, 930B: the second battery lead plate
140,340,440,540,640,740,840,940: the three battery lead plate
150,350,450,550,650,750,850,950: thermoelement
1150,1250,1350,1450: thermoelectricity pin
152,352,452,552,652,752,852,952: the first diffused barrier layer
154,354,454,554,654,754,854,954: the second diffused barrier layer
156A, 356A, 456AL, 456AH, 556A, 656A, 756AL, 756AH, 856A, 956AL, 956AH: the first type thermoelectric material
156B, 356B, 456BL, 456BH, 556B, 656B, 756BL, 756BH, 856B, 956BL, 956BH: Second-Type thermoelectric material
1156,1256,1356,1456: thermoelectric material
160,360,460,560,660,760,860,960,1360: the first connected structure
170,370,470,570,670,770,870,970,1370: the second connected structure
180,380,480,580,680,780,880,980: insulation protection structure
200: thermoelectricity bulk
453,753,953: the three diffused barrier layer
1152,1154,1252,1254,1352,1354,1452,1454: diffusion barrier structure
S: element installation space
S200, S210, S220, S230: the step of thermoelectricity bulk manufacture method
S300, S310, S320, S400, S410, S420, S430, S600, S610, S620, S630, S900, S910, S920, S930: the step of electrothermal module manufacture method
Detailed description of the invention
It is said that in general, the current application of temperature of electrothermal module is constantly improve.High temperature load causes that thermoelectric material can produce spontaneous volatilization and precipitate out.In the related, electrothermal module is generally only at its one layer of sealing ring of peripheral cladding, it is ensured that the temperature stabilization of inside modules, but often excessive temperature is likely to result in material oxidation or air blasting behavior.Additionally, be applied in the electrothermal module of middle high temperature, diffused barrier layer therein is under high temperature load, it is impossible to restrain the diffusion reaction between thermoelectric material and the material of connected structure.Diffusion reaction between the material of each structure is easily caused the generation of Jie's metallic compound, hole and crackle.
The present invention proposes to utilize resistant to elevated temperatures insulating cement material directly to cover around thermoelectricity bulk, as insulation protection structure, to avoid high temperature for causing oxidation, material volatilization around thermoelement and precipitating out.In the present invention, the form of insulation protection structure cladding thermoelement at least can be divided into two kinds.One of which is such as thermoelectricity pin cladding, and the insulation protection structure of this kind of form is to directly overlay the surface beyond as the two ends of each thermoelement of thermoelectricity pin, and fits tightly, that is around the insulation protection structure of this example substantially cover heating electric device.Another kind is such as that module space is completely coated with, and the insulation protection structure of this kind of form is substantially fully filled with inside electrothermal module by the space between substrate, battery lead plate and thermoelectric material three.That is the substantially complete space filled up in module of insulation protection structure of this example.It addition, the insulation protection structure of the present invention can also be disposed on the barrier structure on substrate.This barrier structure is around all thermoelements within electrothermal module, and forms the confined space of a vacuum state with upper and lower base plate or battery lead plate.On the other hand; the present invention is in conjunction with resistant to elevated temperatures insulation protection structure, when thermoelectric material is when preparing into bulk, and can in hot pressing; complete together with thermoelectric material and diffusion barrier structure batch (batch), thus reduce Making programme and the time of electrothermal module.
Additionally, the present invention provides utilizes dystectic material, for instance glass, glaze paint or pottery, as the insulation protection structure of middle high temperature thermoelectric module, thermoelectric material generating gasification and vaporization behaviors under middle high temperature load can be avoided, affect properties of materials.It addition, modular thermoelement quickly by diffusion barrier structure and thermoelectric material batch hot pressing, to form array thermoelectricity pin, can be greatly reduced material Production Time.The thermoelectric module architecture of the present invention also utilizes suitable metal material to hinder structure as the diffusion group of electrothermal module, the material of metal material or contact alloys and thermoelectric material to restrain connected structure produces cross-diffusion impact, prevent hole or crackle from generating, it is to avoid to affect element reliability.Multiple exemplary embodiment set forth below illustrates the present invention, but the present invention is not limited only to illustrated multiple exemplary embodiment.Suitable combination is also still allowed for again between exemplary embodiment.
Fig. 1 illustrates the schematic diagram of the structure of the electrothermal module of the present invention one exemplary embodiment.Refer to Fig. 1, the electrothermal module 100 of this exemplary embodiment includes first substrate 110, second substrate 120 and at least one thermoelement 150.Thermoelement 150 includes one first battery lead plate 130A, one second battery lead plate 130B, one the 3rd battery lead plate 140.First substrate 110, thermoelement 150 and second substrate 120 form stacked arrangement.First battery lead plate 130A and the second battery lead plate 130B is arranged on first substrate 110 as one end of thermoelement 150.3rd battery lead plate 140 is arranged on the first type thermoelectric material 156A and Second-Type thermoelectric material 156B as the other end of thermoelement 150.In this exemplary embodiment, the assembling of electrothermal module 100 is such as with hard solder method or solid-liquid diffusing joining method or utilizes nano silver material to engage each element and layer structure, and to form stacked structure, but the present invention is not any limitation as.In an exemplary embodiment, the assembling of electrothermal module 100 can also be reach electric connection in the way of direct pressing.
In this exemplary embodiment; the surrounding of thermoelement 150 includes an insulation protection structure 180; the first type thermoelectric material 156A and Second-Type thermoelectric material 156B at least can be avoided by producing oxidation, material volatilization under high temperature load, precipitating out or deterioration, have influence on the output performance of electrothermal module 100.In this exemplary embodiment, the material of insulation protection structure 180 be chosen from glass, glaze paint and pottery three one of them, but the present invention is not any limitation as.In this exemplary embodiment, insulation protection structure 180 is completely to be coated with the space within electrothermal module 100.It is to say, insulation protection structure 180 to be substantially fully filled with electrothermal module 100 internal by first substrate the 110, first battery lead plate 130A, the second battery lead plate 130B, the first type thermoelectric material 156A, Second-Type thermoelectric material 156B, space between the 3rd battery lead plate 140 and second substrate 120.In an exemplary embodiment, insulation protection structure 180 also can be not filled with the space between the internal first type thermoelectric material 156A and Second-Type thermoelectric material 156B of electrothermal module 100, makes to keep between the two the state of cavity.
In this exemplary embodiment, thermoelement 150 also includes the first type thermoelectric material 156A, Second-Type thermoelectric material 156B and a diffusion barrier structure.This diffusion barrier structure is arranged respectively at the two ends of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B, in this exemplary embodiment, the two ends of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B include diffusion barrier structure, i.e. the first diffused barrier layer 152 and the second diffused barrier layer 154, respectively in order to stop the material of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B and first, second connected structure 160,170 to spread each other.In this exemplary embodiment, the two ends being positioned at the first type thermoelectric material 156A and Second-Type thermoelectric material 156B are first, second diffused barrier layer 152,154 of simple layer respectively, its material be such as chosen from silver, copper, aluminum and germanium one of them.In another exemplary embodiment, diffusion barrier structure can include the diffused barrier layer of multiple structure, the combination of its material be such as chosen from silver/germanium, copper/germanium, silver/carbon and copper/carbon one of them, can effectively stop the material composition diffusion of its both sides and reduce stress, also the unmatched problem of thermal coefficient of expansion (coefficientofthermalexpansionmismatch, CTEmismatch) can be improved further.It should be noted that in this exemplary embodiment, be positioned at the quantity of the diffused barrier layer included by diffusion barrier structure at the two ends of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B and the selection of material thereof only in order to illustrate, the present invention is not limited to this.In an exemplary embodiment, the diffused barrier layer of multiple structure can integrate, by heterogeneity and the material layer of concentration constitute, form the diffused barrier layer of a functionally gradient (functionalgrade), it is possible to effectively stop the material composition diffusion of its both sides and reduce stress.In this instance, the material that diffused barrier layer can also be progressive composition forms, and has stress buffer and improves the unmatched problem of thermal coefficient of expansion.In another exemplary embodiment, the diffusion barrier structure at the two ends being positioned at the first type thermoelectric material 156A and Second-Type thermoelectric material 156B also can be combined into a single layer structure by first, second connected structure 160,170 each stacking with it.
In this exemplary embodiment, the first type thermoelectric material 156A and Second-Type thermoelectric material 156B is electrically connected to each other with the first battery lead plate 130A, the second battery lead plate 130B and the 3rd battery lead plate 140.First type thermoelectric material 156A and Second-Type thermoelectric material 156B can be connect resistance state connection or resistance state connection in parallel, and the present invention is not any limitation as.In this exemplary embodiment, electrothermal module 100 also includes the first connected structure 160 and the second connected structure 170.First connected structure 160 is arranged between the first type thermoelectric material 156A and the first battery lead plate 130A, and is arranged between Second-Type thermoelectric material 156B and the second battery lead plate 130B.Therefore, one end of the first type thermoelectric material 156A electrically connects with the first battery lead plate 130A, and one end of Second-Type thermoelectric material 156B electrically connects with the second battery lead plate 130B.Second connected structure 170 is arranged between the first type thermoelectric material 156A and the three battery lead plate 140, and is arranged between Second-Type thermoelectric material 156B and the three battery lead plate 140.Therefore, the other end of the first type thermoelectric material 156A and the other end and the 3rd battery lead plate 140 of Second-Type thermoelectric material 156B electrically connect.First connected structure 160 and the second connected structure 170 are in order to as assembling solder, engage the first diffused barrier layer 152 and the first battery lead plate 130A, the second battery lead plate 130B of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B respectively, and engage second diffused barrier layer 154 and the 3rd battery lead plate 140 of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B.In this exemplary embodiment, the first connected structure 160 and the second connected structure 170 include can by the metal of conduction or nonmetallic materials, and the present invention is not any limitation as.In this exemplary embodiment, the forming method of the first connected structure 160 and the second connected structure 170 includes but not limited to include galvanizing process, electroless plating program, sputter use or chemical vapour deposition procedure.In the exemplary embodiment assembling electrothermal module 100 with solid-liquid diffusing joining method, the first connected structure 160 and the second connected structure 170 can be tin metal thin film.
Though it should be noted that Fig. 1 only illustrates electrothermal module 100 includes two the first type thermoelectric material 156A and Second-Type thermoelectric material 156B thermoelectricity pin as thermoelement 150, but its quantity is only in order to illustrate, the present invention is not any limitation as.From depression angle, the first type thermoelectric material 156A and Second-Type thermoelectric material 156B is arranged on first substrate 110 in the form of an array, to form multiple thermoelement 150.In this exemplary embodiment, the first type thermoelectric material 156A and Second-Type thermoelectric material 156B includes can by the material that hot-cast socket is electricity, and it can be P type thermoelectric material or N-type thermoelectric material.For example, each thermoelectric material 156 includes Bi2Te3、GeTe、PbTe、CoSb3Or Zn4Sb3Series alloy material, but the invention is not restricted to this.In this exemplary embodiment, the first type thermoelectric material 156A is such as P type thermoelectric material, and Second-Type thermoelectric material 156B is such as N-type thermoelectric material.But the present invention is not any limitation as, in an exemplary embodiment, the first type thermoelectric material 156A is such as N-type thermoelectric material, and Second-Type thermoelectric material 156B is such as P type thermoelectric material.
In this exemplary embodiment, material and the first type thermoelectric material 156A and Second-Type thermoelectric material 156B of diffused barrier layer can form Jie's metallic compound, at least can strengthen the operating characteristics of thermoelement 150.Material at diffused barrier layer is in the exemplary embodiment that silver-colored and each thermoelectric material is PbTe alloy material, can form Ag between diffused barrier layer and each thermoelectric material2Jie's metallic compound of Te, can improve the thermoelectric figure of merit coefficient of thermoelement.
Fig. 2 illustrates the manufacture method of the thermoelectricity bulk of the present invention one exemplary embodiment.Fig. 3 a and Fig. 3 b illustrates upper schematic diagram and the schematic side view of the insulation protection structure model of Fig. 2 respectively.Refer to Fig. 1 to Fig. 3 b, electrothermal module 100 for Fig. 1, before substrate the 110,120, first battery lead plate 130A, the second battery lead plate 130B, the 3rd battery lead plate 140 being engaged with the first type thermoelectric material 156A and Second-Type thermoelectric material 156B, the present invention batch making in advance can include the thermoelectricity bulk 200 of the first type thermoelectric material 156A and Second-Type thermoelectric material 156B and diffusion barrier structure 152,154.In this exemplary embodiment, the model of insulation protection structure 180 is to be initially formed multiple element installation space S, step S200 as shown in Figure 2 with array way arrangement on insulation protection bulk.Therefore, Fig. 3 a and Fig. 3 b illustrated only include the model of insulation protection structure 180, not yet form the first type thermoelectric material 156A and Second-Type thermoelectric material 156B in its element installation space S.Then, in step S210, in each element installation space S, the first diffused barrier layer 152 is formed.Afterwards, in step S220, the first different diffused barrier layers 152 forms the first type thermoelectric material 156A and Second-Type thermoelectric material 156B respectively.Then, in step S230, the first type thermoelectric material 156A and Second-Type thermoelectric material 156B forms the second diffused barrier layer 154 respectively.So far, the thermoelectricity bulk 200 of this exemplary embodiment completes, and in its element installation space S, each self-forming is as the first type thermoelectric material 156A and Second-Type thermoelectric material 156B of thermoelectricity pin.That is, first diffused barrier layer the 152, first type thermoelectric material 156A, Second-Type thermoelectric material 156B and the second diffused barrier layer 154 form the thermoelectricity pin of stacked structure in each element installation space S.In this exemplary embodiment, the forming method of first, second diffused barrier layer 152,154 includes but not limited to include galvanizing process, electroless plating program, sputter use or chemical vapour deposition procedure.In this exemplary embodiment; the manufacture method of thermoelectricity bulk 200 such as may utilize the direct hot pressing of model of resistant to elevated temperatures insulation protection structure; to form array thermoelectricity bulk 200; it is simultaneously hot-forming with thermoelectric material that its each element installation space S comprises diffused barrier layer, makes and module assembled time-histories thus thermoelectricity bulk can be reduced.
Fig. 4 illustrates the manufacture method of the electrothermal module of the present invention one exemplary embodiment.Refer to Fig. 1 and Fig. 4, for the electrothermal module 100 of Fig. 1, in this exemplary embodiment, first, in step S400, it is provided that second substrate 120, it has been pre-formed the 3rd battery lead plate 140 and the second connected structure 170.Then, in step S410, thermoelectricity bulk 200 is arranged on first substrate 110.In this step, first substrate 110 has been pre-formed the first battery lead plate 130A, the second battery lead plate 130B and the first connected structure 160.In this exemplary embodiment, thermoelectricity bulk 200 is such as carry out a batch manufacture with the manufacture method illustrated in Fig. 2 to complete, but the present invention is not any limitation as.Afterwards, in the step s 420, first substrate 110 and second substrate 120 are assembled, forms the stacked structure of first substrate the 110, first battery lead plate 130A, the second battery lead plate 130B, the first type thermoelectric material 156A, Second-Type thermoelectric material 156B, the 3rd battery lead plate 140 and second substrate 120.In this step, the assembling mode of electrothermal module 100 is such as with hard solder method or solid-liquid diffusing joining method or utilizes nano silver material to engage each element and layer structure, to form stacked structure.In an exemplary embodiment, the assembling mode of electrothermal module 100 can also be by a pressurized, heated program, or directly pressing program engages each element and layer structure, and the present invention is not any limitation as.Then, in step S430, then insulation protection structure 180 is filled the space of full electrothermal module 100, with each element and the layer structure of adequately protecting.
Fig. 5 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 1 and Fig. 5, the electrothermal module 500 of this exemplary embodiment is similar to the electrothermal module 100 of Fig. 1 exemplary embodiment, but the electrothermal module 500 that difference main between the two is such as in that this exemplary embodiment does not include second substrate 170.In this exemplary embodiment, it does not have including the electrothermal module 500 of second substrate when thermo-electric conversion is applied, its 3rd battery lead plate 540 is such as directly against being attached to thermal source not over second substrate.This mode can avoid second substrate to cause the material degradation of second substrate because being attached to thermal source for a long time, or produces between the material of second substrate and the 3rd battery lead plate 540 physically or chemically to change the conversion efficiency of thermoelectric and the output performance that affect electrothermal module 500.
Fig. 6 illustrates the manufacture method of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 4 to Fig. 6, the manufacture method of the electrothermal module of this exemplary embodiment is similar to the manufacture method of the electrothermal module of Fig. 4 exemplary embodiment, but difference main between the two is such as follows.For the electrothermal module 500 of Fig. 5, in this exemplary embodiment, step S600 is provided the 3rd battery lead plate 540, and it has been pre-formed the second connected structure 570.Additionally, in step S620, the stacked structure being completed includes first substrate the 510, first battery lead plate 530A, the second battery lead plate 530B, the first type thermoelectric material 556A, Second-Type thermoelectric material 556B and the 3rd battery lead plate 540, it does not have include second substrate.
It addition, the electrothermal module 500 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Fig. 1 to Fig. 4 exemplary embodiment, therefore can repeat no more.
Fig. 7 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 1 and Fig. 7, the electrothermal module 700 of this exemplary embodiment is similar to the electrothermal module 100 of Fig. 1 exemplary embodiment, but difference main between the two be such as in that the electrothermal module 700 of this exemplary embodiment be Second-Type thermoelectric material 756BH, 756BL structure using first type thermoelectric material 756AH, 756AL of stack and stack as thermoelectricity pin, promote the output performance of electrothermal module 700.Thermoelectric material 756AH, 756AL, 756BH, 756BL can select corresponding material system according to different temperatures end.When thermo-electric conversion is applied, first substrate 710 and second substrate 720 are such as proximate to the application end of low-temperature receiver and thermal source respectively, and therefore, thermoelectric material 756AH, 756AL, 756BH, 756BL may select applicable material system, to meet practical application request.In this exemplary embodiment, one the 3rd diffused barrier layer 753 is also included between first type thermoelectric material 756AH, 756AL, and also include the 3rd diffused barrier layer 753 between Second-Type thermoelectric material 756BH, 756BL, spread each other between the material molecule of thermoelectric material 756AH, 756AL, 756BH, 756BL in order to stop, affect conversion efficiency of thermoelectric and the output performance of electrothermal module 700.In another exemplary embodiment, electrothermal module 700 can not also include second substrate 170.
It addition, the electrothermal module 700 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Fig. 1 to Fig. 6 exemplary embodiment, therefore can repeat no more.
Fig. 8 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 1 and Fig. 8, the electrothermal module 800 of this exemplary embodiment is similar to the electrothermal module 100 of Fig. 1 exemplary embodiment, but the insulation protection structure 880 that difference main between the two is such as in that this exemplary embodiment is thermoelectricity pin cladding form.In this exemplary embodiment; insulation protection structure 880 be directly overlay as the first type thermoelectric material 856A of thermoelectricity pin, Second-Type thermoelectric material 856B two ends beyond surface; and fit tightly, that is the insulation protection structure 880 of this example is that substantially cover heating electric device 850 is around.
Fig. 9 illustrates the manufacture method of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 8 and Fig. 9, the manufacture method of the electrothermal module of this exemplary embodiment is similar to the manufacture method of the electrothermal module of Fig. 4 exemplary embodiment, but difference main between the two is such as follows.Electrothermal module 800 for Fig. 8, in this exemplary embodiment, the first substrate 810 that step S910 provides, it has been pre-formed the first battery lead plate 830A, the second battery lead plate 830B and the first connected structure 860, and batch has completed multiple thermoelement 850 with array way arrangement.In this step, surrounding's not yet coated insulation protection structure 880 of the first type thermoelectric material 856A, Second-Type thermoelectric material 856B.In addition; in step S930; again by assembling, the electrothermal module 800 that engaged is immersed in liquid or dissolve the high temperature insulation material of state then extract solidification out or mist spill (spray) high temperature insulation material around the first type thermoelectric material 856A, Second-Type thermoelectric material 856B (namely by spraying or in the way of soaking around the first type thermoelectric material 856A, Second-Type thermoelectric material 856B formation high temperature insulation material), to form insulation protection structure 880 to protect each element and layer structure.Therefore, in the exemplary embodiment of the present invention, insulation protection structure is not necessarily required to extend to around substrate.
It addition, the electrothermal module 800 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Fig. 1 to Fig. 4 exemplary embodiment, therefore can repeat no more.
Figure 10 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 8 and Figure 10, the electrothermal module 300 of this exemplary embodiment is similar to the electrothermal module 800 of Fig. 8 exemplary embodiment, but the electrothermal module 300 that difference main between the two is such as in that this exemplary embodiment does not include second substrate 820.In this exemplary embodiment, it does not have including the electrothermal module 300 of second substrate when thermo-electric conversion is applied, its 3rd battery lead plate 340 is such as directly against being attached to thermal source not over second substrate.This mode can avoid second substrate to cause the material degradation of second substrate because being attached to thermal source for a long time, or produces between the material of second substrate and the 3rd battery lead plate physically or chemically to change the conversion efficiency of thermoelectric and the output performance that affect electrothermal module 300.
It addition, the electrothermal module 300 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Fig. 6, Fig. 8 and Fig. 9 exemplary embodiment, therefore can repeat no more.
Figure 11 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 8 and Figure 11, the electrothermal module 400 of this exemplary embodiment is similar to the electrothermal module 800 of Fig. 8 exemplary embodiment, but difference main between the two is such as in that the electrothermal module 400 of this exemplary embodiment uses Second-Type thermoelectric material 456BH, 456BL of first type thermoelectric material 456AH, 456AL of stack and stack as thermoelectricity pin, promotes the output performance of electrothermal module 400.Thermoelectric material 456AH, 456AL, 456BH, 456BL can select corresponding material system according to different temperatures end.When thermo-electric conversion is applied, first substrate 410 and second substrate 420 are such as proximate to the application end of low-temperature receiver and thermal source respectively, and therefore, thermoelectric material 456AH, 456AL, 456BH, 456BL may select applicable material system, to meet practical application request.In this exemplary embodiment, one the 3rd diffused barrier layer 453 is also included between thermoelectric material 456AH, 456AL, and also include the 3rd diffused barrier layer 453 between thermoelectric material 456AH, 456AL, spread each other between the material molecule of thermoelectric material 456AH, 456AL, 456BH, 456BL in order to stop, affect conversion efficiency of thermoelectric and the output performance of electrothermal module 400.In another exemplary embodiment, electrothermal module 400 can not also include second substrate 870.
It addition, the electrothermal module 400 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Fig. 8 to Figure 10 exemplary embodiment, therefore can repeat no more.
Figure 12 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Fig. 1 and Figure 12, the electrothermal module 600 of this exemplary embodiment is similar to the electrothermal module 100 of Fig. 1 exemplary embodiment, but difference main between the two is such as in that the barrier structure that the insulation protection structure 680 of this exemplary embodiment is disposed on substrate.This barrier structure 680 is around all thermoelements within electrothermal module 650, and forms the confined space of a vacuum state with upper and lower base plate or battery lead plate, to protect each element within electrothermal module 600 and layer structure.It is to say, from the schematic diagram of Figure 12 depicted, this exemplary embodiment the obstruct plate washer (dambar) disposed about of electrothermal module 600 as barrier structure 680 so that it is form closed structure.Electrothermal module 600 is internal is vacuum state, and it is identical with insulant that this intercepts plate washer, all can avoid material at high temperature oxidation and the deterioration of each element and layer structure.
Figure 13 illustrates the manufacture method of the electrothermal module of another exemplary embodiment of the present invention.Refer to Figure 12 and Figure 13, the manufacture method of the electrothermal module of this exemplary embodiment is similar to the manufacture method of the electrothermal module of Fig. 8 exemplary embodiment, but difference main between the two is such as follows.Electrothermal module 600 for Figure 12; in this exemplary embodiment; the first substrate 610 that step S310 provides; it is pre-formed insulation protection structure the 680, first battery lead plate 630A the second battery lead plate 630B and the first connected structure 660, and batch has completed multiple the first type thermoelectric material 656A, Second-Type thermoelectric material 656B with array way arrangement.In this step, the generation type of insulation protection structure 680 can be the barrier structure additionally configured on substrate.Or; it is similar to the step S200 of Fig. 2; an insulation protection bulk is initially formed a complete element installation space; its size is enough to the first type thermoelectric material 656A, the Second-Type thermoelectric material 656B of accommodating multiple arrays arrangement; afterwards, then by multiple first type thermoelectric material 656A, Second-Type thermoelectric material 656B it is arranged in described element installation space.Additionally, in this exemplary embodiment, step S300 to S320 carries out under vacuum conditions, to guarantee that electrothermal module 600 is internal for vacuum state.In an exemplary embodiment, if electrothermal module 600 inside is not vacuum state, nitrogen can also be filled in the inside of electrothermal module 600, to avoid the material at high temperature of each element and layer structure to aoxidize and deterioration.
It addition, the electrothermal module 600 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Fig. 1 to Fig. 4 exemplary embodiment, therefore can repeat no more.
Figure 14 illustrates the schematic diagram of the structure of the electrothermal module of another exemplary embodiment of the present invention.Refer to Figure 12 and Figure 14, the electrothermal module 900 of this exemplary embodiment is similar to the electrothermal module 600 of Figure 12 exemplary embodiment, but difference main between the two is such as in that the electrothermal module 900 of this exemplary embodiment uses Second-Type thermoelectric material 956BH, 956BL of first type thermoelectric material 956AH, 956AL of stack and stack as thermoelectricity pin, promotes the output performance of electrothermal module 900.Thermoelectric material 956AH, 956AL, 956BH, 956BL can select corresponding material system according to different temperatures end.When thermo-electric conversion is applied, first substrate 910 and second substrate 920 are such as proximate to the application end of low-temperature receiver and thermal source respectively, and therefore, thermoelectric material 956AH, 956AL, 956BH, 956BL may select applicable material system, to meet practical application request.In this exemplary embodiment, one the 3rd diffused barrier layer 953 is also included between thermoelectric material 956AL, 956AH, and also include the 3rd diffused barrier layer 953 between thermoelectric material 956BL, 956BH, spread each other between the material molecule of thermoelectric material 956AH, 956AL, 956BH, 956BL in order to stop, affect conversion efficiency of thermoelectric and the output performance of electrothermal module 900.
It addition, the electrothermal module 900 of the exemplary embodiment of the present invention and manufacture method thereof by obtaining enough teaching, suggestion and implementation in the narration of Figure 12 to Figure 13 exemplary embodiment, therefore can repeat no more.
In the present invention, the diffusion barrier structure being positioned at each thermoelectric material two ends can include one to multiple layer diffused barrier layer.Multiple exemplary embodiment set forth below illustrates diffusion barrier structure, but the present invention is not limited only to illustrated multiple exemplary embodiment.Suitable combination is also still allowed for again between exemplary embodiment.
Figure 15 illustrates the schematic diagram of the structure of the thermoelectricity pin of the present invention one exemplary embodiment.Refer to Figure 15, the thermoelectricity pin 1150 of this exemplary embodiment includes a thermoelectric material 1156 and diffusion barrier structure 1152,1154.Diffusion barrier structure 1152,1154 lays respectively at the two ends of thermoelectric material 1156, and three forms stacked arrangement.In this exemplary embodiment, diffusion barrier structure 1152,1154 is the layer structure of simple layer respectively, its material be such as chosen from silver, copper, aluminum and germanium one of them.The selection of the material of first, second diffused barrier layer 1152,1154 can be identical or differ, and the present invention is not any limitation as.Formed at the two ends of thermoelectric material 1156.The method of diffusion barrier structure 1152,1154 includes but not limited to that galvanizing process, electroless plating program, sputter are used or chemical vapour deposition procedure.In this exemplary embodiment, thermoelectric material 1156 is such as P type thermoelectric material or N-type thermoelectric material.
Figure 16 illustrates the schematic diagram of the structure of the thermoelectricity pin of another exemplary embodiment of the present invention.Refer to Figure 16, the thermoelectricity pin 1250 of this exemplary embodiment includes a thermoelectric material 1256 and diffusion barrier structure 1252,1254.Diffusion barrier structure 1252,1254 lays respectively at the two ends of thermoelectric material 1256, and three forms stacked arrangement.In this exemplary embodiment, diffusion barrier structure 1252,1254 is the layer structure of multilamellar respectively.For the layer structure of the three layers of this exemplary embodiment, the combination of its material is such as silver, nickel and copper.For double-deck layer structure, the combination of its material be such as chosen from silver/germanium, copper/germanium, silver/carbon and copper/carbon one of them.The selection of the material of diffusion barrier structure 1252,1254 can be identical or differ, and the present invention is not any limitation as.In this exemplary embodiment, thermoelectric material 1256 is such as P type thermoelectric material or N-type thermoelectric material.
Figure 17 illustrates the structure of the thermoelectricity pin of another exemplary embodiment of the present invention and the schematic diagram of connected structure.Refer to Figure 17, the thermoelectricity pin 1350 of this exemplary embodiment includes a thermoelectric material 1356 and diffusion barrier structure 1352,1354.Diffusion barrier structure 1352,1354 lays respectively at the two ends of thermoelectric material 1356, and three forms stacked arrangement.Figure 17 also depict thermoelectricity pin 1350 be arranged in lower on two-layer first, second connected structure 1360,1370.In this exemplary embodiment, diffusion barrier structure 1352,1354 is such as be made up of the material layer of heterogeneity and concentration, forms the diffused barrier layer of a functionally gradient respectively, it is possible to effectively stops the material composition diffusion of its both sides and reduces stress.In this instance, the material that diffused barrier layer is such as progressive composition forms, and has stress buffer and improves the unmatched problem of thermal coefficient of expansion.In this exemplary embodiment, thermoelectric material 1356 is such as P type thermoelectric material or N-type thermoelectric material.
Figure 18 illustrates the structure of the thermoelectricity pin of another exemplary embodiment of the present invention and the schematic diagram of connected structure.Refer to Figure 18, the thermoelectricity pin 1450 of this exemplary embodiment includes a thermoelectric material 1456 and the diffusion barrier structure 1452,1454 in conjunction with connected structure.Diffusion barrier structure 1452,1454 lays respectively at the two ends of thermoelectric material 1456, and three forms stacked arrangement.In this exemplary embodiment, connected structure and diffusion barrier structure 1452,1454 react to be formed respectively the layer structure of Jie's metallic compound, and namely this layer structure is combined with (solderable) functionally gradient diffused barrier layer of layer.For example, connected structure is such as tin metal thin film, diffusion barrier structure 1452,1454 such as includes silver, nickel or copper metal film, after carrying out a pressing and heat treated program, connected structure and diffusion barrier structure 1452,1454 react to form a silver medal stannum, nickel stannum or signal bronze Jie's metallic compound.In an exemplary embodiment, tin metal thin film complete reaction forms Jie's metallic compound of silver stannum, nickel stannum or signal bronze, and silver, nickel or copper metal film still has part to remain.In this exemplary embodiment, thermoelectric material 1456 is such as P type thermoelectric material or N-type thermoelectric material.
In the present invention, the material of diffused barrier layer and each thermoelectric material can form Jie's metallic compound, at least can strengthen the operating characteristics of thermoelement.Material at diffused barrier layer is in the exemplary embodiment that silver-colored and each thermoelectric material is PbTe alloy material, can form Ag between diffused barrier layer and each thermoelectric material2Jie's metallic compound of Te.
Figure 19 a～Figure 19 d illustrates the pyroelecthc properties figure of the layer structure Ag/PbTe/Ag of the present invention one exemplary embodiment.In this exemplary embodiment, between the diffused barrier layer Ag and each thermoelectric material PbTe of layer structure Ag/PbTe/Ag, Ag can be formed2Jie's metallic compound of Te.Refer to Figure 19 a～Figure 19 d, Figure 19 a and be shown in measuring range, seat seebeck coefficient S (Seebeckcoefficients) of the layer structure Ag/PbTe/Ag seat seebeck coefficient S more than single layer structure PbTe.Figure 19 b shows that both conductivityσs (electricalconductance) reduce along with the increase of temperature.Figure 19 c is shown within the scope of the absolute temperature of 300K-630K, and the overall thermal conductivity κ (ThermalConductivity) of single layer structure PbTe is less than the thermal conductivity κ of layer structure Ag/PbTe/Ag.Further, when absolute temperature is higher than 630K, the thermal conductivity κ of layer structure Ag/PbTe/Ag can be gradually increasing.Figure 19 d shows, utilizes Ag as diffused barrier layer, the thermoelectric material for PbTe, it is possible to provide silver mixes effect (Ag-dopingeffect), improves the thermoelectric figure of merit coefficient ZT of thermoelement.Wherein the efficiency of thermoelectric material can be defined by thermoelectric figure of merit coefficient ZT=S2 σ T/ (κ e+ κ L), and wherein S is thermo-electromotive force or western seebeck coefficient, and σ is electrical conductivity, and T is temperature, the pyroconductivity of κ e and κ L then respectively electronics and phonon.
In sum, the electrothermal module of the present invention include insulation protection structure can avoid each element and layer structure material at high temperature oxidation with deterioration.The manufacture method of the electrothermal module of the present invention batch can make thermoelectric material and diffusion barrier structure, makes and module assembled time-histories thus thermoelectricity bulk can be reduced.The diffusion barrier structure of the single or multiple lift of the electrothermal module of the present invention has buffering and reduces the unmatched function of thermal coefficient of expansion.It addition, the electrothermal module of the present invention is equally applicable to high temperature assembles joint.
Although disclosing the present invention in conjunction with above example; but it is not limited to the present invention; any art has usually intellectual; without departing from the spirit and scope of the present invention; a little change and retouching can be done, therefore protection scope of the present invention should with being as the criterion that the claim enclosed defines.
Claims (21)
1. a structure for electrothermal module, including:
At least one substrate；
Thermoelement, is arranged on this at least one substrate, and wherein this thermoelement includes:
At least three battery lead plate, one first central battery lead plate and one second battery lead plate are arranged on this at least one substrate as one end of this thermoelement；
First type thermoelectric material, is arranged on this first battery lead plate, and one end of this first type thermoelectric material electrically connects with this first battery lead plate；
Second-Type thermoelectric material, is arranged on this second battery lead plate, and one end of this Second-Type thermoelectric material electrically connects with this second battery lead plate,
Wherein one the 3rd battery lead plate in the middle of this at least three battery lead plate is arranged on this first type thermoelectric material and this Second-Type thermoelectric material as the other end of this thermoelement, and the 3rd battery lead plate electrically connects with the other end of this first type thermoelectric material and the other end of this Second-Type thermoelectric material；And
Diffusion barrier structure, is arranged in these two ends of this first type thermoelectric material and this Second-Type thermoelectric material；And
Insulation protection structure, is arranged at around this thermoelement.
2. the structure of electrothermal module as claimed in claim 1, wherein this insulation protection structure covers the surface beyond these two ends of this thermoelement.
3. the structure of electrothermal module as claimed in claim 1, wherein this insulation protection structure is substantially fully filled with the space between this at least one substrate and this thermoelement.
4. the structure of electrothermal module as claimed in claim 1; wherein this at least one substrate includes first substrate and second substrate; this insulation protection structure includes barrier structure; it is arranged between this first substrate and this second substrate; and around this thermoelement, wherein this barrier structure forms a confined space with this second substrate, this first battery lead plate and this second battery lead plate.
5. the structure of electrothermal module as claimed in claim 1, also includes at least one connected structure, is arranged respectively between this at least three battery lead plate and this diffusion barrier structure.
6. the structure of electrothermal module as claimed in claim 5, wherein this diffusion barrier structure includes the first diffused barrier layer and the second diffused barrier layer, this first diffused barrier layer is arranged between this first type thermoelectric material and this first battery lead plate, and it is arranged between this Second-Type thermoelectric material and this second battery lead plate, this second diffused barrier layer is arranged between this first type thermoelectric material and the 3rd battery lead plate, and be arranged between this Second-Type thermoelectric material and the 3rd battery lead plate
Wherein this at least one connected structure includes:
First connected structure, it is arranged between this first diffused barrier layer and this first battery lead plate, and be arranged between this first diffused barrier layer and this second battery lead plate, and engage this first diffused barrier layer and this first battery lead plate respectively, and engage the first diffused barrier layer and this second battery lead plate；And
Second connected structure, is arranged between this second diffused barrier layer and the 3rd battery lead plate, and engages this second diffused barrier layer and the 3rd battery lead plate.
7. the structure of electrothermal module as claimed in claim 5, wherein this diffusion barrier structure includes at least one diffused barrier layer, and this at least one diffused barrier layer and this at least one connected structure form Jie's metallic compound.
8. the structure of electrothermal module as claimed in claim 1, wherein this diffusion barrier structure includes one or more diffused barrier layer, the material of this one or more diffused barrier layer be chosen from silver, copper, aluminum, germanium, silver/germanium, copper/germanium, silver/carbon and copper/carbon one of them.
9. the structure of electrothermal module as claimed in claim 1, wherein this first type thermoelectric material is chosen from the one in the middle of P type thermoelectric material and N-type thermoelectric material, this Second-Type thermoelectric material is chosen from the another kind in the middle of P type thermoelectric material and N-type thermoelectric material, and P type thermoelectric material or N-type thermoelectric material include Bi2Te3、GeTe、PbTe、CoSb3Or Zn4Sb3Series alloy material.
10. the structure of electrothermal module as claimed in claim 1, wherein this diffusion barrier structure includes at least one diffused barrier layer, and this at least one diffused barrier layer forms Jie's metallic compound with this first type thermoelectric material and this Second-Type thermoelectric material.
11. the structure of electrothermal module as claimed in claim 10, wherein the material of this at least one diffused barrier layer is silver, this the first type thermoelectric material and this Second-Type thermoelectric material are PbTe alloy materials, and this at least one diffused barrier layer forms Ag with this first type thermoelectric material and this Second-Type thermoelectric material2Jie's metallic compound of Te.
12. the structure of electrothermal module as claimed in claim 1, wherein the material of this insulation protection structure be chosen from glass, glaze paint and pottery three one of them.
13. the structure of electrothermal module as claimed in claim 1, wherein this at least one substrate, this at least three battery lead plate, this first type thermoelectric material and this Second-Type thermoelectric material are with hard solder method or solid-liquid diffusing joining method or utilize nano silver material to engage, to form this stacked structure.
14. a manufacture method for electrothermal module, including:
A diffusion barrier structure is formed at the two ends of one first type thermoelectric material and a Second-Type thermoelectric material；
One second battery lead plate of one first battery lead plate sum in the middle of at least three battery lead plate is arranged at least one substrate as one end of a thermoelement, wherein one end of this first type thermoelectric material electrically connects with this first battery lead plate, and one end of this Second-Type thermoelectric material electrically connects with this second battery lead plate；
Respectively these two ends are included this first type thermoelectric material of this diffusion barrier structure and this Second-Type thermoelectric material is arranged on this second battery lead plate of this first battery lead plate sum in the middle of at least three battery lead plate；
One the 3rd battery lead plate in the middle of this at least three battery lead plate is arranged in these two ends as the other end of this thermoelement and includes on this first type thermoelectric material and this Second-Type thermoelectric material of this diffusion barrier structure, to form a thermoelement, wherein the 3rd battery lead plate electrically connects with the other end of this first type thermoelectric material and the other end of this Second-Type thermoelectric material；And
Formation one insulation protection structure around this thermoelement, to form an electrothermal module.
15. the manufacture method of electrothermal module as claimed in claim 14, the step wherein forming this insulation protection structure around this thermoelement includes:
One insulation protection bulk is provided；And
Multiple element installation space is formed in this insulation protection bulk.
16. the manufacture method of electrothermal module as claimed in claim 15, the step wherein forming this diffusion barrier structure at these two ends of this first type thermoelectric material and this Second-Type thermoelectric material includes:
One first diffused barrier layer is formed in respectively this element installation space；
Respectively this first diffused barrier layer is formed this first type thermoelectric material and this Second-Type thermoelectric material；And
This first type thermoelectric material and this Second-Type thermoelectric material are formed one second diffused barrier layer.
17. the manufacture method of electrothermal module as claimed in claim 16, the step wherein forming this insulation protection structure around this thermoelement also includes:
Carry out a pressing and heat treated program so that this first diffused barrier layer, this first type thermoelectric material and this second diffused barrier layer are bonded together in stacked form, and this first diffused barrier layer, this Second-Type thermoelectric material and this second diffused barrier layer are bonded together in stacked form.
18. the manufacture method of electrothermal module as claimed in claim 14, also include:
One first substrate, this first battery lead plate and this second battery lead plate are provided；
This first substrate configures this first battery lead plate and this second battery lead plate, and on this first battery lead plate and this second battery lead plate, forms one first connected structure；
3rd battery lead plate is provided；And
3rd battery lead plate is formed one second connected structure,
Wherein respectively these two ends are included this first type thermoelectric material of this diffusion barrier structure and step that this Second-Type thermoelectric material is arranged on this second battery lead plate of this first battery lead plate sum in the middle of at least three battery lead plate include:
This first type thermoelectric material that these two ends are included respectively this diffusion barrier structure by this first connected structure is bonded together with this first battery lead plate, and this Second-Type thermoelectric material that these two ends include this diffusion barrier structure is bonded together with this second battery lead plate
The 3rd battery lead plate in the middle of this at least three battery lead plate is wherein arranged in the step that these two ends include on this first type thermoelectric material of this diffusion barrier structure and this Second-Type thermoelectric material include:
Respectively these two ends are included by this second connected structure this first type thermoelectric material and the 3rd battery lead plate of this diffusion barrier structure, and this Second-Type thermoelectric material that these two ends include this diffusion barrier structure is bonded together with the 3rd battery lead plate.
19. the manufacture method of electrothermal module as claimed in claim 18, also include:
One second substrate is provided；And
This second substrate configures the 3rd battery lead plate.
20. the manufacture method of electrothermal module as claimed in claim 19, the step wherein forming this insulation protection structure around this thermoelement includes:
This first substrate configures a barrier structure, with around this thermoelement, and forms a confined space with this second substrate, this first battery lead plate and this second battery lead plate.
21. the manufacture method of electrothermal module as claimed in claim 18, the step wherein forming this insulation protection structure around this thermoelement includes:
In the way of spraying or immersion, the surface of this thermoelement is covered this insulation protection structure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN109411592A (en) * | 2016-11-11 | 2019-03-01 | 优材科技有限公司 | Thermoelectric material structure |
| JP2020150215A (en) * | 2019-03-15 | 2020-09-17 | 三菱マテリアル株式会社 | Thermoelectric conversion module |
| CN113860873A (en) * | 2021-10-19 | 2021-12-31 | 西安交通大学 | Bismuth telluride thermoelectric device and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI608638B (en) | 2016-12-15 | 2017-12-11 | 財團法人工業技術研究院 | Thermoelectric module |
| JP7196432B2 (en) | 2017-06-29 | 2022-12-27 | 三菱マテリアル株式会社 | Thermoelectric conversion module and method for manufacturing thermoelectric conversion module |
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| TWI557957B (en) | 2016-11-11 |
| TW201622189A (en) | 2016-06-16 |
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