CN103928605A - Manufacturing method of thermoelectric device - Google Patents
Manufacturing method of thermoelectric device Download PDFInfo
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- CN103928605A CN103928605A CN201410182366.5A CN201410182366A CN103928605A CN 103928605 A CN103928605 A CN 103928605A CN 201410182366 A CN201410182366 A CN 201410182366A CN 103928605 A CN103928605 A CN 103928605A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 165
- 239000007772 electrode material Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000007731 hot pressing Methods 0.000 claims abstract description 12
- 238000004826 seaming Methods 0.000 claims description 36
- 238000005245 sintering Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 10
- 229910018989 CoSb Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910004767 CaSn Inorganic materials 0.000 claims description 4
- 229910017639 MgSi Inorganic materials 0.000 claims description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 abstract 9
- 210000002683 foot Anatomy 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- NPVASHFELHRKPC-UHFFFAOYSA-N [Mg].[Si].[Sn] Chemical compound [Mg].[Si].[Sn] NPVASHFELHRKPC-UHFFFAOYSA-N 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000002305 electric material Substances 0.000 description 3
- 239000007770 graphite material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UFIKNOKSPUOOCL-UHFFFAOYSA-N antimony;cobalt Chemical compound [Sb]#[Co] UFIKNOKSPUOOCL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000004078 cryogenic material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention provides a manufacturing method of a thermoelectric device. The manufacturing method of the thermoelectric device at least comprises the following steps that S1 a mould is provided, the mould comprises a main body with a through hole, an upper pressing head, a lower pressing head and an interval part, the upper pressing head and the lower pressing head are arranged in the through hole and can move up and down, the interval part is arranged between the upper pressing head and the lower pressing head and is matched with the upper pressing head, and at least one pair of intervals are formed in the interval part; S2 electrode materials are laid on the upper surface of the lower pressing head in the through hole, the interval part is placed in the through hole, P-type thermoelectric materials and N-type thermoelectric materials are arranged in each pair of intervals respectively, and then the upper pressing head covers the through hole; S3 the mould is put in a hot-pressing furnace to be sintered in a pressurization mode, and a phi type thermoelectric device unit block is obtained. The manufacturing method achieves connection of the P-type thermoelectric materials, the N-type thermoelectric materials and an electrode while manufacturing the thermoelectric materials, prevents the thermoelectric materials from being subjected to a high-temperature process again in the manufacturing process of the thermoelectric device, and effectively maintains the stability of the performance of the thermoelectric materials.
Description
Technical field
The invention belongs to thermoelectric device field, relate to the manufacture method of a kind of thermoelectric device unit.
Background technology
Seebeck (Seebeck) effect, is called again the first thermoelectric effect, and it refers to the pyroelectric phenomena that cause two kinds of voltage differences between material due to two kinds of different electric conductors or semi-conductive temperature contrast.Thermoelectric material can utilize the Seebeck effect of semi-conducting material that heat energy is directly converted to electric energy, belongs to a kind of clean, and free of contamination generation technology, has huge application potential in fields such as aviation, used heat waste heat recycling, vehicle exhaust processing, underground heat.So, along with being on the rise of global warming and energy problem, the thermoelectric power generation material as one of clean energy resource and the research of device thereof are also come into one's own gradually.
Although with Bi
2te
3for the preparation of cryogenic material thermoelectric power generation and the refrigeration device of representative and apply and stepped into commercialization stage, CoSb
3, MgSi
xse
1-x, CaSn
2sb
2, Yb
14mnSb
11, the investigation of materials of high-temperature region has also obtained larger progress in lead telluride, SiGe etc., but the device of middle high-temperature region thermoelectric material is subject to middle high-temperature technology condition bottom electrode to connect difficulty always, the puzzlement of the factors such as interface thermal stability is low, cannot further apply.Patent US5969290A proposed a kind of the thermoelectric material of P type and N-type and electrode material is hot-forming respectively after, what replace is connected and is obtained thermoelectric device with P type with the electrode that N-type thermoelectric element is connected by soldering.Patent ZL200710044771 proposed a kind of the antimony cobalt thermoelectric material of P type and N-type is hot-forming side by side after, after welding electrode, cut into from the side the thermoelectric device unit of π type structure.But said method all exists thermoelectric material to need again to experience the required pyroprocess of welding in device process being prepared into, and after thermoelectric material is hot-forming, need cutting to obtain the shape of needs, also existence waste of material to a certain degree.
Based on the shortcoming of above prior art, the present invention proposes a kind of method of utilizing mould synchronously to realize thermoelectric material preparation and device cell moulding by hot-pressing technique.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide the manufacture method of a kind of thermoelectric device unit, in electrode connection procedure, repeatedly experience for solving high-temperature region thermoelectric device in prior art the problem that pyroprocess easily causes material property to change.
For achieving the above object and other relevant objects, the invention provides the manufacture method of a kind of thermoelectric device unit, at least comprise the following steps:
S1 a: mould is provided, and described mould comprises a main body that is provided with through hole, be arranged in described through hole seaming chuck moving up and down and push-down head and be arranged at the distance piece matching between described seaming chuck and push-down head and with described seaming chuck; In described distance piece, be provided with at least one pair of space; Described seaming chuck comprises lid and is connected at least one pair of presser feet matching with described space of described lid below;
S2: electrode material is layed in to the upper surface of push-down head described in described through hole, then puts into described distance piece in described through hole, insert respectively P type thermoelectric material and N-type thermoelectric material in every pair of slits; Cover again described seaming chuck;
S3: described mould is put into hot pressing furnace and carry out pressure sintering, obtain π type thermoelectric device unit block.
Alternatively, in described step S2, after electrode material being layed in to the upper surface of push-down head described in described through hole, then lay and stop enhancement layer material at described electrode material upper surface, and then in described through hole, put into described distance piece, in every pair of slits, insert respectively P type thermoelectric material and N-type thermoelectric material; Cover again described seaming chuck.
Alternatively, described in general, stop that enhancement layer material is layed in described electrode material layer upper surface with powder, film or paillon foil form.
Alternatively, described in, stop that enhancement layer material comprises one or more in Mo, W, Ti, Al, Nb, Ta or Ni element.
Alternatively, in described distance piece, be provided with a pair of strip space, after described step S3, further cut described electrode material, P type thermoelectric material and N-type thermoelectric material, obtain some single π type thermoelectric device unit.
Alternatively, in described distance piece, be provided with at least two pairs of spaces, after described step S3, further cut described electrode material, obtain at least two single π type thermoelectric device unit.
Alternatively, be provided with a pair of space in described distance piece, in described step S3, the described π type thermoelectric device unit block obtaining is single π type thermoelectric device unit.
Alternatively, the described distance piece structure that is formed in one, comprises a square ring type frame and is arranged at least one dividing plate in described frame; Described frame enclosed space is divided at least one pair of space by described dividing plate.
Alternatively, in described step S2, described electrode material is layed in to described push-down head upper surface with powder or block form.
Alternatively, in described step S2, the described P type thermoelectric material of laying and N-type thermoelectric material are powder or prefabricated block.
Alternatively, in described step S1, also comprise the step of described mould being cleaned and being sprayed release agent, in described step S3, after sintering, directly from described mould, take out described π type thermoelectric device unit block.
Alternatively, in described step S3, adopt discharge plasma sintering, thermal resistance heating pressure sintering or induction heating pressure sintering method to obtain π type thermoelectric device unit block.
Alternatively, in described step S2, in every pair of slits, insert respectively after P type thermoelectric material and N-type thermoelectric material, then lay cold junction electrode material at described P type thermoelectric material and N-type thermoelectric material upper surface respectively, and then cover described seaming chuck.
Alternatively, described mould is made by the one in graphite, alloy, alumina-based ceramic, silicon-nitride-based ceramic, types of silicon carbide-based ceramics or at least two kinds of combinations obtain.
Alternatively, described thermoelectric material comprises CoSb
3, MgSi
xse
1-x, CaSn
2sb
2, Yb
14mnSb
11, lead telluride, SiGe and Bi
2te
3in at least one, wherein, 0<x<1.
Alternatively, in described seaming chuck, described lid is fixedly connected with or contacts with described presser feet and is connected.
As mentioned above, the manufacture method of thermoelectric device of the present invention unit, there is following beneficial effect: the present invention is placed in electrode material, diffusion enhanced layer material and P type and N-type thermoelectric material the relevant position of mould in order successively, adopt hot press forming technology one-shot forming, produce one or more P-N thermoelectric device unit.Wherein, can realize separated from one another in hot pressing of P, n type material by Design of Dies, the thermoelectric device unit of disposable formation π type structure, reduces the phase counterdiffusion of element in pyroprocess between P, N-type thermoelectric material; And the present invention realizes P in preparing thermoelectric material, N-type thermoelectric material is connected with temperature end electrode, avoid thermoelectric material in device preparation process, to suffer again pyroprocess, effectively maintain the stable of pyroelectric material performance; According to the type of thermoelectric material, by selecting suitable electrode material and stopping enhancement layer material, the intensity that effectively intensifier electrode is combined with thermoelectric material and hot matching degree, reduce contact resistance, lays the foundation for obtaining high efficiency thermoelectric device.
Brief description of the drawings
Fig. 1 is shown as the process chart of the manufacture method of thermoelectric device of the present invention unit.
Fig. 2 is shown as the cross-sectional view of the mould using in the manufacture method of thermoelectric device of the present invention unit.
Fig. 3 is shown as the plan structure schematic diagram of the main body in mould.
Fig. 4 is shown as distance piece in the mould plan structure schematic diagram in embodiment mono-.
Fig. 5 is shown as distance piece in the mould plan structure schematic diagram in embodiment bis-.
Fig. 6 is shown as distance piece in the mould plan structure schematic diagram in embodiment tri-.
Element numbers explanation
S1～S3 step
1 main body
11 through holes
2 seaming chucks
21 lids
22 presser feets
3 push-down heads
4 distance pieces
41 frames
42 dividing plates
43 spaces
5 electrode materials
6 stop enhancement layer material
7 P type thermoelectric materials
8 N-type thermoelectric materials
Embodiment
Below, by specific instantiation explanation embodiments of the present invention, those skilled in the art can understand other advantages of the present invention and effect easily by the disclosed content of this specification.The present invention can also be implemented or be applied by other different embodiment, and the every details in this specification also can be based on different viewpoints and application, carries out various modifications or change not deviating under spirit of the present invention.
Refer to Fig. 1 to Fig. 6.It should be noted that, the diagram providing in the present embodiment only illustrates basic conception of the present invention in a schematic way, satisfy and only show with assembly relevant in the present invention in graphic but not component count, shape and size drafting while implementing according to reality, when its actual enforcement, kenel, quantity and the ratio of each assembly can be a kind of random change, and its assembly layout kenel also may be more complicated.
The manufacture method that the invention provides a kind of thermoelectric device unit, refers to Fig. 1, is shown as the process chart of the method, at least comprises the following steps:
Step S1 a: mould is provided, Fig. 2 shows the cross-sectional view of this mould, as shown in Figure 2, described mould comprises a main body 1 that is provided with through hole 11, is arranged at the interior seaming chuck 2 moving up and down of described through hole 11 and push-down head 3 and is arranged at the distance piece 4 matching between described seaming chuck 2 and push-down head 3 and with described seaming chuck 2; In described distance piece 4, be provided with at least one pair of space; Described seaming chuck 2 comprises lid 21 and is connected at least one pair of presser feet 22 matching with described space of described lid 21 belows.Fig. 3 has shown the plan structure schematic diagram of described main body 1.
Concrete, described mould is made by the one in graphite, alloy, alumina-based ceramic, silicon-nitride-based ceramic, types of silicon carbide-based ceramics or at least two kinds of combinations obtain, be in described mould, main body 1, seaming chuck 2, push-down head 3 and distance piece 4 can adopt identical material, also can adopt different materials.
Concrete, in described seaming chuck 2, described lid is fixedly connected with or contacts with described presser feet and is connected, and is preferably contact and connects, and can reduce the probability of described presser feet fracture.
Step S2: electrode material is layed in to the upper surface of push-down head described in described through hole, then puts into described distance piece in described through hole, insert respectively P type thermoelectric material and N-type thermoelectric material in every pair of slits; Cover again described seaming chuck.
Concrete, before mould, first described mould cleaned and spray release agent using.Described electrode material adopts metal, nonmetal conductor material or alloy material, includes but not limited to one or more in the elements such as gold, silver, copper, iron, tungsten, nickel, chromium, makes the electrode finally obtaining have satisfactory electrical conductivity.Described thermoelectric material includes but not limited to CoSb
3, MgSi
xse
1-x(0<x<1), CaSn
2sb
2, Yb
14mnSb
11, the high-temperature region material such as lead telluride, SiGe, certain described thermoelectric material also can adopt Bi
2te
3deng low-temperature space material.
Concrete, for dissimilar thermoelectric material, can select suitable electrode material, make electrode material and corresponding thermoelectric material coefficient of expansion matched well.The influencing factor of the matched coefficients of thermal expansion of thermoelectric material and electrode material is many, for example, the thermal coefficient of expansion difference of different materials under different temperatures, the thickness of thermoelectric material and electrode material contact-making surface two layers of material and contact-making surface big or small difference also can affect the effect that coefficient of thermal expansion mismatch produces.Described electrode material and described P type thermoelectric material or the thermal coefficient of expansion of N-type thermoelectric material under sintering temperature differ and are preferably no more than 20%, are preferably and are no more than 10% (taking the coefficient of expansion of thermoelectric material as radix).For example,, when thermoelectric material is magnesium silicon tin material or CoSb
3time, described electrode material can adopt the coefficient of expansion to be greater than magnesium silicon tin material or CoSb
3copper, silver and the coefficient of expansion be less than magnesium silicon tin material or CoSb
3the alloy of the metal such as tungsten, molybdenum as electrode.When thermoelectric material adopts when germanium silicon material, can adopt the coefficient of expansion with it close graphite material as electrode material.
Concrete, according to the type of electrode material and P type, N-type thermoelectric material, if electrode material and thermoelectric material can directly be realized good bond strength in follow-up sintering, form ohmic contact, without laying and stop enhancement layer material between electrode material and thermoelectric material.For example, for N-type germanium silicon thermoelectric material, can directly adopt graphite as electrode material, centre need not add and stop that enhancement layer material also can form good contact.If electrode material and thermoelectric material can not directly be realized good bond strength in follow-up sintering, in this step, after electrode material being layed in to the upper surface of push-down head described in described through hole, can then lay and stop enhancement layer material at described electrode material upper surface, and then in described through hole, put into described distance piece, in every pair of slits, insert respectively P type thermoelectric material and N-type thermoelectric material; Cover again described seaming chuck.Describedly stop that enhancement layer material can effectively prevent on the one hand the mutual diffusion between element in electrode material and thermoelectric material in follow-up high-temperature sintering process, on the other hand can intensifier electrode material and P type, N-type thermoelectric material between bond strength, ensure to form effective ohmic contact between the two, weaken the impact of contact resistance on device performance.Describedly stop that enhancement layer material includes but not limited to one or more in Mo, W, Ti, Al, Nb, Ta or Ni element.For example,, for CoSb
3thermoelectric material, can adopt one or more in the elements such as Mo, W, Ti as stopping enhancement layer material, for magnesium silicon tin material base thermoelectricity material, can adopt one or more in the elements such as Mo, Al, NI as stopping enhancement layer material.
In Fig. 2, also shown described electrode material 5, stopped enhancement layer material 6, P type thermoelectric material 7 and N-type thermoelectric material 8 be layed in the relative position in described mould, as shown in the figure, in mould, described distance piece 4 is separated from one another to P type thermoelectric material 7 and N-type thermoelectric material 8, once forms phase counterdiffusion in the process of π type structure thermoelectric device unit thereby can reduce P type, N-type thermoelectric material at follow-up high temperature hot pressing.
Concrete, described electrode material 5 is layed in described push-down head 3 upper surfaces with powder or block form.Compared to the block type electrode of densification, in the present invention, described electrode material 5 is with powder type or pass through precompressed but the not block form of densification laying, the moulding of electrode and moulding and the densification of densification and thermoelectric material are completed simultaneously, interface has chimeric effect, more tight in conjunction with obtaining, can also reduce the impact of impurity on combination interface simultaneously, can obtain higher bond strength and lower contact resistance.
Concrete, described in stop that enhancement layer material 6 is layed in described electrode material layer upper surface taking powder, film (thickness is as 1～100 micron) or paillon foil (thickness is greater than 100 microns) form.For powder type, will stop that enhancement layer material powder is laid between electrode material and thermoelectric material; For form of film, can adopt the methods such as plating, spraying to form.Describedly stop that enhancement layer material 6 can be for individual layer or lamination layer structure.
Concrete, described P type thermoelectric material 7 and N-type thermoelectric material 8 are laid with powder or prefabricated block form.
Step S3: described mould is put into hot pressing furnace and carry out pressure sintering, obtain π type thermoelectric device unit block.
Concrete, hot pressing furnace is widely used in carbide alloy, functional ceramic, powder metallurgy etc. and under high temperature, high vacuum condition, carries out hot pressed sintering processing, also can be in gas-filled protective situation hot forming sintering, sintering processing has multiple choices.In the present invention, can adopt discharge plasma sintering, thermal resistance heating pressure sintering or induction heating pressure sintering method to obtain π type thermoelectric device unit block.Owing to spraying in advance release agent, after sintering, can directly from described mould, take out hot-forming π type thermoelectric device unit block.
In the mould that the present invention uses, described distance piece 4 structure that is formed in one, comprises a square ring type frame and is arranged at least one dividing plate in described frame; Described frame enclosed space is divided at least one pair of space by described dividing plate.The present invention is by changing the specific design of the distance piece in mould, one or more π type thermoelectric devices unit of can producing once.Describe in detail below by several specific embodiments.
Embodiment mono-
Refer to Fig. 4, be shown as the vertical view of distance piece 4 in the mould that the present embodiment uses, as shown in the figure, described distance piece 4 comprises a square ring type frame 41 and is arranged at a dividing plate 42 in described frame 41; Described frame 41 enclosed spaces are divided into a pair of strip space by described dividing plate 42.
The method of making thermoelectric device unit in the present embodiment comprises the following steps:
(1) adopt the mould of graphite material, described mould is cleaned and sprays release agent.The profile of described mould as shown in Figure 1, comprises main body 1, seaming chuck 2, push-down head 3 and vertical view distance piece 4 as shown in Figure 4.
(2) described push-down head 3 vertical direction are positioned in the through hole of described main body 1, by electrode material 5, stop that enhancement layer material 6 is laid on the upper surface of described push-down head 3 successively, then put described distance piece 4, P type thermoelectric material 7 and N-type thermoelectric material 8 are inserted respectively in a pair of space 43 that described distance piece 4 forms, then cover described seaming chuck 2, the presser feet 22 of described seaming chuck is pressed in described gap 43, and then the mould that fills material is put into hot pressing furnace Thermocompressed sintering and forming and removed, obtain the long strip type P-N thermoelectric device block of π type structure.
(3) cutting of size as required of the thermoelectric device unit block sintering is obtained to some single π type thermoelectric device unit, by deburring and make surface clean, for making bulk thermoelectric device.
In the present embodiment, can once make multiple π type thermoelectric devices unit, hot junction electrode and thermoelectric material are one-body molded, and electrode just completes and is connected and forms ohmic contact in hot-forming process with thermoelectric material, avoided thermoelectric material in device preparation process, to suffer again pyroprocess, thereby effective maintaining heat electric material is stable.
Embodiment bis-
The present embodiment and embodiment mono-adopt essentially identical scheme, and difference is the material difference of mould and the structure difference of distance piece.
Refer to Fig. 5, be shown as the vertical view of distance piece 4 in the mould that the present embodiment uses, as shown in the figure, described distance piece 4 comprises a square ring type frame 41 and is arranged at least two dividing plates 42 in described frame 41; Described frame 41 enclosed spaces are divided at least two pairs of spaces by described dividing plate 42.As example, in the present embodiment to be divided into three pairs of spaces as example.
The method of making thermoelectric device unit in the present embodiment comprises the following steps:
(1) adopt the mould of carbide alloy material, described mould is cleaned and sprays release agent.The profile of described mould as shown in Figure 1, comprises main body 1, seaming chuck 2, push-down head 3 and vertical view distance piece 4 as shown in Figure 4.
(2) described push-down head 3 vertical direction are positioned in the through hole of described main body 1, by electrode material 5, stop that enhancement layer material 6 is laid on the upper surface of described push-down head 3 successively, then put described distance piece 4, P type thermoelectric material 7 and N-type thermoelectric material 8 are inserted respectively in the every a pair of space 43 that described distance piece 4 forms, then cover described seaming chuck 2, the presser feet 22 of described seaming chuck is pressed in described gap 43, and then the mould that fills material is put into hot pressing furnace Thermocompressed sintering and forming and removed, obtain comprising that electrode part divides three connected π type construction units.
(3) the electrode material part of the thermoelectric device unit block sintering is cut, obtain three single π type thermoelectric device unit, by deburring and make surface clean, for making bulk thermoelectric device.
In the present embodiment, can once make at least two π type thermoelectric device unit, only the cutting of electrode material part can need be obtained to some single π type thermoelectric device unit.Thermoelectric material between different units just completes and cuts apart in sintering process, can avoid bulk thermoelectric material problem due to the excessive generation of stress crack in sintering process, improves the stability of device.Simultaneously, hot junction electrode and thermoelectric material are one-body molded, and electrode just completes and is connected and forms ohmic contact with thermoelectric material in hot-forming process, avoided thermoelectric material in device preparation process, to suffer again pyroprocess, thereby effective maintaining heat electric material is stable.
Embodiment tri-
The present embodiment and embodiment mono-, two adopt essentially identical scheme, and difference is that in embodiment mono-, two, mould each several part adopts identical material, and in the present embodiment, mould each several part can adopt unlike material, uses assembling die.In addition, in the present embodiment, the structure of the distance piece of mould is also different.
Refer to Fig. 6, be shown as the vertical view of distance piece 4 in the mould that the present embodiment uses, as shown in the figure, described distance piece 4 comprises a square ring type frame 41 and is arranged at a dividing plate 42 in described frame 41; Described frame 41 enclosed spaces are divided into a pair of space by described dividing plate 42.Different from embodiment mono-, longitudinal width in a pair of space in the present embodiment is shorter, consistent with single π type thermoelectric device unit as required.
The method of making thermoelectric device unit in the present embodiment comprises the following steps:
(1) adopt assembling die, the profile of described mould as shown in Figure 1, described in comprise main body 1, seaming chuck 2, push-down head 3 and vertical view distance piece 4 as shown in Figure 4, wherein, described main body 1, seaming chuck 2 and push-down head 3 are made up of graphite, and described distance piece 4 is made up of ceramic material.Described mould is cleaned and sprays release agent.
(2) described push-down head 3 vertical direction are positioned in the through hole of described main body 1, by electrode material 5, stop that enhancement layer material 6 is laid on the upper surface of described push-down head 3 successively, then put described distance piece 4, P type thermoelectric material 7 and N-type thermoelectric material 8 are inserted respectively in a pair of space 43 that described distance piece 4 forms, then cover described seaming chuck 2, the presser feet 22 of described seaming chuck is pressed in described gap 43, and then the mould that fills material is put into hot pressing furnace Thermocompressed sintering and forming and removed, obtain single π type structure P-N thermoelectric device block.
(3) by the single thermoelectric device unit deburring sintering and make surface clean, for making bulk thermoelectric device.
In the present embodiment, can once make single π type thermoelectric device unit, hot junction electrode and thermoelectric material are one-body molded, and electrode just completes and is connected and forms ohmic contact in hot-forming process with thermoelectric material, avoided thermoelectric material in device preparation process, to suffer again pyroprocess, thereby effective maintaining heat electric material is stable.In the present embodiment, use assembling die, can bring into play the advantage of each mold materials, graphite material relatively, ceramic material intensity is higher, and anti-pressure ability is stronger, and ceramic material, as spacer materia, can make thermoelectric material molding effect better.
Embodiment tetra-
In embodiment mono-, two or three, in every pair of slits, insert respectively after P type thermoelectric material and N-type thermoelectric material, then lay cold junction electrode material at described P type thermoelectric material and N-type thermoelectric material upper surface respectively, and then cover described seaming chuck, and carry out pressure sintering.
In the present embodiment, except making hot junction electrode complete and be connected in device forming process with thermoelectric material, can also make cold junction electrode in this process, complete connection equally, farthest ensure to reduce the change of thermoelectric material at device preparation process performance.
In sum, the manufacture method of thermoelectric device of the present invention unit is placed in electrode material, diffusion enhanced layer material and P type and N-type thermoelectric material the relevant position of mould in order successively, adopt hot press forming technology one-shot forming, produce one or more P-N thermoelectric device unit.Wherein, can realize separated from one another in hot pressing of P, n type material by Design of Dies, the thermoelectric device unit of disposable formation π type structure, reduces the phase counterdiffusion of element in pyroprocess between P, N-type thermoelectric material; And the present invention realizes P in preparing thermoelectric material, N-type thermoelectric material is connected with temperature end electrode, avoid thermoelectric material in device preparation process, to suffer again pyroprocess, effectively maintain the stable of pyroelectric material performance; According to the type of thermoelectric material, by selecting suitable electrode material and stopping enhancement layer material, the intensity that effectively intensifier electrode is combined with thermoelectric material and hot matching degree, reduce contact resistance, lays the foundation for obtaining high efficiency thermoelectric device.So the present invention has effectively overcome various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all can, under spirit of the present invention and category, modify or change above-described embodiment.Therefore, such as in affiliated technical field, have and conventionally know that the knowledgeable, not departing from all equivalence modifications that complete under disclosed spirit and technological thought or changing, must be contained by claim of the present invention.
Claims (16)
1. a manufacture method for thermoelectric device unit, is characterized in that, at least comprises the following steps:
S1 a: mould is provided, and described mould comprises a main body that is provided with through hole, be arranged in described through hole seaming chuck moving up and down and push-down head and be arranged at the distance piece matching between described seaming chuck and push-down head and with described seaming chuck; In described distance piece, be provided with at least one pair of space; Described seaming chuck comprises lid and is connected at least one pair of presser feet matching with described space of described lid below;
S2: electrode material is layed in to the upper surface of push-down head described in described through hole, then puts into described distance piece in described through hole, insert respectively P type thermoelectric material and N-type thermoelectric material in every pair of slits; Cover again described seaming chuck;
S3: described mould is put into hot pressing furnace and carry out pressure sintering, obtain π type thermoelectric device unit block.
2. the manufacture method of thermoelectric device according to claim 1 unit, it is characterized in that: in described step S2, after electrode material being layed in to the upper surface of push-down head described in described through hole, then lay and stop enhancement layer material at described electrode material upper surface, and then in described through hole, put into described distance piece, in every pair of slits, insert respectively P type thermoelectric material and N-type thermoelectric material; Cover again described seaming chuck.
3. the manufacture method of thermoelectric device according to claim 2 unit, is characterized in that: described in inciting somebody to action, stop that enhancement layer material is layed in described electrode material layer upper surface with powder, film or paillon foil form.
4. the manufacture method of thermoelectric device according to claim 2 unit, is characterized in that: described in stop that enhancement layer material comprises one or more in Mo, W, Ti, Al, Nb, Ta or Ni element.
5. the manufacture method of thermoelectric device according to claim 1 and 2 unit, it is characterized in that: in described distance piece, be provided with a pair of strip space, after described step S3, further cutting described electrode material, P type thermoelectric material and N-type thermoelectric material, obtains some single π type thermoelectric device unit.
6. the manufacture method of thermoelectric device according to claim 1 and 2 unit, it is characterized in that: in described distance piece, be provided with at least two pairs of spaces, after described step S3, further cut described electrode material, obtain at least two single π type thermoelectric device unit.
7. the manufacture method of thermoelectric device according to claim 1 and 2 unit, is characterized in that: in described distance piece, be provided with a pair of space, in described step S3, the described π type thermoelectric device unit block obtaining is single π type thermoelectric device unit.
8. the manufacture method of thermoelectric device according to claim 1 and 2 unit, is characterized in that: the described distance piece structure that is formed in one, comprises at least one dividing plate in a square ring type frame and setting and described frame; Described frame enclosed space is divided at least one pair of space by described dividing plate.
9. the manufacture method of thermoelectric device according to claim 1 and 2 unit, is characterized in that: in described step S2, described electrode material is layed in to described push-down head upper surface with powder or block form.
10. the manufacture method of thermoelectric device according to claim 1 and 2 unit, is characterized in that: in described step S2, the described P type thermoelectric material of laying and N-type thermoelectric material are powder or prefabricated block.
The manufacture method of 11. thermoelectric device according to claim 1 and 2 unit, it is characterized in that: in described step S1, also comprise the step of described mould being cleaned and being sprayed release agent, in described step S3, after sintering, directly from described mould, take out described π type thermoelectric device unit block.
The manufacture method of 12. thermoelectric device according to claim 1 and 2 unit, it is characterized in that: in described step S3, adopt discharge plasma sintering, thermal resistance heating pressure sintering or induction heating pressure sintering method to obtain π type thermoelectric device unit block.
The manufacture method of 13. thermoelectric device according to claim 1 and 2 unit, it is characterized in that: in described step S2, in every pair of slits, insert respectively after P type thermoelectric material and N-type thermoelectric material, then lay cold junction electrode material at described P type thermoelectric material and N-type thermoelectric material upper surface respectively, and then cover described seaming chuck.
The manufacture method of 14. thermoelectric device according to claim 1 and 2 unit, is characterized in that: described mould is made by the one in graphite, alloy, alumina-based ceramic, silicon-nitride-based ceramic, types of silicon carbide-based ceramics or at least two kinds of combinations obtain.
The manufacture method of 15. thermoelectric device according to claim 1 and 2 unit, is characterized in that: described thermoelectric material comprises CoSb
3, MgSi
xse
1-x, CaSn
2sb
2, Yb
14mnSb
11, lead telluride, SiGe and Bi
2te
3in at least one, wherein, 0<x<1.
The manufacture method of 16. thermoelectric device according to claim 1 and 2 unit, is characterized in that: in described seaming chuck, described lid is fixedly connected with or contacts with described presser feet and is connected.
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