CN106384780B - A method of quickly preparing thermo-electric device - Google Patents
A method of quickly preparing thermo-electric device Download PDFInfo
- Publication number
- CN106384780B CN106384780B CN201610125844.8A CN201610125844A CN106384780B CN 106384780 B CN106384780 B CN 106384780B CN 201610125844 A CN201610125844 A CN 201610125844A CN 106384780 B CN106384780 B CN 106384780B
- Authority
- CN
- China
- Prior art keywords
- electrode layer
- powder
- electric device
- type
- thermo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
Abstract
The present invention provides a kind of method for quickly preparing thermo-electric device, include the following steps: 1) to prepare raw material；2) according to required electrode pattern and thickness, electrode powder is printed upon on insulating substrate (one) using selective laser smelting process；3) p-type, N-shaped thermoelectric compound powder are printed as on the resulting electrode layer one of step 2) respectively by p-type, N-shaped thermoelectric arm using selective laser smelting process；4) electrode powder is printed upon p-type, on N-shaped thermoelectric arm using selective laser smelting process, obtains being printed with the p-type of electrode layer two, on N-shaped thermoelectric arm；5) by insulating substrate two in two surface cover of electrode layer, thermo-electric device is obtained.The present invention is directly from thermoelectric material powder, using laser selective smelting process, thermo-electric device is printed by Layered Manufacturing Technology, cumbersome intermediate link during Conventional thermoelectric device preparation technology is avoided, overcomes the problems, such as that yield rate is low low with raw material availability in traditional welding packaging technology.
Description
Technical field
The present invention relates to a kind of new methods for quickly preparing thermo-electric device, belong to thermoelectric material and device new preparation process.
Background technique
Thermoelectric generation technology includes thermoelectric cooling technology and thermoelectric generation, the former will using the paltie effect of material
Electric energy is converted to thermal energy, and the latter converts heat energy into electric energy using the Seebeck effect of material, as a kind of all solid state novel
Energy conversion technology, thermo-electric device have long-life, Maintenance free and adapt to the advantages such as adverse circumstances.Wherein, thermoelectric cooling skill
Art is applied to the refrigerating field that corresponding noise and space etc. have particular/special requirement, such as uses the red wine cabinet and automobile of thermoelectric cooling technology
The refrigeration of cushion, laser diode realized using miniature thermoelectric refrigerator part, the size of minisize refrigeration device up to 3 ×
3×1mm3, and wherein the sectional area of the basic component units thermoelectric material particle of thermoelectric cooling device is up to 0.1 × 0.1mm2.Heat
Electric generation technology be mainly used in independent electric power supply from far-off regions, waste heat of automotive exhaust gas recycling, Industrial Stoves Waste Heat Recovery and
The fields such as solar photoelectric thermoelectricity compound electricity generation system.Currently, material applied in thermoelectric power generation technology have bismuth telluride and its
Alloy, lead telluride and its alloy and sige alloy, and the thermoelectric material of the better performances of some other laboratory report is due to device
Bottleneck in part technology of preparing and be difficult to realize commercialized application.
The preparation process of existing commercialized thermo-electric device is generally then to be cut using block thermoelectric material is first obtained
At thermoelectric material particle, by welding by p-type and N-shaped thermoelectric material and the flow guide bar knot for being arranged in insulating ceramics on piece
Merging is serially connected together.The mode of this welding has following several disadvantages: 1. complex procedures when preparing thermo-electric device, packet
It is at high cost containing a large amount of manual process；2. with the reduction of thermoelectric material particle size and the increase of quantity, since cutting is lost
It is substantially reduced with stock utilization caused by damage and yield rate；3. heat-affected zone is larger in welding process, to material and connect
There are unpredictable influences for the performance of head.
3D printing technique is in the nearest attention for being increasingly subject to people for 10 years, using the basic principle of layering superposition manufacture, reason
The part of any complicated shape can be printed by upper 3D printing technique, the type of printable material is from plastics, metal again to ceramics
And life entity etc..The feature that selective laser sintering or fusion technology utilize local laser energy density high, by powder part
Heating reaches fusing point or more, is sintered together it, and this technology is widely used in stainless steel, Ti alloy, Ni alloy, CoCr and closes
The 3D printing of the high temperature alloys such as gold and ceramics can be greatly shortened using 3D printing technique from product in the design link of product
Conceptual design sketch is to the molding time, so as to push the exploitation of new product faster.Selective laser fusion technology mesh
Before be mainly used for printing traditional metal parts, belong to structural material.Currently, the material system of exploitation business application is still defined in
The structural materials such as stainless steel, Co base, Ni base, Ti based high-temperature alloy, do not have functional material, such as printing of semiconductor material substantially
Research.Report is disclosed for printing not yet someone of thermoelectric material and device, may be in terms of following two the reason of: 1.
3D printing field, direction concerned by people is structural material, rather than functional material；2. existing thermoelectric material powder technology of preparing
It is difficult to meet the requirement of commercialization selective laser fusion apparatus, existing commercialization selective laser fusion apparatus is difficult in other words
To meet the requirement of thermoelectric material powder printing.This is because the powder shape that current thermoelectric material powder technology of preparing obtains
Shape is irregular, and mobility is not able to satisfy the requirement of commercial equipment powdering；In addition, thermo-electric device includes at least three kinds of different
Material (electrode material, p-type and N-shaped thermoelectric material) can not be completed using existing commercial equipment in a print procedure
The printing of entire device.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of quickly system in view of the deficiency of the prior art
The method of standby thermo-electric device passes through the 3D printing technique and increasing material manufacturing skill for combining inkjet printing and selective laser to melt
Art prints thermo-electric device, avoids cumbersome intermediate link during Conventional thermoelectric device preparation technology, while can directly print micro-
Type device overcomes the problems, such as that yield rate is low low with raw material availability in traditional welding packaging technology.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A method of thermo-electric device quickly being prepared, is included the following steps:
1) prepare raw material, including insulating substrate, electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder
Body；
2) according to required electrode pattern and thickness, electrode powder is printed upon absolutely using selective laser smelting process
On edge substrate (one), the insulating substrate for being printed with electrode layer (one) is obtained；
3) according to the device thermoelectric arm size of design and distribution, using selective laser smelting process respectively by p-type thermoelectricity
Compound powder and N-shaped thermoelectric compound powder are printed as p-type thermoelectric arm and N-shaped heat on the resulting electrode layer of step 2) (one)
Electric arm；
4) according to required electrode pattern and thickness, electrode powder is printed upon p using selective laser smelting process
It on type thermoelectric arm and N-shaped thermoelectric arm, is formed electrode layer (two), p-type thermoelectric arm is connected by the electrode layer (two) with N-shaped thermoelectric arm
It connects；
5) insulating substrate (two) in the electrode layer (two) surface cover, obtains thermo-electric device.
According to the above scheme, the electrode layer (one), electrode layer (two) are printed by the electrode powder described in step 1).
According to the above scheme, the insulating substrate (one), insulating substrate (two) are the insulating substrate that step 1) is prepared, can
With Ceramics insulating substrate.
According to the above scheme, the thermo-electric device size range that the present invention can be prepared is larger, is particularly suitable for preparing minisize thermoelectric
Device, the section side size range of thermoelectricity single armed are 0.1~3mm, and thermo-electric device side size range is 3~100mm.
According to the above scheme, the thermo-electric device that prepared by the structure with traditional handicraft of the thermo-electric device is similar, i.e. electrode layer one
It is distributed on insulating substrate with two, according to the suitable of electrode layer one, thermoelectric arm, electrode layer two, thermoelectric arm and electrode layer one
P-type and N-shaped thermoelectric arm are sequentially connected in series by sequence.Wherein, electrode layer (one), electrode layer (two) thickness preferred 0.1-0.5mm, two
The preferred 3-10mm in interval between electrode layer.
According to the above scheme, in step 1), electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder
Granularity control in 0.1~50 μ m.Preferably, by electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound
Powder, which is scattered in respectively in water or other volatile solvents, is made suspension for inkjet printing, and the solid concentration of suspension is controlled
System is 1~40%.Wherein, other volatile solvents can be selected from ethyl alcohol and acetone etc..
According to the above scheme, for the amount of raw material each in step 1) depending on the size of the thermo-electric device of required printing,
This is not especially limited.
According to the above scheme, the step 2) is repeated when necessary, until reaching thickness required for electrode layer (one)
Degree.
According to the above scheme, the step 3) is repeated when necessary, until reaching p-type thermoelectric arm and N-shaped thermoelectric arm
Required thickness.
According to the above scheme, the step 4) is repeated when necessary, until reaching thickness required for electrode layer (two)
Degree.
According to the above scheme, the electrode powder is in simple substance Ni, Cu, Ag, Al, Mo, W, Ti or NiAl alloy epitaxy etc.
One or more of mixtures in any proportion.
According to the above scheme, the p-type thermoelectric compound is selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、
Zr0.5Hf0.5One of CoSb and PbSe etc.；The N-shaped thermoelectric compound is selected from Bi2Te3-xSex、SnTe、n-Co4Sb12- xTex、Mg2Si1-xSnx, one of ZrNiSn and PbS etc..
According to the above scheme, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser,
Wavelength is 1060~1070nm, and the power control of laser is in 5~100W, and laser scanning line rate control is in 10~500mm/s, gas
Atmosphere control is 0.5~1 atmospheric pressure inert atmosphere (such as nitrogen, argon gas), and single layer powdering thickness is at 30~100 μm.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention is beaten directly from thermoelectric material powder by the 3D for combining inkjet printing and selective laser to melt
Print technology and increases material manufacturing technology print thermo-electric device, avoid cumbersome centre during Conventional thermoelectric device preparation technology
Link, while can directly print microdevice, overcomes in traditional welding packaging technology that yield rate is low low with raw material availability to ask
Topic.
2, the present invention does not need complicated Modeling and Design early period using 3D printing, and printing effect is relatively some complex-shaped
Part want high, can satisfy the compound with regular structure of thermo-electric device and height be generally below the demand of 10mm.
3, the present invention using laser heating process in laser selective smelting process to the heat-affected zone of thermoelectric material compared with
It is small, it can avoid influence of the thermal shock to material property in traditional handicraft welding process.
Detailed description of the invention
Fig. 1 is equipment overall structure schematic diagram；
Fig. 2 a is single nozzle printing equipment schematic diagram；
Fig. 2 b is the side view of Fig. 2 a；
Fig. 3 is gas-circulating system schematic diagram；
Fig. 4 is inkjet printing pattern and laser scanning zone map schematic diagram；
Fig. 5 is more sprinkler equipment overall structure diagrams；
Fig. 6 a is double nozzle printing schematic devices；
Fig. 6 b is the side view of Fig. 6；
Fig. 7 is that three spray head parallel verticals place printing equipment schematic diagram；
Fig. 8 is that the inclination of three spray heads focuses placement printing equipment schematic diagram.
Fig. 9 be the present invention in selective laser melting printing thermo-electric device flow diagram, be followed successively by figure A, figure B, figure C,
Scheme D, while including cross-sectional view and top view.Mark is described as follows in figure: 1 is ceramic substrate；2 be electrode layer one；3 be single layer p
Type thermoelectric arm；4 be single layer of n-type thermoelectric arm；5 be p-type thermoelectric arm of the duplicate printing to setting height；6 be duplicate printing to setting
The N-shaped thermoelectric arm of height；7 be electrode layer two.
Figure 10 is N-shaped Bi in embodiment 12Te2.8Se0.2Thermoelectric arm laser scanning surface texture after molding.
Figure 11 is p-type SnTe thermoelectric arm surface texture after molding in embodiment 2.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Two kinds of 3D printing device and method thereof for combining inkjet printing and selective laser fusion technology are provided in the present invention,
The technical solution of the present invention for quickly preparing thermo-electric device may be implemented.But the present invention realizes and quickly prepares thermo-electric device
Method be not limited to equipment provided below, it is any to can be realized technical solution documented by claims of the present invention
Equipment or equipment could be used for the present invention, and the present invention is without limitation.
1, the first 3D printing device and method thereof for combining inkjet printing and selective laser fusion technology
(1) the 3D printing equipment of a kind of combination inkjet printing and selective laser fusion technology, including storage tank, forming cavity
And gas-recycling plant, the forming cavity top are equipped with laser light incident window, are equipped with inkjet-printing device, institute in the forming cavity
Stating inkjet-printing device includes substrate and inkjet print head, and the storage tank is for storing ink, and by providing ink to described
Inkjet print head, the gas-recycling plant include seal cavity, are equipped with filter layer, drying layer and circulated air inside seal cavity
Machine is tightly connected in the seal cavity with the forming cavity.
Further, in above-mentioned equipment, the inkjet-printing device further includes the pedestal with x to displacement platform, the x to
It places substrate on displacement platform, is arranged with y on pedestal to the bracket of displacement platform, y fixes z on displacement platform to displacement platform, and z is to displacement
Inkjet print head is fixed on platform, the inkjet print head is located above substrate.
Further, in above-mentioned equipment, panel heater is equipped with below the substrate.
Further, in above-mentioned equipment, the molding cavity wall is equipped with to the volatile solvent in gas in cavity
The solvent gas concentration detector that is monitored of content.
Further, in above-mentioned equipment, the molding cavity wall be equipped with to the vapour content in gas in cavity into
The water vapour content detector of row monitoring.
(2) printing technology of above-mentioned combination inkjet printing and the 3D printing equipment of selective laser melting includes following step
It is rapid:
A. the ink in storage tank is injected into inkjet print head；
B. single layer pattern needed for inkjet print head is printed on substrate by the way of inkjet printing；
C. the temperature of control base board makes the solvent in ink quickly volatilize, and passes through the drying layer in gas-recycling plant
It rapidly removes, dry working gas is returned to inside molding cavity；
D. after inkjet print head is removed above substrate, substrate returns to origin, and the pattern on substrate is molten by precinct laser
Row molding and connection are circulated, single layer densified thin layer material is obtained；
E. it repeats above procedure and obtains multiple dense block materials.
Further, in above-mentioned technique, working gas is Ar or N in forming cavity2；
Further, in above-mentioned technique, after step c, the water content of working gas is reduced to 100ppm in forming cavity
After below, step d is just executed.
Further, in above-mentioned technique, after step c, the oxygen content of working gas is reduced to 100ppm in forming cavity
After below, step d is just executed.
(3) in conjunction with attached drawing, this is illustrated in conjunction with the 3D printing equipment of inkjet printing and selective laser fusion technology tool
Body includes forming cavity 1, the storage tank 3 for storing ink, gas-circulating system 4 and the (figure of solvent gas concentration detector 5
1)。
An inkjet-printing device 2 is placed in forming cavity 1, which can move up and down in overall at cavity 1.Inkjet printing
Device 2 (Fig. 2 a, Fig. 2 b) includes the pedestal 21 of a displacement platform with the movement of the direction x, which is sequentially placed a plate on displacement platform
Heater 26 and substrate 25.One bracket 22 is set on pedestal, and with the displacement platform that can be moved in the y-direction on bracket 22, the y is to position
A displacement platform 23 that can be moved in the z-direction is fixed in moving stage again, which fixes an inkjet print head 24, ink-jet on displacement platform 23
Print head 24 is located at 25 top of substrate.
Ink in storage tank 3 can pass through the inkjet print head 24 in pipeline to forming cavity.Gas-circulating system 4
(Fig. 3) includes a seal cavity 31, is provided with an air inlet 36 at the top of cavity, side is provided with an air outlet 32, inside cavity
It is provided with a drying layer 35, filter layer 34 and circulating fan 33 from top to bottom.
Its working method are as follows: the ink in storage tank 3 is transported in inkjet print head 24, and inkjet print head 24 sprays ink
It shoots out and deposits to 25 surface of substrate, the first layer pattern is printed on substrate 25 by the relative motion of spray head 24 and substrate 25,
The temperature control of substrate 25 solvent boiling point hereinafter, aqueous solvent is made quickly to volatilize, vapor and working gas Ar or N2Mixing
It is removed by being adsorbed after gas-recycling plant 4 by drying layer 35.After ink dried, substrate 25 returns to origin.Using solvent gas
Bulk concentration water finder 5 detects the concentration of vapor in mixed gas, molten using selective laser when its content is in 100ppm
The powder layer material on technique substrate 25 melted is scanned and curing molding is simultaneously connected with substrate 25.Above procedure is repeated to obtain
Obtain multilayer compact block material.In the above process, model of the range 42 of selective laser smelting process scanning in inkjet printing
(Fig. 4) is enclosed within 41.
2, the 3D printing device and method thereof of second combination inkjet printing and selective laser fusion technology
(1) the 3D printing equipment of a kind of combination inkjet printing and selective laser fusion technology, is followed comprising forming cavity, gas
Loop device and at least two storage tanks, the forming cavity top are equipped with laser light incident window, beat in the forming cavity equipped with ink-jet
Printing equipment is set, and the inkjet-printing device includes substrate and at least two inkjet print heads, and the storage tank is used to store ink, and
By providing ink to the inkjet print head, the gas-recycling plant includes seal cavity, is equipped with filtering inside seal cavity
Layer, drying layer and circulating fan are tightly connected in the seal cavity with the forming cavity.
Further, in above-mentioned equipment, the inkjet-printing device further includes the pedestal with x to displacement platform, the x to
It places substrate on displacement platform, is arranged with y on pedestal to the bracket of displacement platform, y fixes z on displacement platform to displacement platform, and z is to displacement
Inkjet print head is fixed on platform, the inkjet print head is located above substrate.
Further, in above-mentioned equipment, two or more inkjet print head parallel equidistants are placed, ink injection side
To for vertical direction.
Further, in above-mentioned equipment, the inkjet print head quantity is three, and intermediate inkjet printing head erect is put
It sets, left and right inkjet printing head tilt is symmetrically placed, and inkjet print head center line extended line intersects in substrate surface.
(2) printing technology of the 3D printing equipment of above-mentioned combination inkjet printing and selective laser fusion technology, can be simultaneously
Block part of the printing comprising 2 kinds and the above different materials comprising the steps of:
A. the ink in storage tank is injected under the effect of the pressure in the corresponding inkjet print head of forming cavity；
B. the movement of more a inkjet print head combination substrates prints respective material by the way of inkjet printing on substrate
Single layer pattern；
C. the temperature of control base board makes the solvent in ink quickly volatilize, and passes through the drying layer in gas-recycling plant
It rapidly removes, dry working gas is returned to inside molding cavity；
D. after inkjet print head is removed above substrate, substrate returns to origin, and the pattern on substrate is molten by precinct laser
Row molding and connection are circulated, single layer densified thin layer material is obtained；
E. it repeats above procedure and obtains multiple dense block materials.
Further, in above-mentioned technique, printing type is that multiple inkjet print heads print corresponding material one by one in step b
Material；
Further, in above-mentioned technique, printing type is that multiple inkjet print heads work at the same time printing correspondence in step b
The pattern of material；
Further, in above-mentioned technique, laser scanning methods are successively to scan to different materials in step d；
Further, in above-mentioned technique, laser scanning methods are that spatially arrangement mode successively scans in step d.
(3) in conjunction with attached drawing, citing illustrates second and the 3D of inkjet printing and selective laser fusion technology is combined to beat
Printing apparatus can print a variety of different materials simultaneously, and equipment includes: forming cavity 1, multi-headed ink-jet printing equipment 51 are used to store three
Storage tank 52,53 and 54, gas-circulating system 4 and the solvent gas concentration detector 5 of the different inks of kind.
The multi-headed ink-jet printing equipment 51 can be dual head ink jet device, and the ink-jet placed comprising 2 parallel verticals is beaten
Head 61 and 62 is printed, (Fig. 5) is connected with bracket by spray head stationary fixture 53；
The multi-headed ink-jet printing equipment 51 is also possible to 3 ink discharge devices, includes 3 inkjet print heads (Fig. 6, figure
7), 3 spray heads 71,72 and 73 can parallel vertical placement.
Its working method are as follows: the ink in storage tank 52,53 and 54 is delivered to respectively in inkjet print head 71,72 and 73.
Spray head 71 works first prints that the pattern for material, then spray head 72 and 73 successively works on substrate 25, in substrate 25
The upper corresponding pattern of printing；The temperature of control base board 25 is 80 DEG C, so that the water in ink is quickly volatilized, is recycled by gas
Drying layer 35 in system 4 and rapidly remove, by dry working gas Ar back to inside forming cavity 1；Inkjet print head from
After removing above substrate 25, substrate 25 returns to origin, and the pattern on substrate 25 is formed and connected by precinct laser melting,
Obtain single layer densified thin layer material.It repeats above procedure and obtains multiple dense block materials.
Embodiment 1
A kind of quickly preparation p-type Bi0.5Sb1.5Te3In conjunction with N-shaped Bi2Te2.8Se0.2The method of thermo-electric device, including walk as follows
It is rapid:
1) prepare raw material, weighing group becomes Bi0.5Sb1.5Te3(p-type thermoelectric material) and Bi2Te2.8Se0.2(N-shaped thermoelectricity material
Material) thermoelectric material powder and each 500 grams of electrode powder Cu powder, each material powder cross 400 meshes after, be scattered in respectively
In 300ml, 300ml and 220ml water, it is subsequently placed in the ink in 3 different storage tanks as inkjet printing, in storage tank
Ink is delivered in ink jet printing head under the effect of the pressure；And prepare with a thickness of 1mm, side length is the square Al of 30mm2O3
Ceramic wafer is placed and is fixed on printing substrate；To molding cavity forvacuum 5 minutes of selective laser melting plant, then
Cavity is backfilled to normal pressure using Ar gas, keeps cavity water oxygen content in 100ppm hereinafter, basal plate preheating to 80 DEG C and is kept the temperature simultaneously
10 minutes；
2) the Cu powder in storage tank is paved with ceramic base plate surface described in step 1) using inkjet printing mode first, spread
Powder is with a thickness of 50 microns, then using laser according to region (such as a series of rectangle diagrams being arranged on substrate in length and breadth of setting
Case) Cu powder is scanned, laser scan rate is selected as 30mm/s, and laser power is selected as 100W；Wherein, Cu powder is under laser action
It combines with ceramic wafer after fusing and forms electrode layer, the area of single Cu electrode is 2.5 × 5mm2, repeat the above powdering and laser swept
Retouching process to Cu electrode layers thickness is 0.5mm (see Fig. 9-A) to get to the insulating substrate for being printed with electrode layer (one)；
3) by storage tank p-type and N-shaped thermoelectric material powder interval inkjet printing in the resulting electrode layer of step 2)
(1) surface, the size of the thermoelectric arm of design are 2 × 2 × 2mm2, then using laser according to the thermo-electric device thermoelectric arm of design
Size and distribution are scanned, and print single p-type thermoelectric arm and N-shaped thermoelectric arm；Wherein, when printing p-type and N-shaped thermoelectric arm, paving
For powder with a thickness of 60 microns, laser scan rate is selected as 80mm/s, and laser power is selected as 40W；Repeat beating for the above thermoelectric arm
Print process is until its height is 2mm (see Fig. 9-B, C)；
4) the electrode powder Ag powder in storage tank is layered on the resulting p-type thermoelectric arm of step 3) and N-shaped thermoelectric arm, is used
Laser scan rate is selected as 30mm/s, and laser power is selected as 100W, is scanned printing to Cu powder according to condition and forms electricity
Pole layer (two), electrode layer (two) connect p-type and N-shaped thermoelectric arm (see Fig. 9-D)；The step is repeated until electrode layer (two)
With a thickness of 0.5mm, the size and electrode layer (one) of electrode layer (two) are identical；
5) by insulating substrate (two) in the electrode layer (two) surface cover, Bi is obtained2Te3Thermo-electric device.
Figure 10 is N-shaped Bi2Te2.8Se0.2Thermoelectric arm laser scanning surface texture after molding, it can be seen that at laser melting
Surface after reason or relatively flat.
Embodiment 2
A kind of method of quick preparation p-type SnTe/n type SnSe thermo-electric device, includes the following steps:
1) prepare raw material, weighing group becomes the thermoelectric material powder of SnTe (p-type thermoelectric material) and SnSe (N-shaped thermoelectric material)
Body and each 500 grams of electrode powder Ag powder, after each material powder crosses 400 meshes, be scattered in respectively 230ml, 250ml and
In 250ml water, it is subsequently placed in the ink in 3 different storage tanks as inkjet printing, the ink in storage tank is in pressure
It is transported in ink jet printing head under effect；Prepare the Al with a thickness of 1mm2O3Ceramic wafer is placed and is fixed on printing substrate；It is right
Then the molding cavity forvacuum of selective laser melting plant 5 minutes backfills cavity to normal pressure using Ar gas, keeps cavity
Water oxygen content is in 100ppm hereinafter, basal plate preheating to 80 DEG C and keeps the temperature 10 minutes simultaneously；
2) the Ag powder in storage tank is paved with ceramic base plate surface described in step 1) first, powdering with a thickness of 50 microns,
Then using laser according to the sector scanning Ag powder of setting, laser scan rate is selected as 30mm/s, and laser power is selected as
100W；Wherein, it combines with ceramic wafer after Ag powder melts under laser action and forms electrode layer, repeat the above powdering and laser scanning
Process is to reaching required electrode layers thickness to get to the insulating substrate for being printed with electrode layer (one)；
3) by storage tank p-type and N-shaped thermoelectric material powder interval spread over the resulting electrode layer of step 2) (one) table
Then face is scanned according to the thermo-electric device thermoelectric arm size of design and distribution using laser, is printed as p-type thermoelectric arm and n
Type thermoelectric arm；Wherein, when printing p-type and N-shaped thermoelectric arm, for powdering with a thickness of 50 microns, laser scan rate is selected as 50mm/s,
Laser power is selected as 50W；The print procedure of the above thermoelectric arm is repeated until desired height；
4) the electrode powder Ag powder in storage tank is layered on the resulting p-type thermoelectric arm of step 3) and N-shaped thermoelectric arm, according to
The design of thermo-electric device is scanned printing to Ag powder using laser and forms electrode layer (two), and p-type has been connected with N-shaped thermoelectric arm
Come；
5) by insulating substrate (two) in the electrode layer (two) surface cover, p-SnTe/n-SnSe thermo-electric device is obtained.
Figure 11 is p-type SnTe thermoelectric arm laser scanning surface texture after molding, it can be seen that after laser melting
Surface is very smooth.
Embodiment 3
A kind of quickly preparation p-CeFe4Sb12In conjunction with N-shaped Co4Sb12-xTexThe method of (x=0~0.1) thermo-electric device, including
Following steps:
1) prepare raw material, including Al2O3Ceramic insulation substrate, Cu50Mo50Alloy electrode powder, p-type p-CeFe4Sb12Thermoelectricity
Compound powder and N-shaped Co4Sb12-xTex(x=0~0.1) thermoelectric compound powder, wherein the partial size of each powder material is 50
μm hereinafter, and be scattered in water respectively suspension be made for the inkjet printing in subsequent step, the mass percent of suspension is equal
It is 30%；
2) according to required electrode pattern and thickness, electrode powder suspension is sprayed using selective laser smelting process
Ink is printed upon on insulating substrate (one), obtains the insulating substrate for being printed with electrode layer (one)；
3) according to the device thermoelectric arm size of design and distribution, using selective laser smelting process respectively by p-type thermoelectricity
Compound powder and N-shaped thermoelectric compound powder suspension inkjet printing on the resulting electrode layer of step 2) (one) are warm at p-type
Electric arm and N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is sprayed using selective laser smelting process
Ink is printed upon on p-type thermoelectric arm and N-shaped thermoelectric arm, is formed electrode layer (two), and the electrode layer (two) is by p-type thermoelectric arm and N-shaped
Thermoelectric arm is connected；
5) insulating substrate (two) in the electrode layer (two) surface cover, obtains thermo-electric device.
Wherein, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 3), 4) in laser power be respectively 100W, 80W and 80W；Sweep speed be respectively 80mm/s,
200mm/s, 200mm/s, control climate are 0.5~1 atmospheric pressure inert atmosphere, and single layer powdering thickness is at 30 μm.
Embodiment 4
A kind of quickly preparation p-type MnSi1.75In conjunction with N-shaped Mg2Si1-xSnxThe method of (x=0~1) thermo-electric device, including such as
Lower step:
1) prepare raw material, including Al2O3Ceramic insulation substrate, NiAl alloy epitaxy electrode powder, p-type MnSi1.75Thermoelectric compound
Powder and N-shaped Mg2Si1-xSnx(x=0~1) thermoelectric compound powder, wherein the partial size of each powder material be 50 μm hereinafter, and
It is scattered in water respectively, suspension is made for the inkjet printing in subsequent step, the mass percent of suspension is 40%；
2) according to required electrode pattern and thickness, electrode powder suspension is sprayed using selective laser smelting process
Ink is printed upon on insulating substrate (one), obtains the insulating substrate for being printed with electrode layer (one)；
3) according to the device thermoelectric arm size of design and distribution, using selective laser smelting process respectively by p-type thermoelectricity
Compound powder and N-shaped thermoelectric compound powder suspension inkjet printing on the resulting electrode layer of step 2) (one) are warm at p-type
Electric arm and N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is sprayed using selective laser smelting process
Ink is printed upon on p-type thermoelectric arm and N-shaped thermoelectric arm, is formed electrode layer (two), and the electrode layer (two) is by p-type thermoelectric arm and N-shaped
Thermoelectric arm is connected；
5) insulating substrate (two) in the electrode layer (two) surface cover, obtains thermo-electric device.
Wherein, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 3), 4) in laser power be respectively 100W, 70W and 70W；Sweep speed is respectively 50mm/s, 60mm/
S, 60mm/s, control climate are 0.5~1 atmospheric pressure inert atmosphere, and single layer powdering thickness is at 50 μm.
Embodiment 5
A kind of quickly preparation p-type Zr0.5Hf0.5The method of CoSb combination N-shaped ZrNiSn thermo-electric device, includes the following steps:
1) prepare raw material, including Al2O3Ceramic insulation substrate, Cu50W50Alloy electrode powder, p-type Zr0.5Hf0.5CoSb heat
Electric compound powder and N-shaped ZrNiSn thermoelectric compound powder, wherein the partial size of each powder material is 50 μm hereinafter, and respectively
It is scattered in water and suspension is made for the inkjet printing in subsequent step, the mass percent of suspension is 20%；
2) according to required electrode pattern and thickness, electrode powder suspension is beaten using selective laser smelting process
It is imprinted on insulating substrate (one), obtains the insulating substrate for being printed with electrode layer (one)；
3) according to the device thermoelectric arm size of design and distribution, using selective laser smelting process respectively by p-type thermoelectricity
Compound powder and N-shaped thermoelectric compound powder suspension are printed as p-type thermoelectric arm on the resulting electrode layer of step 2) (one)
With N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is beaten using selective laser smelting process
It is imprinted on p-type thermoelectric arm and N-shaped thermoelectric arm, is formed electrode layer (two), the electrode layer (two) is by p-type thermoelectric arm and N-shaped thermoelectricity
Arm is connected；
5) insulating substrate (two) in the electrode layer (two) surface cover, obtains thermo-electric device.
Wherein, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 3), 4) in laser power be respectively 100W, 90W and 90W；Sweep speed be respectively 20mm/s,
100mm/s, 100mm/s, control climate are 0.5~1 atmospheric pressure inert atmosphere, and single layer powdering thickness is at 60 μm.
Embodiment 6
A kind of method of quick preparation p-type PbSe combination N-shaped PbS thermo-electric device, includes the following steps:
1) prepare raw material, including Al2O3Ceramic insulation substrate, TiAl alloy electrode powder, p-type PbSe thermoelectric compound powder
Body and N-shaped PbS thermoelectric compound powder, wherein the partial size of each powder material is 50 μm hereinafter, and being scattered in water respectively and being made
For suspension for the inkjet printing in subsequent step, the mass percent of suspension is 5%；
2) according to required electrode pattern and thickness, electrode powder suspension is beaten using selective laser smelting process
It is imprinted on insulating substrate (one), obtains the insulating substrate for being printed with electrode layer (one)；
3) according to the device thermoelectric arm size of design and distribution, using selective laser smelting process respectively by p-type thermoelectricity
Compound powder and N-shaped thermoelectric compound powder suspension are printed as p-type thermoelectric arm on the resulting electrode layer of step 2) (one)
With N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is beaten using selective laser smelting process
It is imprinted on p-type thermoelectric arm and N-shaped thermoelectric arm, is formed electrode layer (two), the electrode layer (two) is by p-type thermoelectric arm and N-shaped thermoelectricity
Arm is connected；
5) insulating substrate (two) in the electrode layer (two) surface cover, obtains thermo-electric device.
Wherein, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 3), 4) in laser power be respectively 80W, 50W and 50W；Sweep speed is respectively 80mm/s, 300mm/
S, 300mm/s, control climate are 0.5~1 atmospheric pressure inert atmosphere, and single layer powdering thickness is at 30 μm.
The present invention illustrates embodiments of the present invention by taking the typical thermoelectric material system of embodiment these types as an example respectively,
His known a variety of thermoelectric materials can be by changing electrode material composition appropriate and selective laser smelting process parameter
Thermo-electric device is obtained, example is just not listed one by one herein.But a variety of thermoelectric materials listed in the present invention this be able to achieve this hair
The bright technical solution.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (8)
1. a kind of method for quickly preparing thermo-electric device, it is characterised in that include the following steps:
1) prepare raw material, including insulating substrate, electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder；
2) according to required electrode pattern and thickness, electrode powder is printed upon by insulation base using selective laser smelting process
On plate, the insulating substrate for being printed with electrode layer one is obtained；
3) according to the device thermoelectric arm size of design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder and N-shaped thermoelectric compound powder are printed as p-type thermoelectric arm and N-shaped thermoelectric arm on the resulting electrode layer one of step 2)；
4) according to required electrode pattern and thickness, electrode powder is printed upon p-type heat using selective laser smelting process
Electrode layer two is formed in electric arm and N-shaped thermoelectric arm, p-type thermoelectric arm is connected by the electrode layer two with N-shaped thermoelectric arm；
5) after two surface of electrode layer polishing flat, an insulating substrate is covered, thermo-electric device is obtained；
It disperses water or volatilization respectively by electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder in step 1)
Property solvent in suspension is made for subsequent printing step, the solid concentration of suspension is 1~40wt%；
Step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, wave-length coverage 1060
~1070nm, in 5~100W, laser scanning line rate control is the power control of laser in 10~500mm/s, control climate
0.5~1 atmospheric pressure inert atmosphere, single layer powdering thickness is at 30~100 μm.
2. a kind of method for quickly preparing thermo-electric device according to claim 1, it is characterised in that thermo-electric device side length model
It encloses for 3~100mm, the section side size range of each thermoelectric arm is 0.1~3mm.
3. a kind of method for quickly preparing thermo-electric device according to claim 1, it is characterised in that electrode layer one and two is equal
It is distributed on insulating substrate, according to the suitable of electrode layer one, p-type thermoelectric arm, electrode layer two, N-shaped thermoelectric arm and electrode layer one
P-type and N-shaped thermoelectric arm are sequentially connected in series by sequence.
4. a kind of method for quickly preparing thermo-electric device according to claim 1, it is characterised in that repeat to grasp in step 2)
Make until reaching thickness required for electrode layer one；Repetitive operation in step 4) is until reach thickness required for electrode layer two.
5. a kind of method for quickly preparing thermo-electric device according to claim 1, it is characterised in that repeat to grasp in step 3)
Make until reaching thickness required for p-type thermoelectric arm and N-shaped thermoelectric arm.
6. a kind of method for quickly preparing thermo-electric device according to claim 1, it is characterised in that the electrode powder choosing
From the mixture of one or more of simple substance Ni, Cu, Ag, Al, Mo, W, Ti or NiAl alloy epitaxy in any proportion.
7. a kind of method for quickly preparing thermo-electric device according to claim 1, it is characterised in that the p-type thermoelectricity chemical combination
Object is selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、Cu2Se、Zr0.5Hf0.5Any one in CoSb and PbSe；Institute
It states N-shaped thermoelectric compound and is selected from Bi2Te3-xSex、SnTe、n-Co4Sb12-xTex、Mg2Si1-xSnx, it is any in ZrNiSn and PbS
It is a kind of.
8. thermo-electric device prepared by any one in claim 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610125844.8A CN106384780B (en) | 2016-03-06 | 2016-03-06 | A method of quickly preparing thermo-electric device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610125844.8A CN106384780B (en) | 2016-03-06 | 2016-03-06 | A method of quickly preparing thermo-electric device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106384780A CN106384780A (en) | 2017-02-08 |
| CN106384780B true CN106384780B (en) | 2019-03-19 |
Family
ID=57916639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610125844.8A Active CN106384780B (en) | 2016-03-06 | 2016-03-06 | A method of quickly preparing thermo-electric device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106384780B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6839690B2 (en) * | 2018-09-27 | 2021-03-10 | アイシン高丘株式会社 | How to manufacture a thermoelectric module |
| CN110783448B (en) * | 2019-07-30 | 2020-10-16 | 武汉理工大学 | Method for manufacturing micro thermoelectric device based on femtosecond laser technology |
| CN112885950A (en) * | 2019-11-30 | 2021-06-01 | 中国科学院金属研究所 | Method for manufacturing micro thermoelectric device by using 3D printing technology |
| CN111266579A (en) * | 2020-02-25 | 2020-06-12 | 中国科学院上海硅酸盐研究所 | Full-automatic selective laser melting continuous synthesis equipment and method |
| CN111864043B (en) * | 2020-08-06 | 2023-02-28 | 武汉理工大学 | P-type Cu2 Se-based thermoelectric element and integrated preparation process thereof |
| CN112426734B (en) * | 2020-12-03 | 2021-09-28 | 西安交通大学 | Thermoelectric-driven interface evaporation device |
| CN113241399B (en) * | 2021-05-10 | 2022-07-26 | 北京航空航天大学 | High-density thermoelectric thick film device based on pulse laser direct writing technology and manufacturing method thereof |
| CN114535601A (en) * | 2022-01-24 | 2022-05-27 | 武汉理工大学 | Scraping-free method for printing thermoelectric material by selective laser melting process and scraping-free method for taking thermoelectric powder as printing raw material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903840A (en) * | 2012-10-16 | 2013-01-30 | 上海大学 | Method for assembling thermo-electric device through printed electronics manufacturing technology |
| CN103407296A (en) * | 2013-07-29 | 2013-11-27 | 南京鼎科纳米技术研究所有限公司 | Method for achieving high-melting-point material 3D printing through nanometer ink together with laser melting |
| CN103560203A (en) * | 2013-10-23 | 2014-02-05 | 合肥工业大学 | Simple and efficient film thermobattery structure and manufacturing method thereof |
-
2016
- 2016-03-06 CN CN201610125844.8A patent/CN106384780B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102903840A (en) * | 2012-10-16 | 2013-01-30 | 上海大学 | Method for assembling thermo-electric device through printed electronics manufacturing technology |
| CN103407296A (en) * | 2013-07-29 | 2013-11-27 | 南京鼎科纳米技术研究所有限公司 | Method for achieving high-melting-point material 3D printing through nanometer ink together with laser melting |
| CN103560203A (en) * | 2013-10-23 | 2014-02-05 | 合肥工业大学 | Simple and efficient film thermobattery structure and manufacturing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Selective Laser Melting of a Bishmuth Telluride Thermoelectric Materials;A. El-Desouky 等;《The Twenty-Sixth Annual International Solid Freeform Fabrication (SFF) Symposium – An Additive Manufacturing Conference》;20150812;论文第1043-1049页，表1 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106384780A (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106384780B (en) | A method of quickly preparing thermo-electric device | |
| CN106384779B (en) | A method of being that one step of starting material is supper-fast from simple substance powder prepares thermo-electric device | |
| CN106384778B (en) | A kind of supper-fast method for preparing thermoelectric material powder and device | |
| US8716589B2 (en) | Doped lead tellurides for thermoelectric applications | |
| TWI798165B (en) | Power system that generates at least one of electrical energy and thermal energy | |
| US20060118160A1 (en) | Thermoelectric element and thermoelectric module | |
| KR101791599B1 (en) | Bulk nanocomposite thermoelectric materials, nanocomposite thermoelectric materials powder and method for manufacturing the same | |
| JP2021002523A (en) | Thermophotovoltaic electrical power generator | |
| CN100524867C (en) | Method for manufacturing cobalt stibium antimonide based thermoelectric device | |
| US20070144573A1 (en) | Thermoelectric conversion element and thermoelectric conversion module | |
| JP2017522448A (en) | Method and apparatus for 3D printing by selective sintering | |
| US20100282285A1 (en) | Extrusion process for preparing improved thermoelectric materials | |
| CN101786653B (en) | Preparation method and applications of rare earth element-doped zinc oxide one-dimensional nanomaterial | |
| CN109851377B (en) | Laser-induced high-temperature solid-phase reaction for generating A2B2O7Method for forming thermal barrier coating material | |
| JP2012521648A (en) | Self-organized thermoelectric material | |
| US20110018155A1 (en) | Process for producing thermoelectric semiconductor materials and legs | |
| Baba et al. | Formation and characterization of polyethylene terephthalate-based (Bi0. 15Sb0. 85) 2Te3 thermoelectric modules with CoSb3 adhesion layer by aerosol deposition | |
| CN103555986B (en) | Method for preparing (Bi0.8Sb0.2)2Te3 nano thermoelectric material | |
| CN101514438A (en) | Method for preparing non-homogenous parts by deposition | |
| KR20180022384A (en) | Manufacturing method of Bi-Sb-Te alloy-sintered body for thermoelectric material | |
| JP2013038172A (en) | Manufacturing method of thermoelectric conversion material, thermoelectric conversion material, and thermoelectric conversion module | |
| CN102514282B (en) | Protective coating suitable for CoSb3 base thermoelectric material and preparation method thereof | |
| CN106274110A (en) | A kind of method of low-temp. spraying ink print nano metal pattern | |
| CN109951903A (en) | A kind of nano microcrystalline lattice mutually separate thermo electric material and preparation method thereof | |
| KR101950371B1 (en) | The thermoelectric device manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220126 Address after: 430000 Room 101, floor 1, new plant building / unit 1, new energy R & D base, Science Park, Wuhan University of technology, No. 36, Tangxun Hubei Road, East Lake New Technology Development Zone, Wuhan, Hubei Province Patentee after: Wuhan xinsaier Technology Co.,Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: WUHAN University OF TECHNOLOGY |