CN106384778B - A kind of supper-fast method for preparing thermoelectric material powder and device - Google Patents
A kind of supper-fast method for preparing thermoelectric material powder and device Download PDFInfo
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- CN106384778B CN106384778B CN201610125694.0A CN201610125694A CN106384778B CN 106384778 B CN106384778 B CN 106384778B CN 201610125694 A CN201610125694 A CN 201610125694A CN 106384778 B CN106384778 B CN 106384778B
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
Abstract
The invention discloses a kind of supper-fast methods for preparing thermoelectric material powder and device, the following steps are included: thermoelectric material component elemental powders are first stoichiometrically weighed tabletting after mixing by (1), then pass through self-propagating combustion reaction or thermal expousure, supper-fast to obtain that thermoelectric material powder (2) are supper-fast prepares thermo-electric device: the raw material that sets out of the thermoelectric material powder that insulating substrate, electrode powder and step (1) are obtained alternatively property laser melting technique prepares thermo-electric device by 3 D-printing.The present invention is directly from the simple substance raw material of thermoelectric material, by the 3D printing technique for combining Self- propagating Sintering Synthetic, inkjet printing and selective laser melting, and increases material manufacturing technology prints thermo-electric device, avoid cumbersome intermediate link during Conventional thermoelectric device preparation technology, microdevice can be directly printed simultaneously, 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 supper-fast methods for preparing thermoelectric material powder and device, belong to thermoelectric material and device system
Standby new 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.And the type of printable material from plastics, metal again to pottery
Porcelain and life entity etc., selective laser sintering or the fusion technology feature high using local laser energy density, by powder office
Portion's heating reaches fusing point or more, is sintered together it, this technology is widely used in stainless steel, Ti alloy, Ni alloy, CoCr
The 3D printing of the high temperature alloys such as alloy and ceramics can be greatly shortened using 3D printing technique from production in the design link of product
Product conceptual design sketch is to the molding time, so as to push the exploitation of new product faster.If 3D printing technique used
In the rapid shaping of thermo-electric device, human cost will be greatly saved, while improving the yield rate of device, simultaneously because printing
The heat-affected zone very little of laser in journey, therefore can avoid since thermal shock is to the adverse effect of properties of product reliability.In addition,
The compound with regular structure of thermo-electric device, while height is generally below 10mm, therefore does not need complicated modeling early period using 3D printing and set
Meter, and the relatively some complex-shaped parts of printing effect want high.
The production that 3D printing technique is applied to thermo-electric device is also had into a main technical problem, main bugbear first is that it is low at
The thermoelectric material powder that this acquisition high-volume can be used for printing utilizes selective laser sintering or the 3D of melting currently on the market
The powder amount that printing device needs is all at least in 1Kg or more.Moreover, selective laser fusion technology is mainly used for printing biography at present
The metal parts of system, belongs to structural material.The material system of exploitation business application is still defined in stainless steel, Co base, Ni base, Ti base
The structural materials such as high temperature alloy do not study functional material, such as printing of semiconductor material substantially.For thermoelectric material and device
The reason of printing of part not yet someone discloses report, may be in terms of the following two: 1. in 3D printing field, concerned by people
Direction is structural material, rather than functional material；2. existing thermoelectric material powder technology of preparing is difficult to meet commercialization selectivity
The requirement of laser melting equipment, existing commercialization selective laser fusion apparatus, which is difficult to meet thermoelectric material powder, in other words beats
The requirement of print.This is because the powder that current thermoelectric material powder technology of preparing obtains is in irregular shape, mobility cannot
Meet 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-shapeds
Thermoelectric material), the printing of entire device can not be completed in a print procedure using existing commercial equipment.
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 kind of supper-fast method for preparing thermoelectric material powder and device mainly includes following two step:
(1) supper-fast to prepare thermoelectric material powder: to prepare according to the stoichiometric ratio of each element in p-type thermoelectric compound each
For the simple substance powder of element as reactant, ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains p-type
Thermoelectric material powder；Prepare the simple substance powder of each element as anti-according to the stoichiometric ratio of each element in N-shaped thermoelectric compound
Object is answered, ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains N-shaped thermoelectric material powder；
(2) supper-fast to prepare thermo-electric device: the thermoelectric material powder that insulating substrate, electrode powder and step (1) are obtained
The raw material that sets out of body alternatively property laser melting technique, prepares thermo-electric device by 3 D-printing.
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, the sparking mode that self-propagating combustion reacts in step (1) includes flame ignition, Resistant heating point
Fire and laser ignition；The partial size of each simple substance powder is no more than 50 μm, and purity is not less than 99.9%.
According to the above scheme, 3 D-printing described in step (2) includes 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.
Further, the electrode layer (one), electrode layer (two) are printed by the electrode powder described in step 1).
Further, the insulating substrate (one), insulating substrate (two) are the insulating substrate that step 1) is prepared, can be with
Ceramics insulating substrate.
Further, in step 1), electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder
Granularity is controlled in 0.1~50 μ m.Preferably, in step 1), by electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectricity
Compound powder, which is scattered in respectively in water or other volatile solvents, is made suspension for inkjet printing, and the solid phase of suspension contains
Amount control is 1~40%.Wherein, other volatile solvents can be selected from ethyl alcohol and acetone etc..
Further, for the amount of raw material each in step 1) depending on the size of the thermo-electric device of required printing, herein
It is not especially limited.
Further, the step 2) is repeated when necessary, until reaching thickness required for electrode layer (one).
Further, the step 3) is repeated when necessary, until reaching p-type thermoelectric arm and N-shaped thermoelectric arm institute
The thickness needed.
Further, the step 4) is repeated when necessary, until reaching thickness required for electrode layer (two).
Further, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, wave
A length of 1060~1070nm, the power control of laser is in 5~100W, and laser scanning line rate control is in 10~500mm/s, 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.
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 electrode layer one, p-type thermoelectric arm, electrode layer two, N-shaped thermoelectric arm and electrode layer
P-type and N-shaped thermoelectric arm are sequentially connected in series by one sequence.Wherein, electrode layer (one), the preferred 0.1- of electrode layer (two) thickness
0.5mm, the preferred 3-10mm in interval between two electrode layers.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention is directly from the simple substance raw material of thermoelectric material, by combining Self- propagating Sintering Synthetic, inkjet printing
Thermo-electric device is printed with the 3D printing technique and increases material manufacturing technology of selective laser melting, avoids Conventional thermoelectric device system
Cumbersome intermediate link in standby technical process, while microdevice can be directly printed, overcome finished product in traditional welding packaging technology
The low problem low with raw material availability of rate.
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 is the process flow chart that the present invention prepares thermo-electric device.
Figure 10 is 3 D-printing thermo-electric device flow diagram in step of the present invention (2), is followed successively by figure A, figure B, figure C, figure
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 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 height
The N-shaped thermoelectric arm of degree；7 be electrode layer two.
Figure 11 is the p-type Bi prepared in embodiment 10.5Sb1.5Te3The microscopic appearance of powder.
Figure 12 is N-shaped Bi in embodiment 12Te2.8Se0.2Thermoelectric arm laser scanning surface texture after molding.
Figure 13 is p-type SnTe thermoelectric arm surface texture after molding in embodiment 2.
Specific embodiment
In order to better understand the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not 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) Method of printing 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 method, printing type is that multiple inkjet print heads print corresponding material one by one in step b
Material；
Further, in above-mentioned method, 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 method, laser scanning methods are successively to scan to different materials in step d；
Further, in above-mentioned method, 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 supper-fast method for preparing thermoelectric material powder and device mainly includes the following steps that (1), step (2) two
A step:
Step (1): quickly preparation p-type Bi0.5Sb1.5Te3In conjunction with N-shaped Bi2Te2.8Se0.2Thermoelectric material powder
Bi powder, Te powder and Se powder (being 300 mesh, 4N) are pressed into Bi2Te2.8Se0.2Each element in (N-shaped thermoelectric compound)
Stoichiometric ratio 2:2.8:0.2 prepares total 1Kg as reactant, is placed in ball grinder and is pressed into diameter 80mm's after mixing
Cylindrical body is placed in a vacuum cavity, is lighted a fire using heating graphite flake from upper end and is caused self-propagating combustion process, obtained single-phase
P-type thermoelectric material green body pulverizes green body (i.e. p-type thermoelectric material powder), spare after 400 meshes excessively；
Bi powder, Sb powder and Te powder (being 300 mesh, 4N) are pressed into Bi0.5Sb1.5Te3Each element in (p-type thermoelectric compound)
Stoichiometric ratio 0.5:1.5:3 prepares total 1Kg as reactant, is placed in ball grinder and is pressed into diameter 80mm's after mixing
Cylindrical body is placed in a vacuum cavity, is lighted a fire using heating graphite flake from upper end and is caused self-propagating combustion process, obtained single-phase
N-shaped thermoelectric material green body pulverizes green body (i.e. N-shaped thermoelectric material powder), crosses spare, the powder of acquisition after 400 meshes
Scanning electron microscope is as shown in Figure 11.
Step (2): quickly preparation p-type Bi0.5Sb1.5Te3In conjunction with N-shaped Bi2Te2.8Se0.2The method of thermo-electric device, including such as
Lower step:
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, printing substrate is preheated to 80 DEG C simultaneously simultaneously
Heat preservation 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 Figure 10-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 Figure 10-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 Figure 10-D)；The step is repeated until electrode layer
(2) 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 12 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 supper-fast method for preparing thermoelectric material powder and device mainly includes the following steps that (1), step (2) two
A step:
Step (1): quickly preparation p-type SnTe combination N-shaped SnSe thermoelectric material powder
Sn powder and Se powder (being 300 mesh, 4N) are pressed to the stoichiometric ratio 1 of each element in SnSe (N-shaped thermoelectric compound):
1 prepares total 1Kg as reactant, is placed in the ball grinder full of Ar gas, carries out being sufficiently mixed for 2h using horizontal ball mill, will
Obtained uniformed powder is pressed into the cylindrical body of diameter 80mm, is placed in vacuum cavity, is lighted a fire using heating graphite flake from upper end
Cause self-propagating combustion reaction, obtain single-phase p-type thermoelectric material green body, green body is pulverized (i.e. p-type thermoelectric material powder
Body), cross 400 meshes after it is spare；
Sn powder, Te powder (being 300 mesh, 4N) are pressed to the stoichiometric ratio 1:1 of each element in SnTe (p-type thermoelectric compound)
Prepare total 1Kg as reactant, be placed in the ball grinder full of Ar gas, being sufficiently mixed for 2h is carried out using horizontal ball mill, it will
Obtained uniformed powder is pressed into the cylindrical body of diameter 80mm, is placed in vacuum cavity, is lighted a fire using heating graphite flake from upper end
Cause self-propagating combustion reaction, obtain single-phase N-shaped thermoelectric material green body, green body is pulverized (i.e. N-shaped thermoelectric material powder
Body), cross 400 meshes after it is spare.
Step (2): the quickly method of 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 13 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 supper-fast method for preparing thermoelectric material powder and device mainly includes following two step:
(1) supper-fast to prepare thermoelectric material powder: according to p-type p-CeFe4Sb12The chemistry meter of each element in thermoelectric compound
The simple substance powder than preparing each element is measured as reactant, ground and mixed is uniform, anti-by self-propagating combustion reaction or thermal explosion
It answers, obtains p-type thermoelectric material powder；According to N-shaped Co4Sb12-xTexThe stoichiometric ratio of each element prepares each in (x=0~0.1)
For the simple substance powder of element as reactant, ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains N-shaped
Thermoelectric material powder；
Step (2): p-CeFe is quickly prepared4Sb12In conjunction with N-shaped Co4Sb12-xTexThe method of (x=0~0.1) thermo-electric device,
Include the 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 supper-fast method for preparing thermoelectric material powder and device mainly includes following two step:
(1) supper-fast to prepare thermoelectric material powder: according to p-type MnSi1.75The stoichiometry of each element in thermoelectric compound
Than prepare each element simple substance powder as reactant, ground and mixed is uniform, by self-propagating combustion react or thermal expousure,
Obtain p-type thermoelectric material powder；According to Mg2Si1-xSnxThe stoichiometric ratio of each element prepares the list of each element in (x=0~1)
For matter powder as reactant, ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains N-shaped thermoelectric material
Powder；
Step (2): quickly preparation p-type MnSi1.75In conjunction with N-shaped Mg2Si1-xSnxThe method of (x=0~1) thermo-electric device, packet
Include following steps:
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 supper-fast method for preparing thermoelectric material powder and device mainly includes following two step:
(1) supper-fast to prepare thermoelectric material powder: according to p-type p-CeFe4Sb12The chemistry meter of each element in thermoelectric compound
The simple substance powder than preparing each element is measured as reactant, ground and mixed is uniform, anti-by self-propagating combustion reaction or thermal explosion
It answers, obtains p-type thermoelectric material powder；According to Co4Sb12-xTexThe stoichiometric ratio of each element prepares each member in (x=0~0.1)
For the simple substance powder of element as reactant, ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains N-shaped heat
Electric material powder；
Step (2): quickly preparation p-type p-CeFe4Sb12In conjunction with N-shaped Co4Sb12-xTexThe side of (x=0~0.1) thermo-electric device
Method includes the following steps:
1) prepare raw material, including Al2O3Ceramic insulation substrate, Cu50W50Alloy 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 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 supper-fast method for preparing thermoelectric material powder and device mainly includes following two step:
(1) supper-fast to prepare thermoelectric material powder: quasi- according to the stoichiometric ratio of each element in p-type PbSe thermoelectric compound
For the simple substance powder of standby each element as reactant, ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains
P-type thermoelectric material powder；The simple substance powder for preparing each element according to the stoichiometric ratio of each element in PbS is ground as reactant
Mill is uniformly mixed, and by self-propagating combustion reaction or thermal expousure, obtains N-shaped thermoelectric material powder；
Step (2): the quickly method of 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 (7)
1. a kind of supper-fast method for preparing thermoelectric material powder and device, it is characterised in that mainly include following two step:
(1) supper-fast to prepare thermoelectric material powder: to prepare each element according to the stoichiometric ratio of each element in p-type thermoelectric compound
Simple substance powder as reactant, ground and mixed is uniform, pass through self-propagating combustion reaction or thermal expousure, obtain p-type thermoelectricity
Material powder；Prepare the simple substance powder of each element as reactant according to the stoichiometric ratio of each element in N-shaped thermoelectric compound,
Ground and mixed is uniform, by self-propagating combustion reaction or thermal expousure, obtains N-shaped thermoelectric material powder；
(2) supper-fast to prepare thermo-electric device: the thermoelectric material powder that insulating substrate, electrode powder and step (1) are obtained is made
For the raw material that sets out of selective laser smelting process, thermo-electric device is prepared by 3 D-printing；
In step (2), the 3 D-printing includes the following steps:
1) prepare raw material, including insulating substrate, electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder；
In step 1), the granularity of electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder is controlled 0.1~50
μ m；It disperses water respectively by electrode powder, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder or volatility is molten
Suspension is made in agent for subsequent printing step, the solid concentration of suspension is controlled 1~40%；
2) according to required electrode pattern and thickness, electrode powder is printed upon by insulation base using selective laser smelting process
On plate 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 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
In electric arm and N-shaped thermoelectric arm, electrode layer two is formed, p-type thermoelectric arm is connected by the electrode layer two with N-shaped thermoelectric arm；
5) insulating substrate two in two surface cover of electrode layer, obtains thermo-electric device.
2. the supper-fast method for preparing thermoelectric material powder and device of one kind according to claim 1, it is characterised in that institute
It states electrode powder and is selected from one or more of simple substance Ni, Cu, Ag, Al, Mo, W, Ti or NiAl alloy epitaxy in any proportion mixed
Close object.
3. the supper-fast method for preparing thermoelectric material powder and device of one kind according to claim 1, it is characterised in that institute
It states p-type thermoelectric compound and is selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、Zr0.5Hf0.5One in CoSb and PbSe
Kind；The N-shaped thermoelectric compound is selected from Bi2Te3-xSex、SnTe、n-Co4Sb12-xTex、Mg2Si1-xSnx, in ZrNiSn and PbS
One kind.
4. the supper-fast method for preparing thermoelectric material powder and device of one kind according to claim 1, which is characterized in that institute
It states step 2) to be repeated when necessary, until reaching thickness required for electrode layer one；The step 3) needs when necessary
It is repeated, until reaching thickness required for p-type thermoelectric arm and N-shaped thermoelectric arm；The step 4) needs to carry out when necessary weight
It is multiple, until reaching thickness required for electrode layer two.
5. the supper-fast method for preparing thermoelectric material powder and device of one kind according to claim 4, it is characterised in that step
It is rapid 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is 1060~1070nm, is swashed
The power control of light is in 5~100W, and for laser scanning line rate control in 10~500mm/s, control climate is 0.5~1 atmospheric pressure
Inert atmosphere, single layer powdering thickness is at 30~100 μm.
6. the supper-fast method for preparing thermoelectric material powder and device of one kind according to claim 1, it is characterised in that heat
Electrical part side size range is 3~100mm, and the section side size range of each thermoelectric arm is 0.1~3mm.
7. thermo-electric device prepared by any one in claim 1-6.
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| CN107324293A (en) * | 2017-02-27 | 2017-11-07 | 武汉理工大学 | The supper-fast method for preparing high-performance p-type SnTe block thermoelectric materials of one step |
| CN109599479A (en) * | 2018-11-16 | 2019-04-09 | 清华大学深圳研究生院 | A kind of thermoelectric material and preparation method thereof |
| 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 |
| CN110729391B (en) * | 2019-07-30 | 2023-09-19 | 上海彩石激光科技有限公司 | Method and device for preparing magnesium silicide thermoelectric material block and thermoelectric material block |
| 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 |
| CN111446358B (en) * | 2020-05-22 | 2022-08-05 | 北京航空航天大学杭州创新研究院 | High-precision rapid thin-film thermoelectric device based on pulse laser ablation and preparation method thereof |
| CN112201743B (en) * | 2020-11-06 | 2023-06-16 | 武汉理工大学 | Preparation method of n-type bismuth telluride-based thermoelectric material |
| CN113594347A (en) * | 2021-08-31 | 2021-11-02 | 南京工业大学 | High-performance Bi2Te2.7Se0.3Preparation method of-graphite composite thermoelectric material |
| CN115401212A (en) * | 2022-08-05 | 2022-11-29 | 西安交通大学 | P type Cu 2 Additive manufacturing method of Se-based thermoelectric material |
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