CN106384779B - A method of being that one step of starting material is supper-fast from simple substance powder prepares thermo-electric device - Google Patents
A method of being that one step of starting material is supper-fast from simple substance powder prepares thermo-electric device Download PDFInfo
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- CN106384779B CN106384779B CN201610125708.9A CN201610125708A CN106384779B CN 106384779 B CN106384779 B CN 106384779B CN 201610125708 A CN201610125708 A CN 201610125708A CN 106384779 B CN106384779 B CN 106384779B
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Abstract
The present invention provides it is a kind of from simple substance powder be the supper-fast method for preparing thermo-electric device of one step of starting material, specific steps are as follows: 1) prepare raw material；2) in selective laser fusion apparatus, according to required electrode pattern and thickness, electrode material melting and solidification is shaped by laser, obtains the insulating substrate for being printed with electrode layer (one)；3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, N-shaped thermoelectric compound powder and p-type thermoelectric compound powder are generated by laser in-situ；4) N-shaped thermoelectric arm and p-type thermoelectric arm are respectively obtained after solidifying using laser melting；5) according to required electrode pattern and thickness, electrode layer (two) is printed on N-shaped thermoelectric arm and p-type thermoelectric arm, obtain thermo-electric device.Present invention effectively prevents intermediate links cumbersome during Conventional thermoelectric device preparation technology, while overcoming the low problem low with raw material availability of yield rate in traditional welding packaging technology.
Description
Technical field
It is the supper-fast method for preparing thermo-electric device of starting material that the present invention relates to a kind of from simple substance powder, belongs to thermoelectricity material
Material and device new preparation process.
Background technique
Thermoelectric generation technology includes thermoelectric cooling technology and thermoelectric generation, the former utilizes the Peltier effect of material
Thermal energy is converted electrical energy into, the latter converts heat energy into electric energy using the Seebeck effect of material, as a kind of all solid state new
Type energy conversion technology, thermo-electric device have long-life, Maintenance free and adapt to the advantages such as adverse circumstances.Wherein, thermoelectric cooling
Technology is applied to the refrigerating field that corresponding noise and space etc. have particular/special requirement, such as uses the red wine cabinet and vapour of thermoelectric cooling technology
The refrigeration of vehicle cushion, laser diode realizes that the size of minisize refrigeration device is up to 3 using miniature thermoelectric refrigerator part
×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。
Thermoelectric power generation technology is mainly used in independent electric power supply from far-off regions, waste heat of automotive exhaust gas recycling, Industrial Stoves Waste Heat Recovery
With the fields such as solar photoelectric thermoelectricity compound electricity generation system.Currently, material applied in thermoelectric power generation technology has Bi2Te3And its
Alloy, PbTe 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 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 from simple substance in view of the deficiency of the prior art
Powder is the supper-fast method for preparing thermo-electric device of one step of starting material, highly shortened the time of thermoelectric material synthesis, has
Intermediate link cumbersome during avoiding Conventional thermoelectric device preparation technology is imitated, while being overcome in traditional welding packaging technology
The low problem low with raw material availability of yield rate.
The present invention be solve the problems, such as it is set forth above used by technical solution are as follows:
A method of being that one step of starting material is supper-fast from simple substance powder prepares thermo-electric device, includes the following steps:
1) prepare raw material: preparing each elemental powders according to the stoichiometric ratio of each element in p-type thermoelectric compound, and lazy
It is sufficiently mixed under property gas shield, obtains the material powder of p-type thermoelectric compound；Simultaneously according to each member in N-shaped thermoelectric compound
The stoichiometric ratio of element prepares each elemental powders, and is sufficiently mixed under inert gas protection, obtains the original of N-shaped thermoelectric compound
Feed powder body；And prepare electrode material powder and insulating substrate；
2) electrode material powder is sprawled on insulating substrate, according to required electrode pattern and thickness, passes through selectivity
Laser melting technique shapes electrode material melting and solidification, obtains the insulating substrate (one) for being printed with electrode layer one；
3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, by N-shaped thermoelectricity
The material powder interval of the material powder and p-type thermoelectric compound that close object is layered on the resulting electrode layer one of step 2), passes through choosing
Selecting property laser melting technique causes the Self- propagating Sintering Synthetic reaction of material powder, respectively in-situ preparation N-shaped thermoelectric compound powder
Body and p-type thermoelectric compound powder；
4) selective laser is used to the N-shaped thermoelectric compound powder and p-type thermoelectric compound powder that generate in step 3)
Smelting process is scanned printing respectively, and N-shaped thermoelectric arm and p-type thermoelectric arm are respectively obtained after melting and solidification；
5) according to required electrode pattern and thickness, electrode material powder is sprawled on N-shaped thermoelectric arm and p-type thermoelectric arm
Then body is printed on formation electrode layer two, institute on p-type thermoelectric arm and N-shaped thermoelectric arm using selective laser smelting process
It states electrode layer two and p-type thermoelectric arm is connected with N-shaped thermoelectric arm；
6) by an insulating substrate (two) in two surface cover of electrode layer, thermo-electric device is obtained.
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, size can be 3 × 3mm2~80 × 80mm2。
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, the material powder of p-type thermoelectric compound and N-shaped thermoelectricity chemical combination
The granularity of the material powder of object is controlled in 0.1~100 μ m.Preferably, by electrode powder, the raw material of p-type thermoelectric compound
The material powder of powder and N-shaped thermoelectric compound, which is scattered in respectively in water or other volatile solvents, is made suspension for printing
Step, the solid concentration of suspension are controlled 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；The step 4) is repeated when necessary, until reaching thickness required for electrode layer (two).
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 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, it is rapid 2), 4), 5) 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, and single layer powdering thickness is at 30~200 μm；Selective laser in step 3) melts work
In skill, the type of laser is continuous laser, and wavelength is 1060~1070nm, and the power control of laser is in 10~50W, laser scanning
Line rate control is 0.5~1atm as protective atmosphere, pressure in 10~300mm/s, inert gas, and single layer powdering thickness is 30
~200 μm.
The present invention provides that a kind of to be more specifically that one step of starting material is supper-fast from simple substance powder prepare thermo-electric device
Method includes the following steps:
1) prepare raw material: preparing each elemental powders according to the stoichiometric ratio of each element in p-type thermoelectric compound, and lazy
It is sufficiently mixed under property gas shield, obtains the material powder of p-type thermoelectric compound；Simultaneously according to each member in N-shaped thermoelectric compound
The stoichiometric ratio of element prepares each elemental powders, and is sufficiently mixed under inert gas protection, obtains the original of N-shaped thermoelectric compound
Feed powder body；And prepare electrode material powder and insulating substrate；The granularity of each material powder is at 1~100 μm；
2) material powder of p-type thermoelectric compound, the material powder of N-shaped thermoelectric compound and electrode material powder are distinguished
It is put into different 3 powder feeder of selective laser melting plant；And it is fixed on the printing substrate of the working cavity of device
Then good pre-prepd ceramic insulation substrate uses inert gas cycle purge, is in holding cavity to cavity forvacuum
0.5~1 atmospheric pressure, water oxygen content are in 100ppm hereinafter, basal plate preheating to 100~300 DEG C and is kept the temperature simultaneously；
3) in selective laser fusion apparatus, electrode material powder is sprawled on insulating substrate by powder feeder, according to
Required electrode pattern and thickness shape electrode material melting and solidification by laser, and print thickness is 0.1 on ceramic wafer
The electrode layer (one) of~0.5mm, obtains the insulating substrate for being printed with electrode layer (one)；
In selective laser melting process in the step, using laser parallel sweep mode, energy and power of laser control
In 40~80W, laser scanning line rate control is controlled in 10~50mm/s, sweep span in 0.03~0.1mm, and control climate is
0.5~1atm Ar or N2, single layer powdering thickness is in 10~100mm；
4) it is finished to electrode layer (one) printing, the scraper of powder feeder is every time respectively by the material powder of N-shaped thermoelectric compound
The surface for spreading over electrode layer (one) by the interval of 0.1~1mm with the material powder of p-type thermoelectric compound, then according to difference
Thermoelectric material type select different laser power density and scanning line rate, print p-type thermoelectric arm and N-shaped thermoelectric arm；
In the print procedure of the step, the material powder of thermoelectric compound carries out reacting-melt under laser heat effect-
The process of cooling and solidifying, with the progress of print procedure, simple substance raw material powder is gradated as corresponding compound or alloy heat
Electric material simultaneously forms p-type and N-shaped thermoelectric arm；
5) after the height of thermoelectric arm in step 4) reaches requirement, powder feeder switches to guide layer raw material powder (i.e. electrode
Material powder), at the same the power density of switched laser and line scan rate (technological parameter range of choice is identical as step 3)), paving
Electrode layer (two) are printed after powder to connect p-type and N-shaped thermoelectric arm, are divided into 3- between electrode layer (one), electrode layer (two)
10mm；
6) after the electrode layer in step 5) (two) printing, by an insulating substrate in the electrode layer (two) surface cover,
Removal devices gap powder obtains thermo-electric device after being cleaned.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention is directly from the simple substance powder material of composition thermoelectric material, using laser selective smelting process,
By Self- propagating Sintering Synthetic technology and Layered Manufacturing Technology, a step completes the synthesis of target thermoelectric compound in print procedure
With molding and obtain thermo-electric device, highly shortened in this way thermoelectric material synthesis time, effectively prevent Conventional thermoelectric device
Cumbersome intermediate link in part preparation process, while the technology can overcome traditional welding to assemble when printing microdevice
The low problem low with raw material availability of yield rate in technique.
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 the single-phase N-shaped Bi obtained under laser action2Te2.7Se0.3XRD spectrum.
Figure 11 is to obtain single-phase p-type Bi under laser action0.5Sb1.5Te3XRD spectrum.
Figure 12 be selective laser melting preparation p-type, N-shaped bismuth telluride-based thermoelectric arm array (thermoelectric arm sectional area be 2 ×
2mm2)。
Figure 13 is to obtain the XRD spectrum of single-phase SnTe compound under laser action.
Figure 14 is the XRD spectrum of single-phase SnSe compound under laser action.
Figure 15 be selective laser melting preparation SnTe and SnSe thermoelectric arm array (thermoelectric arm sectional area be 2 ×
2mm2)。
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 solely 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,
May be implemented it is of the present invention from simple substance powder be the supper-fast technical solution for preparing thermo-electric device of one step of starting material.But
The present invention realizes that the method for quickly preparing thermo-electric device is not limited to equipment provided below, any to can be realized power of the present invention
The equipment or equipment of technical solution documented by sharp claim 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
The device is used to prepare N-shaped Bi from simple substance powder for one step of starting material is supper-fast2Te2.7Se0.3, p-type
Bi0.5Sb1.5Te3The method of thermo-electric device, includes the following steps:
1) prepare raw material: according to p-type thermoelectric compound Bi0.5Sb1.5Te3The stoichiometric ratio of middle each element prepares simple substance powder
Last Bi powder, Sb powder, Te powder (being 300 mesh, 4N) total 1Kg are carried out on horizontal ball mill as being filled in the ball grinder of Ar gas
2h's is sufficiently mixed, and obtains the material powder of p-type thermoelectric compound；Simultaneously according to N-shaped thermoelectric compound Bi2In Te2.7Se0.3
The stoichiometric ratio of each element prepares elemental powders Bi powder, Te powder, Se powder (being 300 mesh, 4N) total 1Kg, as being filled with Ar gas
Ball grinder in, carry out 2h on horizontal ball mill and be sufficiently mixed, obtain the material powder of N-shaped thermoelectric compound；And prepare
Electrode material Cu powder (300 mesh) and insulating substrate；
2) material powder of p-type thermoelectric compound, the material powder of N-shaped thermoelectric compound and electrode material Cu powder are distinguished
It is put into different 3 powder feeder of selective laser fusion apparatus, and is fixed in advance on the printing substrate of working cavity
40 × the 40mm prepared2Then ceramic wafer used high-purity Ar gas cycle purge to cavity forvacuum 5 minutes, keep in cavity
It is 1 atmospheric pressure, water oxygen content in 100ppm hereinafter, basal plate preheating to 150 DEG C and keeps the temperature 10 minutes simultaneously；
3) in selective laser fusion apparatus, Cu powder is paved with by ceramic base plate surface by powder feeder, then using sharp
Light combines with ceramic wafer after Cu powder melts under laser action according to the sector scanning Cu powder of setting and forms electrode layer, repeat with
Upper powdering and laser scanning process to Cu electrode layers thickness are 0.5mm, obtain the insulating substrate (one) for being printed with electrode layer (one)；
Wherein, powdering thickness is selected as 50 microns, and control climate is 0.5~1atm Ar or N2, laser scan rate is selected as 30mm/
S, laser power are selected as 100W；
4) it is finished to electrode layer (one) printing, the scraper of powder feeder is every time respectively by the material powder of N-shaped thermoelectric compound
The surface for spreading over electrode layer (one) by the interval of 0.1~1mm with the material powder of p-type thermoelectric compound, then according to difference
Thermoelectric material type select different laser power density and scanning line rate, print p-type thermoelectric arm and N-shaped thermoelectric arm；
To Bi2Te2.7Se0.3Powdering region uses laser power size for 23W, scanning speed 50mm/s, in powdering layer
Central part scan a 0.5 × 0.5mm2It is rectangular, cause Self- propagating Sintering Synthetic react to obtain Bi2Te2.7Se0.3Chemical combination
Object, phase composition are as shown in Figure 10；To Bi0.5Sb1.5Te3Paving subregion uses laser power size for 30W, laser scanning speed
For 30mm/s, a 0.5 × 0.5mm is scanned in the central part of powdering layer2It is rectangular, cause Self- propagating Sintering Synthetic react
To Bi0.5Sb1.5Te3Compound, phase composition are as shown in figure 11；
To obtained Bi2Te2.7Se0.3Compound carries out selective melting using laser according to the size and shape of design,
Laser power size is 25W, scanning speed 80mm/s, sweep span 0.05mm, and scanning mode is unidirectional parallel sweep, is melted
Still single-phase Bi is obtained after the completion of melting2Te2.7Se0.3As shown in Figure 10；To obtained Bi0.5Sb1.5Te3Compound, using laser function
Rate size is 35W, scanning speed 50mm/s, sweep span 0.03mm, and scanning mode is single-phase parallel sweep, and melting is completed
Single-phase Bi is still obtained afterwards0.5Sb1.5Te3As shown in figure 11；It repeats above procedure and obtains N-shaped Bi2Te2.7Se0.3, p-type
Bi0.5Sb1.5Te3Thermoelectric arm is as shown in figure 12；
5) after the height of thermoelectric arm in step 4) reaches requirement, powder feeder switches to guide layer raw material powder (i.e. electrode
Material powder), at the same the power density of switched laser and line scan rate (technological parameter range of choice is identical as step 3)), paving
Electrode layer (two) (i.e. guide layer) is printed after powder to connect p-type and N-shaped thermoelectric arm；
6) it after the electrode layer in step 5) (two) printing, after selective laser fusion apparatus cavity is opened, is making pottery
Removal devices gap powder on porcelain substrate obtains thermo-electric device after being cleaned.
Embodiment 2
The device is used to prepare N-shaped SnSe, p-type SnTe thermo-electric device from simple substance powder for one step of starting material is supper-fast
Method includes the following steps:
1) prepare raw material: according in p-type thermoelectric compound SnTe each element stoichiometric ratio prepare elemental powders Sb powder,
Te powder (being 300 mesh, 4N) total 1Kg carries out the abundant mixed of 2h as being filled in the ball grinder of Ar gas on horizontal ball mill
It closes, obtains the material powder of p-type thermoelectric compound；Simultaneously according to the stoichiometric ratio of each element in N-shaped thermoelectric compound SnSe
Prepare elemental powders Sn powder, Se powder (being 300 mesh, 4N) total 1Kg, as being filled in the ball grinder of Ar gas, in horizontal ball mill
It is upper to carry out being sufficiently mixed for 2h, obtain the material powder of N-shaped thermoelectric compound；And prepare electrode material Cu powder (300 mesh) and absolutely
Edge substrate；
2) material powder of p-type thermoelectric compound, the material powder of N-shaped thermoelectric compound and electrode material Cu powder are distinguished
It is put into different 3 powder feeder of selective laser fusion apparatus, and is fixed in advance on the printing substrate of working cavity
30 × the 40mm prepared2Then ceramic wafer used high-purity Ar gas cycle purge to cavity forvacuum 5 minutes, keep in cavity
It is 1 atmospheric pressure, water oxygen content in 100ppm hereinafter, basal plate preheating to 150 DEG C and keeps the temperature 10 minutes simultaneously；
3) in selective laser fusion apparatus, Cu powder is paved with by ceramic base plate surface by powder feeder, then using sharp
Light combines with ceramic wafer after Cu powder melts under laser action according to the sector scanning Cu powder of setting and forms electrode layer, repeat with
Upper powdering and laser scanning process to Cu electrode layers thickness are 0.5mm, obtain the insulating substrate (one) for being printed with electrode layer (one)；
Wherein, powdering thickness is selected as 50 microns, and control climate is 0.5~1atm Ar or N2, laser scan rate is selected as 30mm/
S, laser power are selected as 100W；
4) it is finished to electrode layer (one) printing, the scraper of powder feeder is every time respectively by the material powder of N-shaped thermoelectric compound
The surface for spreading over electrode layer (one) by the interval of 0.1~1mm with the material powder of p-type thermoelectric compound, then according to difference
Thermoelectric material type select different laser power density and scanning line rate, print p-type thermoelectric arm and N-shaped thermoelectric arm；
Use laser power size for 20W in SnTe powdering region, scanning speed 30mm/s, in the central portion of powdering layer
One 0.5 × 0.5mm of bit scan2It is rectangular, cause Self- propagating Sintering Synthetic and react to obtain SnTe compound, phase composition is as schemed
Shown in 13；Use laser power size for 10W in SnSe powdering region, laser scanning speed 20mm/s, in powdering layer
Position is entreated to scan a 0.5 × 0.5mm2It is rectangular, cause Self- propagating Sintering Synthetic react to obtain SnSe compound, phase composition
As shown in figure 14；
To obtained SnTe compound, selective melting, laser function are carried out using laser according to the size and shape of design
Rate size is 15W, scanning speed 30mm/s, sweep span 0.05mm, and scanning mode is unidirectional parallel sweep, and melting is completed
It is as shown in figure 13 that single-phase SnTe is still obtained afterwards；To obtained SnSe compound, use laser power size for 12W, scanning speed
Degree is 20mm/s, and sweep span 0.03mm, scanning mode is single-phase parallel sweep, and single-phase SnSe is still obtained after the completion of melting
As shown in figure 14；It is as shown in figure 15 that repetition above procedure obtains N-shaped SnSe, p-type SnTe thermoelectric arm；
5) after the height of thermoelectric arm in step 4) reaches requirement, powder feeder switches to guide layer raw material powder (i.e. electrode
Material powder), at the same the power density of switched laser and line scan rate (technological parameter range of choice is identical as step 3)), paving
Electrode layer (two) (i.e. guide layer) is printed after powder to connect p-type and N-shaped thermoelectric arm；
6) after the guide layer printing in step 5), after selective laser fusion apparatus cavity is opened, in ceramic base
Removal devices gap powder on plate obtains thermo-electric device after being cleaned.
Embodiment 3
One kind from simple substance powder be the supper-fast preparation p-CeFe of one step of starting material4Sb12In conjunction with N-shaped Co4Sb12-xTex(x=
0~0.1) method of thermo-electric device, includes the following steps:
1) prepare raw material: according to p-type CeFe4Sb12The stoichiometric ratio of each element prepares each simple substance powder in thermoelectric compound
End, and be sufficiently mixed under inert gas protection, obtain the material powder of p-type thermoelectric compound；Simultaneously according to N-shaped Co4Sb12- xTexThe stoichiometric ratio of each element prepares each elemental powders in (x=0~0.1) thermoelectric compound, and under inert gas protection
It is sufficiently mixed, obtains the material powder of N-shaped thermoelectric compound；And prepare Cu50Mo50Alloy electrode powder and ceramic insulating substrate；
Wherein, the granularity of the material powder of electrode powder, the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
Control is at 90 μm hereinafter, and by electrode powder, the material powder of the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
It is dispersed in water respectively and suspension is made for printing step, the solid concentration of suspension is controlled 30%；
2) electrode material powder is sprawled on insulating substrate, according to required electrode pattern and thickness, passes through selectivity
Laser melting technique shapes electrode material melting and solidification, obtains the insulating substrate (one) for being printed with electrode layer one；
3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, by N-shaped thermoelectricity
The material powder interval of the material powder and p-type thermoelectric compound that close object is layered on the resulting electrode layer one of step 2), passes through choosing
Selecting property laser melting technique causes the Self- propagating Sintering Synthetic reaction of material powder, and printing in situ generates N-shaped thermoelectricity chemical combination respectively
Powder and p-type thermoelectric compound powder；
4) selective laser is used to the N-shaped thermoelectric compound powder and p-type thermoelectric compound powder that generate in step 3)
Smelting process is scanned printing respectively, and N-shaped thermoelectric arm and p-type thermoelectric arm are respectively obtained after melting and solidification；
5) according to required electrode pattern and thickness, electrode material powder is sprawled on N-shaped thermoelectric arm and p-type thermoelectric arm
Then body is printed on formation electrode layer two, institute on p-type thermoelectric arm and N-shaped thermoelectric arm using selective laser smelting process
It states electrode layer two and p-type thermoelectric arm is connected with N-shaped thermoelectric arm；
6) by an insulating substrate (two) in two surface cover of electrode layer, thermo-electric device is obtained.
Step 2), 4), 5) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 4), 5) 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；In step 3)
Selective laser smelting process in, the type of laser is continuous laser, and wavelength is 1060~1070nm, the power control of laser
In 30W, laser scanning line rate control is in 200mm/s, and for inert gas as protective atmosphere, pressure is 0.5~1atm, single berth
Powder thickness is at 50 μm.
Embodiment 4
One kind from simple substance powder be the supper-fast preparation p-type MnSi of one step of starting material1.75In conjunction with N-shaped Mg2Si1-xSnx(x=0
~1) method of thermo-electric device, includes the following steps:
1) prepare raw material: according to p-type MnSi1.75The stoichiometric ratio of each element prepares each simple substance powder in thermoelectric compound
End, and be sufficiently mixed under inert gas protection, obtain the material powder of p-type thermoelectric compound；Simultaneously according to N-shaped Mg2Si1- xSnxThe stoichiometric ratio of each element prepares each elemental powders in (x=0~1) thermoelectric compound, and fills under inert gas protection
Divide mixing, obtains the material powder of N-shaped thermoelectric compound；And prepare NiAl alloy epitaxy electrode powder and Al2O3Ceramic insulation substrate；
Wherein, the granularity of the material powder of electrode powder, the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
Control is at 50 μm hereinafter, and by electrode powder, the material powder of the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
It is dispersed in water respectively and suspension is made for printing step, the solid concentration of suspension is controlled 40%；
2) electrode material powder is sprawled on insulating substrate, according to required electrode pattern and thickness, passes through selectivity
Laser melting technique shapes electrode material melting and solidification, obtains the insulating substrate (one) for being printed with electrode layer one；
3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, by N-shaped thermoelectricity
The material powder interval of the material powder and p-type thermoelectric compound that close object is layered on the resulting electrode layer one of step 2), passes through choosing
Selecting property laser melting technique causes the Self- propagating Sintering Synthetic reaction of material powder, and printing in situ generates N-shaped thermoelectricity chemical combination respectively
Powder and p-type thermoelectric compound powder；
4) selective laser is used to the N-shaped thermoelectric compound powder and p-type thermoelectric compound powder that generate in step 3)
Smelting process is scanned printing respectively, and N-shaped thermoelectric arm and p-type thermoelectric arm are respectively obtained after melting and solidification；
5) according to required electrode pattern and thickness, electrode material powder is sprawled on N-shaped thermoelectric arm and p-type thermoelectric arm
Then body is printed on formation electrode layer two, institute on p-type thermoelectric arm and N-shaped thermoelectric arm using selective laser smelting process
It states electrode layer two and p-type thermoelectric arm is connected with N-shaped thermoelectric arm；
6) by an insulating substrate (two) in two surface cover of electrode layer, thermo-electric device is obtained.
Step 2), 4), 5) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 4), 5) 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；Selectivity in step 3)
In laser melting technique, the type of laser is continuous laser, and wavelength is 1060~1070nm, and the power control of laser swashs in 50W
The control of optical scanning line rate is 0.5~1atm as protective atmosphere, pressure in 10mm/s, inert gas, and single layer powdering thickness exists
200μm。
Embodiment 5
One kind from simple substance powder be the supper-fast preparation p-type Zr of one step of starting material0.5Hf0.5CoSb combination N-shaped ZrNiSn heat
The method of electrical part, includes the following steps:
1) prepare raw material: according to p-type Zr0.5Hf0.5The stoichiometric ratio of each element prepares each list in CoSb thermoelectric compound
Matter powder, and be sufficiently mixed under inert gas protection, obtain the material powder of p-type thermoelectric compound；Simultaneously according to N-shaped
The stoichiometric ratio of each element prepares each elemental powders in ZrNiSn thermoelectric compound, and sufficiently mixed under inert gas protection
It closes, obtains the material powder of N-shaped thermoelectric compound；And prepare Cu50W50Alloy electrode powder and Al2O3Ceramic insulation substrate；
Wherein, the granularity of the material powder of electrode powder, the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
Control is at 30 μm hereinafter, and by electrode powder, the material powder of the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
It is dispersed in water respectively and suspension is made for printing step, the solid concentration of suspension is controlled 20%；
2) electrode material powder is sprawled on insulating substrate, according to required electrode pattern and thickness, passes through selectivity
Laser melting technique shapes electrode material melting and solidification, obtains the insulating substrate (one) for being printed with electrode layer one；
3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, by N-shaped thermoelectricity
The material powder interval of the material powder and p-type thermoelectric compound that close object is layered on the resulting electrode layer one of step 2), passes through choosing
Selecting property laser melting technique causes the Self- propagating Sintering Synthetic reaction of material powder, and printing in situ generates N-shaped thermoelectricity chemical combination respectively
Powder and p-type thermoelectric compound powder；
4) selective laser is used to the N-shaped thermoelectric compound powder and p-type thermoelectric compound powder that generate in step 3)
Smelting process is scanned printing respectively, and N-shaped thermoelectric arm and p-type thermoelectric arm are respectively obtained after melting and solidification；
5) according to required electrode pattern and thickness, electrode material powder is sprawled on N-shaped thermoelectric arm and p-type thermoelectric arm
Then body is printed on formation electrode layer two, institute on p-type thermoelectric arm and N-shaped thermoelectric arm using selective laser smelting process
It states electrode layer two and p-type thermoelectric arm is connected with N-shaped thermoelectric arm；
6) by an insulating substrate (two) in two surface cover of electrode layer, thermo-electric device is obtained.
Step 2), 4), 5) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 4), 5) 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；In step 3)
Selective laser smelting process in, the type of laser is continuous laser, and wavelength is 1060~1070nm, the power control of laser
In 40W, laser scanning line rate control is in 100mm/s, and for inert gas as protective atmosphere, pressure is 0.5~1atm, single berth
Powder thickness is at 50 μm.
Embodiment 6
It is a kind of from simple substance powder be one step of starting material it is supper-fast preparation p-type PbSe combination N-shaped PbS thermo-electric device side
Method includes the following steps:
1) prepare raw material: preparing each elemental powders according to the stoichiometric ratio of each element in p-type PbSe thermoelectric compound, and
It is sufficiently mixed under inert gas protection, obtains the material powder of p-type thermoelectric compound；Simultaneously according to N-shaped PbS thermoelectric compound
The stoichiometric ratio of middle each element prepares each elemental powders, and is sufficiently mixed under inert gas protection, obtains N-shaped thermoelectricity chemical combination
The material powder of object；And prepare TiAl alloy electrode powder and Al2O3Ceramic insulation substrate；
Wherein, the granularity of the material powder of electrode powder, the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
Control is at 20 μm hereinafter, and by electrode powder, the material powder of the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound
It is scattered in ethyl alcohol respectively and suspension is made for printing step, the solid concentration of suspension is controlled 5%；
2) electrode material powder is sprawled on insulating substrate, according to required electrode pattern and thickness, passes through selectivity
Laser melting technique shapes electrode material melting and solidification, obtains the insulating substrate (one) for being printed with electrode layer one；
3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, by N-shaped thermoelectricity
The material powder interval of the material powder and p-type thermoelectric compound that close object is layered on the resulting electrode layer one of step 2), passes through choosing
Selecting property laser melting technique causes the Self- propagating Sintering Synthetic reaction of material powder, and printing in situ generates N-shaped thermoelectricity chemical combination respectively
Powder and p-type thermoelectric compound powder；
4) selective laser is used to the N-shaped thermoelectric compound powder and p-type thermoelectric compound powder that generate in step 3)
Smelting process is scanned printing respectively, and N-shaped thermoelectric arm and p-type thermoelectric arm are respectively obtained after melting and solidification；
5) according to required electrode pattern and thickness, electrode material powder is sprawled on N-shaped thermoelectric arm and p-type thermoelectric arm
Then body is printed on formation electrode layer two, institute on p-type thermoelectric arm and N-shaped thermoelectric arm using selective laser smelting process
It states electrode layer two and p-type thermoelectric arm is connected with N-shaped thermoelectric arm；
6) by an insulating substrate (two) in two surface cover of electrode layer, thermo-electric device is obtained.
Step 2), 4), 5) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is
1064nm, step 2), 4), 5) 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；Selection in step 3)
Property laser melting technique in, the type of laser is continuous laser, and wavelength is 1060~1070nm, the power control of laser in 10W,
Laser scanning line rate control exists in 300mm/s, inert gas as protective atmosphere, pressure 0.5atm, single layer powdering thickness
30μm。
The present invention respectively to illustrate embodiments of the present invention by taking the typical thermoelectric material system of embodiment these types as an example,
Other known a variety of thermoelectric materials can be by changing electrode material composition appropriate and selective laser smelting process parameter
And 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
The invention 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. it is a kind of from simple substance powder be the supper-fast method for preparing thermo-electric device of one step of starting material, it is characterised in that including as follows
Step:
1) prepare raw material: preparing each elemental powders according to the stoichiometric ratio of each element in p-type thermoelectric compound, and in indifferent gas
It is sufficiently mixed under body protection, obtains the material powder of p-type thermoelectric compound；Simultaneously according to each element in N-shaped thermoelectric compound
Stoichiometric ratio prepares each elemental powders, and is sufficiently mixed under inert gas protection, obtains the raw material powder of N-shaped thermoelectric compound
Body；And prepare electrode material powder and insulating substrate；
2) electrode material powder is sprawled on insulating substrate, according to required electrode pattern and thickness, passes through selective laser
Smelting process shapes electrode material melting and solidification, obtains the insulating substrate for being printed with electrode layer one；
3) on the insulating substrate that step 2) obtains, according to the device thermoelectric arm size of design and distribution, by N-shaped thermoelectric compound
Material powder and the material powder interval of p-type thermoelectric compound be layered on the resulting electrode layer one of step 2), pass through selectivity
Laser melting technique causes the Self- propagating Sintering Synthetic reaction of material powder, and printing in situ generates N-shaped thermoelectric compound powder respectively
Body and p-type thermoelectric compound powder；
4) the N-shaped thermoelectric compound powder and p-type thermoelectric compound powder that generate in step 3) are melted using selective laser
Technique is printed respectively, respectively obtains N-shaped thermoelectric arm and p-type thermoelectric arm；
5) according to required electrode pattern and thickness, electrode material powder is sprawled on N-shaped thermoelectric arm and p-type thermoelectric arm, so
Formation electrode layer two, the electrode on p-type thermoelectric arm and N-shaped thermoelectric arm are printed on using selective laser smelting process afterwards
P-type thermoelectric arm is connected by layer two with N-shaped thermoelectric arm；
6) by an insulating substrate in two surface cover of electrode layer, thermo-electric device is obtained；
The material powder of electrode powder, the material powder of p-type thermoelectric compound and N-shaped thermoelectric compound is divided respectively in step 1)
It dissipates and suspension is made in water or volatile solvent for subsequent printing step, the solid concentration of suspension is 1~40wt%；
Step 2), 4), 5) in selective laser smelting process in, the type of laser is continuous laser, wavelength is 1060~
1070nm, the power control of laser is in 5~100W, and laser scanning line rate control is in 10~500mm/s, control climate 0.5
~1 atmospheric pressure inert atmosphere, single layer powdering thickness is at 30~200 μm；In selective laser smelting process in step 3), laser
Type be continuous laser, wavelength be 1060~1070nm, the power control of laser is in 10~50W, laser scanning line rate control
System is 0.5~1atm as protective atmosphere, pressure in 10~300mm/s, inert gas, and single layer powdering thickness is at 30~200 μm.
2. it is according to claim 1 it is a kind of from simple substance powder be the supper-fast side for preparing thermo-electric device of one step of starting material
Method, it is characterised in that the thermo-electric device side size range is 3~100mm, the section side size range of each thermoelectric arm is 0.1~
3mm。
3. it is according to claim 1 it is a kind of from simple substance powder be the supper-fast side for preparing thermo-electric device of one step of starting material
Method, it is characterised in that electrode layer one and two is distributed on insulating substrate, according to electrode layer one, p-type thermoelectric arm, electrode layer
Two, p-type and N-shaped thermoelectric arm are sequentially connected in series by the sequence of N-shaped thermoelectric arm and electrode layer one.
4. it is according to claim 1 it is a kind of from simple substance powder be the supper-fast side for preparing thermo-electric device of one step of starting material
Method, it is characterised in that the step 2) repetitive operation, until reaching thickness required for electrode layer one；The step 4) repeats to grasp
Make, until reaching thickness required for electrode layer two.
5. it is according to claim 1 it is a kind of from simple substance powder be the supper-fast side for preparing thermo-electric device of one step of starting material
Method, it is characterised in that the step 3) repetitive operation, until reaching thickness required for p-type thermoelectric arm and N-shaped thermoelectric arm.
6. it is according to claim 1 it is a kind of from simple substance powder be the supper-fast side for preparing thermo-electric device of one step of starting material
Method, it is characterised in that the electrode powder is selected from one of simple substance Ni, Cu, Ag, Al, Mo, W, Ti or NiAl alloy epitaxy or several
The mixture of kind in any proportion.
7. it is according to claim 1 it is a kind of from simple substance powder be the supper-fast side for preparing thermo-electric device of one step of starting material
Method, it is characterised in that the p-type thermoelectric compound is selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、
Zr0.5Hf0.5One of CoSb and PbSe；The N-shaped thermoelectric compound is selected from Bi2Te3-xSex、SnTe、n-Co4Sb12-xTex、
Mg2Si1-xSnx, one of ZrNiSn and PbS.
8. thermo-electric device prepared by any one in claim 1-7.
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| EP4355062A1 (en) * | 2022-10-14 | 2024-04-17 | Commissariat à l'énergie atomique et aux énergies alternatives | Method for manufacturing a thermoelectric structure |
| EP4355063A1 (en) * | 2022-10-14 | 2024-04-17 | Commissariat à l'énergie atomique et aux énergies alternatives | Method for metallizing a thermoelectric structure |
| FR3140994A1 (en) * | 2022-10-14 | 2024-04-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD FOR METALIZING A THERMOELECTRIC ELEMENT |
| FR3140993A1 (en) * | 2022-10-14 | 2024-04-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | METHOD FOR MANUFACTURING A THERMOELECTRIC STRUCTURE |
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