CN106384778A - Method of manufacturing thermoelectric material powder and device in superfast way - Google Patents
Method of manufacturing thermoelectric material powder and device in superfast way Download PDFInfo
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- CN106384778A CN106384778A CN201610125694.0A CN201610125694A CN106384778A CN 106384778 A CN106384778 A CN 106384778A CN 201610125694 A CN201610125694 A CN 201610125694A CN 106384778 A CN106384778 A CN 106384778A
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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
- H10N10/01—Manufacture or treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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 method of manufacturing a thermoelectric material powder and a device in a superfast way. The method comprises the following steps of (1) weighing and mixing thermoelectric material composition element simple substance powders according to a stoichiometric ratio, then tabletting, and then through a self-propagating combustion reaction or a thermal explosion reaction, acquiring a thermoelectric material powder in the superfast way; (2) manufacturing a thermoelectric device in the superfast way: taking an insulation substrate, an electrode powder and the thermoelectric material powder acquired from the step (1) as starting raw materials of a selective laser fusion technology, and through three dimensional printing, manufacturing the thermoelectric device. In the invention, from a simple substance raw material of the thermoelectric material, through combining self-propagating combustion synthesis, inkjet printing and a 3D printing technology of selective laser fusion and through a material increase manufacturing technology, the thermoelectric device is printed, tedious intermediate links during a traditional thermoelectric device manufacturing technology process are avoided, simultaneously, a miniature device can be directly printed and problems that a yield and a raw material utilization rate are low in a traditional welding and assembling technology are overcome.
Description
Technical field
The present invention relates to a kind of supper-fast method preparing thermoelectric material powder and device, belong to thermoelectric material and new work prepared by device
Skill.
Background technology
Thermoelectric generation technology comprises thermoelectric cooling technology and thermoelectric generation, and electric energy is turned by the former using the paltie effect of material
It is changed to heat energy, 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 has long-life, Maintenance free and adapts to the advantages such as adverse circumstances.Wherein, thermoelectric cooling technology is applied to
Corresponding noise and space etc. have the refrigerating field of particular/special requirement, such as using red wine cabinet and the automobile cushion of thermoelectric cooling technology, laser
The refrigeration of diode to be realized using miniature thermoelectric refrigerator part, and the size of minisize refrigeration device is up to 3 × 3 × 1mm3, and
The sectional area of the wherein basic component units thermoelectric material particle of thermoelectric cooling device is up to 0.1 × 0.1mm2.Thermoelectric power generation technology
It is mainly used in independent electric power supply from far-off regions, waste heat of automotive exhaust gas recovery, Industrial Stoves Waste Heat Recovery and solar energy electric heating
The fields such as electric compound electricity generation system.At present, the material applied in thermoelectric power generation technology have Tellurobismuthite. 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 the bottle in device technology of preparing
Neck and be difficult to realize business-like application.
The preparation technology of existing business-like thermo-electric device is generally using first acquisition block thermoelectric material, is then cut into thermoelectricity
P-type and N-shaped thermoelectric material are combined and phase by way of welding by material particles with the flow guide bar being arranged on insulating ceramic film
Mutually it is cascaded.The mode of this welding has following several shortcoming when preparing thermo-electric device：1. complex procedures, comprise big
The manual process of amount, high cost；2. the increase of the reduction with thermoelectric material particle size and quantity, due to cutting loss and
Damage the stock utilization causing and yield rate substantially reduces；3. in welding process, heat-affected zone is larger, to material and joint
Performance there is unpredictable impact.
3D printing technique, in the nearest attention being increasingly subject to people for 10 years, is superimposed, using layering, the ultimate principle manufacturing, in theory
3D printing technique can print the part of any complicated shape.And the species of printable material from plastics, metal again to pottery with
And life entity etc., selective laser sintering or fusion technology utilize the high feature of local laser energy density, by powder body local heating
Reach more than fusing point so as to be sintered together, this technology is widely used in rustless steel, Ti alloy, Ni alloy, CoCr conjunction
The high temperature alloys such as gold and the 3D printing of pottery, can be greatly shortened from product using 3D printing technique in the design link of product
Product conceptual design sketch to the time of molding, such that it is able to the faster exploitation promoting new product.If 3D printing technique is used
In the rapid shaping of thermo-electric device, will greatly save human cost, improve the yield rate of device simultaneously, simultaneously because printed
The heat-affected zone very little of laser in journey, therefore can avoid due to thermal shock the adverse effect to properties of product reliability.In addition,
The compound with regular structure of thermo-electric device, height generally below 10mm simultaneously, the early stage modeling of complexity is not therefore needed using 3D printing
Design, and printing effect will height relative to some complex-shaped parts.
The production that 3D printing technique is applied to thermo-electric device also has main technical barrier, and one of main bugbear is inexpensive
Obtain the thermoelectric material powder that high-volume can be used for printing, utilize the 3D printing of selective laser sintering or melting in the market
The powder body amount that equipment needs is all at least in more than 1Kg.And, current selective laser fusion technology is mainly used in printing tradition
Metal parts, belong to structural material.The material system of exploitation business application is still defined in rustless steel, Co base, Ni base, Ti
The structural materials such as based high-temperature alloy, to functional material, the printing of such as semi-conducting material is not studied substantially.For thermoelectric material and
The printing of device not yet someone is open to be reported, may for following two aspect the reason：1. in 3D printing field, Ren Menguan
The direction of note is structural material, rather than functional material；2. existing thermoelectric material powder technology of preparing is difficult to meet commercialization selection
The requirement of property lf equipment, in other words existing commercialization selective laser fusion apparatus be difficult to meet thermoelectric material powder and beat
The requirement of print.This is because, the powder body that current thermoelectric material powder technology of preparing obtains is in irregular shape, and its mobility can not
Meet the requirement of commercial equipment powdering；In addition, thermo-electric device comprise at least 3 kinds different materials (electrode material, p-type and
N-shaped thermoelectric material), the printing of whole device can not possibly be completed in a print procedure using existing commercial equipment.
Content of the invention
The technical problem to be solved is to provide one kind quickly to prepare thermoelectricity device for the deficiency of above-mentioned prior art presence
The method of part, by the 3D printing technique with reference to inkjet printing and selective laser melting, and increases material manufacturing technology prints heat
Electrical part, it is to avoid loaded down with trivial details intermediate link during Conventional thermoelectric device preparation technology, directly can print microdevice simultaneously, gram
Take that yield rate in traditional welding packaging technology is low and the low problem of raw material availability.
The present invention by solving the problems, such as adopted technical scheme set forth above is：
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes following two steps：
(1) supper-fast prepare thermoelectric material powder：Stoichiometric proportion according to each element in p-type thermoelectric compound prepares each unit
The simple substance powder body of element uniformly, is reacted by self-propagating combustion or thermal expousure as reactant, ground and mixed, obtains p-type heat
Electric material powder body；Stoichiometric proportion according to each element in N-shaped thermoelectric compound prepares the simple substance powder body of each element as reaction
Thing, ground and mixed uniformly, is reacted by self-propagating combustion or thermal expousure, obtains N-shaped thermoelectric material powder；
(2) supper-fast prepare thermo-electric device：The thermoelectric material powder that insulated substrate, electrode powder body and step (1) are obtained
Alternatively the raw material that sets out of property lf technique, prepares thermo-electric device by 3 D-printing.
By such scheme, described electrode powder body is selected from simple substance Ni, Cu, Ag, Al, Mo, W, Ti or NiAl alloy epitaxy etc.
One or more of mixture in any proportion.
By such scheme, described p-type thermoelectric compound is selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、
Zr0.5Hf0.5One of CoSb and PbSe etc.；Described N-shaped thermoelectric compound is selected from Bi2Te3-xSex、SnTe、n-Co4Sb12- xTex、Mg2Si1-xSnx, one of ZrNiSn and PbS etc..
By such scheme, in step (1), the sparking mode of self-propagating combustion reaction includes flame ignition, Resistant heating igniting
And laser ignition；The particle diameter of each simple substance powder body is less than 50 μm, and purity is not less than 99.9%.
By such scheme, the 3 D-printing described in step (2) comprises the steps：
1) prepare raw material, including insulated substrate, electrode powder body, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder
Body；
2) according to required electrode pattern and thickness, electrode powder body is printed upon by the base that insulate using selective laser smelting process
On plate (), obtain being printed with the insulated substrate of electrode layer (one)；
3) the device thermoelectric arm size according to design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder and N-shaped thermoelectric compound powder are in step 2) it is printed as p-type thermoelectric arm and N-shaped heat on the electrode layer () of gained
Electric arm；
4) according to required electrode pattern and thickness, electrode powder body is printed upon p-type heat using selective laser smelting process
In electric arm and N-shaped thermoelectric arm, form electrode layer (two), described electrode layer (two) is by p-type thermoelectric arm and N-shaped thermoelectric arm phase
Connect；
5) insulated substrate (two) in described electrode layer (two) surface cover, obtains thermo-electric device.
Further, described electrode layer (), electrode layer (two) are by step 1) described in electrode powder body print form.
Further, described insulated substrate (), insulated substrate (two) are step 1) insulated substrate that prepared, can
With Ceramics insulated substrate.
Further, for step 1) in, electrode powder body, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder
Task-size Controlling is in 0.1～50 μ m.Preferably, step 1) in, by electrode powder body, p-type thermoelectric compound powder and N-shaped
Thermoelectric compound powder is scattered in water or other volatile solvents respectively makes suspension for inkjet printing, the solid phase of suspension
Content all controls 1～40%.Wherein, other volatile solvents can be selected from ethanol and acetone etc..
Further, for step 1) in each raw material the size of thermo-electric device according to required printing for the amount depending on, here is not made
Concrete restriction.
Further, described step 2) need if necessary to be repeated, until it reaches the thickness required for electrode layer ().
Further, described step 3) need if necessary to be repeated, until it reaches needed for p-type thermoelectric arm and N-shaped thermoelectric arm
The thickness wanted.
Further, described step 4) need if necessary to be repeated, until it reaches the thickness required for electrode layer (two).
Further, step 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, ripple
A length of 1060～1070nm, in 5～100W, laser scanning line rate controlled is in 10～500mm/s, gas for the Power Control of laser
Atmosphere is controlled to 0.5～1 atmospheric pressure inert atmosphere (as nitrogen, argon etc.), and monolayer powdering thickness is at 30～100 μm.
By such scheme, the thermo-electric device size range that the present invention can be prepared is larger, is particularly suitable for preparing micro thermoelectric device,
The section side size range of thermoelectricity single armed is 0.1～3mm, and thermo-electric device side size range is 3～100mm.
By such scheme, the thermo-electric device that the structure of described thermo-electric device is prepared with traditional handicraft is similar, and that is, electrode layer one and two is equal
It is distributed on insulated substrate, according to electrode layer one, p-type thermoelectric arm, electrode layer two, N-shaped thermoelectric arm and electrode layer one
P-type and N-shaped thermoelectric arm are sequentially connected in series and form by order.Wherein, electrode layer (), the preferred 0.1- of electrode layer (two) thickness
0.5mm, the preferred 3-10mm in the interval between two electrode layers.
Compared with prior art, the invention has the beneficial effects as follows：
1st, the present invention is directly from the simple substance raw material of thermoelectric material, by with reference to Self- propagating Sintering Synthetic, inkjet printing and choosing
The 3D printing technique of selecting property lf, and increases material manufacturing technology printing thermo-electric device, it is to avoid work prepared by Conventional thermoelectric device
Loaded down with trivial details intermediate link during skill, directly can print microdevice simultaneously, overcome yield rate in traditional welding packaging technology low and
The low problem of raw material availability.
2nd, the present invention does not need the early stage Modeling and Design of complexity using 3D printing, and printing effect is complex-shaped relative to some
Part will height, the compound with regular structure that disclosure satisfy that thermo-electric device and the demand being highly generally below 10mm.
3rd, the present invention adopts LASER HEATING process in laser selective smelting process less to the heat-affected zone of thermoelectric material, can
Avoid the impact to material property for the thermal shock in traditional handicraft welding process.
Brief description
Fig. 1 is equipment overall structure schematic diagram；
Fig. 2 a is single spraying head 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 many shower nozzles equipment overall structure schematic diagram；
Fig. 6 a is double nozzle printing schematic device；
Fig. 6 b is the side view of Fig. 6；
Fig. 7 is that three shower nozzle parallel vertical place printing equipment schematic diagram；
Fig. 8 is that three shower nozzles tilt to focus on placement printing equipment schematic diagram.
Fig. 9 prepares the process chart of thermo-electric device for the present invention.
Figure 10 be step of the present invention (2) in 3 D-printing thermo-electric device schematic flow sheet, be followed successively by figure A, figure B, figure C,
Figure D, includes sectional view and top view simultaneously.In figure indicates and is described as follows：1 is ceramic substrate；2 is electrode layer one；3 are
Single p-type thermoelectric arm；4 is single layer of n-type thermoelectric arm；5 is the p-type thermoelectric arm to setting height for the duplicate printing；6 is to repeat
Print to the N-shaped thermoelectric arm of setting height；7 is electrode layer two.
Figure 11 is p-type Bi of preparation in embodiment 10.5Sb1.5Te3The microscopic appearance of powder body.
Figure 12 is N-shaped Bi in embodiment 12Te2.8Se0.2Surface texture after thermoelectric arm laser scanning molding.
Figure 13 is the surface texture after p-type SnTe thermoelectric arm molding in embodiment 2.
Specific embodiment
In order to be better understood from the present invention, it is further elucidated with present disclosure with reference to embodiment, but present disclosure is simultaneously
It is not limited solely to the following examples.
Two kinds of 3D printing Apparatus for () and method therefors combining inkjet printing and selective laser fusion technology are provided in the present invention, permissible
Realize the technical scheme quickly preparing thermo-electric device of the present invention.But the method that thermo-electric device is quickly prepared in present invention realization
Be not limited to equipment provided below, the equipment of any technical scheme being capable of described in claims of the present invention or
Equipment could be used for the present invention, and the present invention is without limitation.
1st, the first combines the 3D printing Apparatus for () and method therefor of 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, described shaping top of chamber is provided with laser light incident window, and described molding intracavity is provided with inkjet-printing device, institute
State inkjet-printing device and include substrate and ink jet-print head, described storage tank is used for storing ink, and by providing ink to described spray
Black printhead, described gas-recycling plant includes seal cavity, is provided with filter layer, drying layer and circulated air inside seal cavity
Machine, described seal cavity is tightly connected with described forming cavity.
Further, in above-mentioned equipment, described inkjet-printing device also includes the base with x to displacement platform, and described x is to position
Substrate is placed on moving stage, base arranges the support to displacement platform with y, y fixes z to displacement platform on displacement platform, and z is to position
Ink jet-print head is fixed, described ink jet-print head is located at surface in moving stage.
Further, in above-mentioned equipment, below described substrate, it is provided with panel heater.
Further, in above-mentioned equipment, described molding cavity wall is provided with the content to the volatile solvent in gas in cavity
The solvent gas concentration detector being monitored.
Further, in above-mentioned equipment, described molding cavity wall is provided with and the vapour content in gas in cavity is monitored
Water vapour content detector.
(2) printing technology of the 3D printing equipment of above-mentioned combination inkjet printing and selective laser melting, comprises following step
Suddenly：
A. the ink in storage tank is injected in ink jet-print head；
B. ink jet-print head single layer pattern needed for printing on substrate by the way of inkjet printing；
C. the temperature of control base board, makes the solvent in ink quickly volatilize, quick by the drying layer in gas-recycling plant
Remove, the working gas being dried is returned to inside molding cavity；
D. after surface is removed, substrate returns to initial point to ink jet-print head, the pattern on substrate by precinct laser melt into
Row molding and connection, obtain monolayer densified thin layer material；
E. repeat above procedure and obtain multiple dense block materials.
Further, in above-mentioned technique, molding intracavity working gas is Ar or N2；
Further, in above-mentioned technique, after step c, the water content of molding intracavity working gas be reduced to 100ppm with
After lower, ability execution step d.
Further, in above-mentioned technique, after step c, the oxygen content of molding intracavity working gas be reduced to 100ppm with
After lower, ability execution step d.
(3) combine accompanying drawing, the 3D printing equipment illustrating this with reference to inkjet printing and selective laser fusion technology is concrete
Include forming cavity 1, storage tank 3, gas-circulating system 4 and solvent gas concentration detector 5 (figure for storing ink
1).
An inkjet-printing device 2 is placed, this part can move up and down in overall becoming in cavity 1 in forming cavity 1.Inkjet printing fills
Put the base 21 that 2 (Fig. 2 a, Fig. 2 b) comprise the displacement platform of a band x direction motion, this x is sequentially placed one on displacement platform
Panel heater 26 and substrate 25.One support 22 is arranged on base, support 22 carries the displacement that can move in the y-direction
Platform, this y fixes a displacement platform 23 that can move in the z-direction again on displacement platform, and this z fixes an ink-jet on displacement platform 23
Printhead 24, ink jet-print head 24 are located above substrate 25.
Ink in storage tank 3 can be by the ink jet-print head 24 of pipeline to molding intracavity.Gas-circulating system 4 (figure
3) comprise a seal cavity 31, cavity top is provided with an air inlet 36, 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 method of work is：Ink in storage tank 3 is transported in ink jet-print head 24, and ink jet-print head 24 is by ink injection
Out deposit to substrate 25 surface, the first layer pattern printed on substrate 25 by the relative motion of shower nozzle 24 and substrate 25,
The temperature control of substrate 25, below the boiling point of solvent, makes aqueous solvent quickly volatilize, vapor and working gas Ar or N2Mixed
Close and removed by being adsorbed by drying layer 35 after gas-recycling plant 4.After ink dried, substrate 25 returns to initial point.Using molten
Agent gas concentration water finder 5 detects the concentration of vapor in mixed gas, when its content is in 100ppm, using selectivity
Powder layer material on the technique substrate 25 of lf be scanned and curing molding and and substrate 25 connect.More than repetition
Process obtains multiple dense block materials.In the above process, the scope 42 of selective laser smelting process scanning is beaten in ink-jet
Within the scope 41 of print (Fig. 4).
2nd, second combines the 3D printing Apparatus for () and method therefor of inkjet printing and selective laser fusion technology
(1) the 3D printing equipment of a kind of combination inkjet printing and selective laser fusion technology, comprises forming cavity, gas follows
Loop device and at least two storage tanks, described shaping top of chamber is provided with laser light incident window, and described molding intracavity is provided with inkjet printing
Device, described inkjet-printing device includes substrate and at least two ink jet-print heads, and described storage tank is used for storing ink, and will
To described ink jet-print head, described gas-recycling plant includes seal cavity to providing ink, be provided with inside seal cavity filter layer,
Drying layer and circulating fan, described seal cavity is tightly connected with described forming cavity.
Further, in above-mentioned equipment, described inkjet-printing device also includes the base with x to displacement platform, and described x is to position
Substrate is placed on moving stage, base arranges the support to displacement platform with y, y fixes z to displacement platform on displacement platform, and z is to position
Ink jet-print head is fixed, described ink jet-print head is located at surface in moving stage.
Further, in above-mentioned equipment, two or more ink jet-print head parallel equidistant are placed, and ink injection direction is
Vertical direction.
Further, in above-mentioned equipment, described ink jet-print head quantity is three, and middle inkjet printing head erect is placed, left
Right inkjet printing head tilt is symmetrically placed, and ink jet-print head centrage 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 beat simultaneously
Print comprises the block part of 2 kinds and above different materials, comprises the steps of：
A. the ink in storage tank is injected in the corresponding ink jet-print head of forming cavity under the effect of the pressure；
B. many ink jet-print heads are combined the mobile of substrate and are printed respective material monolayer figure by the way of inkjet printing on substrate
Case；
C. the temperature of control base board, makes the solvent in ink quickly volatilize, quick by the drying layer in gas-recycling plant
Remove, the working gas being dried is returned to inside molding cavity；
D. after surface is removed, substrate returns to initial point to ink jet-print head, the pattern on substrate by precinct laser melt into
Row molding and connection, obtain monolayer densified thin layer material；
E. repeat above procedure and obtain multiple dense block materials.
Further, in above-mentioned method, in step b, printing type prints respective material one by one for multiple ink jet-print heads；
Further, in above-mentioned method, in step b, printing type is multiple ink jet-print heads active print respective material simultaneously
Pattern；
Further, in above-mentioned method, in step d, laser scanning methodses are that different materials are scanned successively；
Further, in above-mentioned method, in step d, laser scanning methodses are that spatially arrangement mode scans successively.
(3) combine accompanying drawing, citing illustrates the 3D printing that second combines inkjet printing and selective laser fusion technology
Equipment, can print multiple different materials simultaneously, and equipment comprises：Forming cavity 1, multi-headed ink-jet printing equipment 51, be used for storage three
Plant storage tank 52,53 and 54, gas-circulating system 4 and the solvent gas concentration detector 5 of different inks.
Described multi-headed ink-jet printing equipment 51 can be dual head ink jet device, comprise the ink jet-print head that 2 parallel vertical are placed
61 and 62, (Fig. 5) is connected by shower nozzle stationary fixture 53 and support；
Described multi-headed ink-jet printing equipment 51 can also be 3 ink discharge devices, comprises 3 ink jet-print heads (Fig. 6, figure
7), 3 shower nozzles 71,72 and 73 can parallel vertical be placed.
Its method of work is：Ink in storage tank 52,53 and 54 is delivered in ink jet-print head 71,72 and 73 respectively.Shower nozzle
71 be operated in first print on the substrate 25 of pattern to(for) material, then shower nozzle 72 and 73 work successively, in substrate 25
The each self-corresponding pattern of upper printing；The temperature of control base board 25 is 80 DEG C, so that the water in ink is quickly volatilized, by gas
Drying layer 35 in blood circulation 4 and rapidly remove, the working gas Ar being dried is returned to inside forming cavity 1；Ink-jet is beaten
After print head is removed above substrate 25, substrate 25 returns to initial point, and the pattern on substrate 25 is melted into by precinct laser
Type and connection, obtain monolayer densified thin layer material.Repeat above procedure and obtain multiple dense block materials.
Embodiment 1
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes the following steps that (1), step (2) two
Step：
Step (1)：Quick 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 Bi2Te2.8Se0.2(N-shaped thermoelectric compound) Zhong Geyuan
The stoichiometric proportion 2 of element：2.8：0.2 prepares common 1Kg as reactant, is pressed into diameter after inserting mix homogeneously in ball grinder
The cylinder of 80mm, inserts in a vacuum cavity, is lighted a fire from upper end using heating graphite flake and causes self-propagating combustion process, obtains
Obtain single-phase p-type thermoelectric material base substrate, base substrate is pulverized (i.e. p-type thermoelectric material powder), cross 400 mesh sieve standby
With；
Bi powder, Sb powder and Te powder (being 300 mesh, 4N) are pressed Bi0.5Sb1.5Te3(p-type thermoelectric compound) Zhong Geyuan
The stoichiometric proportion 0.5 of element：1.5：3 prepare common 1Kg as reactant, are pressed into diameter after inserting mix homogeneously in ball grinder
The cylinder of 80mm, inserts in a vacuum cavity, is lighted a fire from upper end using heating graphite flake and causes self-propagating combustion process, obtains
Obtain single-phase N-shaped thermoelectric material base substrate, base substrate is pulverized (i.e. N-shaped thermoelectric material powder), cross 400 mesh sieve standby
With the powder body scanning electron microscope of acquisition is as shown in Figure 11.
Step (2)：Quick preparation p-type Bi0.5Sb1.5Te3In conjunction with N-shaped Bi2Te2.8Se0.2The method of thermo-electric device, including as follows
Step：
1) prepare raw material, weigh and consist of 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 body Cu powder, each material powder all cross 400 mesh sieves after, disperse respectively
In 300ml, 300ml and 220ml water, it is subsequently placed in the ink as inkjet printing in 3 different storage tanks, storage
Ink in batch can is delivered in ink jet printing head under the effect of the pressure；And preparing thickness for 1mm, the length of side is 30mm
Square Al2O3Ceramic wafer is placed and fixing on printing substrate；The molding cavity of selective laser melting plant is taken out very in advance
Empty 5 minutes, then adopt Ar gas backfill cavity to normal pressure, keep cavity water oxygen content in below 100ppm, print simultaneously
Basal plate preheating to 80 DEG C and is incubated 10 minutes；
2) first the Cu powder in storage tank is paved with step 1 using inkjet printing mode) described in ceramic base plate surface, powdering
Thickness is 50 microns, then adopts laser according to the region setting (as a series of rectangle diagrams being arranged in length and breadth on substrate
Case) scan Cu powder, laser scan rate is chosen as 30mm/s, and laser power is chosen as 100W；Wherein, Cu powder is swashing
Electrode layer is combined to form with ceramic wafer, the area of single Cu electrode is 2.5 × 5mm after melting under light action2, repeat with upper berth
Powder and laser scanning process are 0.5mm (see Figure 10-A) to Cu electrode layers thickness, that is, obtain being printed with electrode layer ()
Insulated substrate；
3) p-type in storage tank and N-shaped thermoelectric material powder are spaced inkjet printing in step 2) electrode layer of gained
(1) surface, the size of the thermoelectric arm of design is 2 × 2 × 2mm2, then adopt 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, p-type and N-shaped thermoelectric arm are printed
When, powdering thickness is 60 microns, and laser scan rate is chosen as 80mm/s, and laser power is chosen as 40W；More than repetition
The print procedure of thermoelectric arm is until it is highly 2mm (see Figure 10-B, C)；
4) the electrode powder body Ag powder in storage tank is layered on step 3) on the p-type thermoelectric arm and N-shaped thermoelectric arm of gained, adopt
Laser scan rate is chosen as 30mm/s, and laser power is chosen as 100W, Cu powder is scanned print shape according to condition
Become electrode layer (two), p-type and N-shaped thermoelectric arm are coupled together (see Figure 10-D) by electrode layer (two)；Repeat this step straight
It is 0.5mm to electrode layer (two) thickness, the size of electrode layer (two) is identical with electrode layer ()；
5) by insulated substrate (two) in described electrode layer (two) surface cover, obtain Bi2Te3Thermo-electric device.
Figure 12 is N-shaped Bi2Te2.8Se0.2Surface texture after thermoelectric arm laser scanning molding is it can be seen that after laser melting
Surface still compare smooth.
Embodiment 2
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes the following steps that (1), step (2) two
Individual step：
Step (1)：Quick preparation p-type SnTe combines N-shaped SnSe thermoelectric material powder
Sn powder and Se powder (being 300 mesh, 4N) are pressed the stoichiometric proportion of each element in SnSe (N-shaped thermoelectric compound)
1：1 prepares common 1Kg as reactant, is placed in the ball grinder full of Ar gas, carries out the abundant of 2h using horizontal ball mill
Mixing, the uniformed powder obtaining is pressed into the cylinder of diameter 80mm, is placed in vacuum cavity, using heating graphite flake from
Upper end igniting causes self-propagating combustion reaction, obtains single-phase p-type thermoelectric material base substrate, and base substrate is pulverized, and (i.e. p-type is hot
Electric material powder body), standby after 400 mesh sieves excessively；
Sn powder, Te powder (being 300 mesh, 4N) are pressed the stoichiometric proportion of each element in SnTe (p-type thermoelectric compound)
1：1 prepares common 1Kg as reactant, is placed in the ball grinder full of Ar gas, carries out the abundant of 2h using horizontal ball mill
Mixing, the uniformed powder obtaining is pressed into the cylinder of diameter 80mm, is placed in vacuum cavity, using heating graphite flake from
Upper end igniting causes self-propagating combustion reaction, obtains single-phase N-shaped thermoelectric material base substrate, and base substrate is pulverized, and (i.e. N-shaped is warm
Electric material powder body), standby after 400 mesh sieves excessively.
Step (2)：The quick method preparing p-type SnTe/n type SnSe thermo-electric device, comprises the steps：
1) prepare raw material, weigh and consist of SnTe (p-type thermoelectric material) and the thermoelectric material of SnSe (N-shaped thermoelectric material)
Powder body and each 500 grams of electrode powder body Ag powder, each material powder all cross 400 mesh sieves after, be scattered in respectively 230ml, 250
In ml and 250ml water, it is subsequently placed in the ink as inkjet printing in 3 different storage tanks, the ink in storage tank exists
It is transported in ink jet printing head in the presence of pressure；Prepare the Al that thickness is 1mm2O3Ceramic wafer is placed on printing substrate
And it is fixing；Molding cavity forvacuum 5 minutes to selective laser melting plant, then adopts Ar gas backfill cavity to normal
Pressure, holding cavity water oxygen content to 80 DEG C and is incubated 10 minutes in below 100ppm, simultaneously basal plate preheating；
2) first the Ag powder in storage tank is paved with step 1) described in ceramic base plate surface, powdering thickness be 50 microns,
Then adopt laser according to the sector scanning Ag powder setting, laser scan rate is chosen as 30mm/s, and laser power is chosen as
100W；Wherein, combine to form electrode layer with ceramic wafer after Ag powder melts under laser action, repeat above powdering and laser is swept
Process of retouching to reaching required electrode layers thickness, that is, obtains being printed with the insulated substrate of electrode layer (one)；
3) p-type in storage tank and N-shaped thermoelectric material powder interval are spread over step 2) electrode layer (one) table of gained
Face, is then 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, powdering thickness is 50 microns, and laser scan rate is chosen as 50
Mm/s, laser power is chosen as 50W；The print procedure repeating above thermoelectric arm is up to desired height；
4) the electrode powder body Ag powder in storage tank is layered on step 3) on the p-type thermoelectric arm and N-shaped thermoelectric arm of gained, according to
The laser that is designed with of thermo-electric device is scanned to Ag powder printing formation electrode layer (two), and p-type and N-shaped thermoelectric arm are connected
Pick up；
5) by insulated substrate (two) in described electrode layer (two) surface cover, obtain p-SnTe/n-SnSe thermo-electric device.
Figure 13 is surface texture after the thermoelectric arm laser scanning molding of p-type SnTe it can be seen that surface after laser melting
Very smooth.
Embodiment 3
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes following two steps：
(1) supper-fast prepare thermoelectric material powder：According to p-type p-CeFe4Sb12The stoichiometry of each element in thermoelectric compound
Ratio prepares the simple substance powder body of each element as reactant, and ground and mixed uniformly, is reacted by self-propagating combustion or thermal expousure,
Obtain p-type thermoelectric material powder；According to N-shaped Co4Sb12-xTexIn (x=0～0.1), the stoichiometric proportion of each element prepares each element
Simple substance powder body as reactant, ground and mixed uniformly, is reacted by self-propagating combustion or thermal expousure, obtains N-shaped thermoelectricity
Material powder；
Step (2)：Quick preparation p-CeFe4Sb12In conjunction with N-shaped Co4Sb12-xTexThe method of (x=0～0.1) thermo-electric device, bag
Include following steps：
1) prepare raw material, including Al2O3Ceramic insulation substrate, Cu50Mo50Alloy electrode powder body, p-type p-CeFe4Sb12Heat
Electric compound powder body and N-shaped Co4Sb12-xTex(x=0～0.1) thermoelectric compound powder, the particle diameter of wherein each powder material is
Less than 50 μm, and be scattered in water respectively and make suspension for the inkjet printing in subsequent step, the mass percent of suspension
It is 30%；
2) according to required electrode pattern and thickness, using selective laser smelting process, electrode powder suspension ink-jet is beaten
It is imprinted on insulated substrate (), obtain being printed with the insulated substrate of electrode layer (one)；
3) the device thermoelectric arm size according to design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder is with N-shaped thermoelectric compound powder suspension in step 2) the upper inkjet printing of the electrode layer () of gained becomes p-type thermoelectricity
Arm and N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is beaten using selective laser smelting process ink-jet
It is imprinted on p-type thermoelectric arm and N-shaped thermoelectric arm, forms electrode layer (two), described electrode layer (two) is by p-type thermoelectric arm and n
Type thermoelectric arm is connected；
5) insulated substrate (two) in described 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 is respectively 80
Mm/s, 200mm/s, 200mm/s, control climate is 0.5～1 atmospheric pressure inert atmosphere, and monolayer powdering thickness exists
30μm.
Embodiment 4
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes following two steps：
(1) supper-fast prepare thermoelectric material powder：According to p-type MnSi1.75In thermoelectric compound, the stoichiometric proportion of each element is accurate
The simple substance powder body of standby each element uniformly, is reacted by self-propagating combustion or thermal expousure as reactant, ground and mixed, obtains
P-type thermoelectric material powder；According to Mg2Si1-xSnxIn (x=0～1), the stoichiometric proportion of each element prepares the simple substance powder body work of each element
For reactant, ground and mixed uniformly, is reacted by self-propagating combustion or thermal expousure, obtains N-shaped thermoelectric material powder；
Step (2)：Quick preparation p-type MnSi1.75In conjunction with N-shaped Mg2Si1-xSnxThe method of (x=0～1) thermo-electric device, including
Following steps：
1) prepare raw material, including Al2O3Ceramic insulation substrate, NiAl alloy epitaxy electrode powder body, p-type MnSi1.75Thermoelectric compound
Powder body and N-shaped Mg2Si1-xSnx(x=0～1) thermoelectric compound powder, the particle diameter of wherein each powder material is less than 50 μm,
And be scattered in water respectively and make suspension for the inkjet printing in subsequent step, the mass percent of suspension is 40%；
2) according to required electrode pattern and thickness, using selective laser smelting process, electrode powder suspension ink-jet is beaten
It is imprinted on insulated substrate (), obtain being printed with the insulated substrate of electrode layer (one)；
3) the device thermoelectric arm size according to design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder is with N-shaped thermoelectric compound powder suspension in step 2) the upper inkjet printing of the electrode layer () of gained becomes p-type thermoelectricity
Arm and N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is beaten using selective laser smelting process ink-jet
It is imprinted on p-type thermoelectric arm and N-shaped thermoelectric arm, forms electrode layer (two), described electrode layer (two) is by p-type thermoelectric arm and n
Type thermoelectric arm is connected；
5) insulated substrate (two) in described 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 50
Mm/s, 60mm/s, 60mm/s, control climate is 0.5～1 atmospheric pressure inert atmosphere, and monolayer powdering thickness is at 50 μm.
Embodiment 5
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes following two steps：
(1) supper-fast prepare thermoelectric material powder：According to p-type p-CeFe4Sb12The stoichiometry of each element in thermoelectric compound
Ratio prepares the simple substance powder body of each element as reactant, and ground and mixed uniformly, is reacted by self-propagating combustion or thermal expousure,
Obtain p-type thermoelectric material powder；According to Co4Sb12-xTexIn (x=0～0.1), the stoichiometric proportion of each element prepares the list of each element
Matter powder body uniformly, is reacted by self-propagating combustion or thermal expousure as reactant, ground and mixed, obtains N-shaped thermoelectric material
Powder body；
Step (2)：Quick preparation p-type p-CeFe4Sb12In conjunction with N-shaped Co4Sb12-xTexThe method of (x=0～0.1) thermo-electric device,
Comprise the steps：
1) prepare raw material, including Al2O3Ceramic insulation substrate, Cu50W50Alloy electrode powder body, p-type p-CeFe4Sb12Thermoelectricity
Compound powder and N-shaped Co4Sb12-xTex(x=0～0.1) thermoelectric compound powder, the particle diameter of wherein each powder material is 50 μm
Hereinafter, and respectively it is scattered in water and makes suspension for the inkjet printing in subsequent step, the mass percent of suspension is
20%；
2) according to required electrode pattern and thickness, using selective laser smelting process, electrode powder suspension is printed upon
On insulated substrate (), obtain being printed with the insulated substrate of electrode layer (one)；
3) the device thermoelectric arm size according to design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder and N-shaped thermoelectric compound powder suspension are in step 2) be printed as on the electrode layer () of gained p-type thermoelectric arm and
N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is printed upon using selective laser smelting process
On p-type thermoelectric arm and N-shaped thermoelectric arm, form electrode layer (two), described electrode layer (two) will be hot to p-type thermoelectric arm and N-shaped
Electric arm is connected；
5) insulated substrate (two) in described 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 is respectively 20
Mm/s, 100mm/s, 100mm/s, control climate is 0.5～1 atmospheric pressure inert atmosphere, and monolayer powdering thickness exists
60μm.
Embodiment 6
A kind of supper-fast method preparing thermoelectric material powder and device, mainly includes following two steps：
(1) supper-fast prepare thermoelectric material powder：Stoichiometric proportion according to each element in p-type PbSe thermoelectric compound prepares
The simple substance powder body of each element uniformly, is reacted by self-propagating combustion or thermal expousure as reactant, ground and mixed, obtains p
Type thermoelectric material powder；Stoichiometric proportion according to each element in PbS prepares the simple substance powder body of each element as reactant, grinds
Mix homogeneously, is reacted by self-propagating combustion or thermal expousure, obtains N-shaped thermoelectric material powder；
Step (2)：The method that quick preparation p-type PbSe combines N-shaped PbS thermo-electric device, comprises the steps：
1) prepare raw material, including Al2O3Ceramic insulation substrate, TiAl alloy electrode powder body, p-type PbSe thermoelectric compound powder
Body and N-shaped PbS thermoelectric compound powder, the particle diameter of wherein each powder material is less than 50 μm, and is scattered in water system respectively
Become the inkjet printing that suspension is used in subsequent step, the mass percent of suspension is 5%；
2) according to required electrode pattern and thickness, using selective laser smelting process, electrode powder suspension is printed upon
On insulated substrate (), obtain being printed with the insulated substrate of electrode layer (one)；
3) the device thermoelectric arm size according to design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder and N-shaped thermoelectric compound powder suspension are in step 2) be printed as on the electrode layer () of gained p-type thermoelectric arm and
N-shaped thermoelectric arm；
4) according to required electrode pattern and thickness, electrode powder suspension is printed upon using selective laser smelting process
On p-type thermoelectric arm and N-shaped thermoelectric arm, form electrode layer (two), described electrode layer (two) will be hot to p-type thermoelectric arm and N-shaped
Electric arm is connected；
5) insulated substrate (two) in described 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 80
Mm/s, 300mm/s, 300mm/s, control climate is 0.5～1 atmospheric pressure inert atmosphere, and monolayer powdering thickness exists
30μm.
The present invention illustrates embodiments of the present invention as a example this several typical thermoelectric material system by embodiment respectively, known to other
Multiple thermoelectric materials all can obtain thermoelectricity device by changing suitable electrode material composition and selective laser smelting process parameter
Part, here just differs an illustrative example.But the multiple thermoelectric materials listed in the present invention this all enable technology of the present invention
Scheme.
The above is only the preferred embodiment of the present invention it is noted that for the person of ordinary skill of the art,
On the premise of the invention design, some modifications and variations can also be made, these broadly fall into the protection model of the present invention
Enclose.
Claims (10)
1. a kind of supper-fast method preparing thermoelectric material powder and device is it is characterised in that mainly include following two steps：
(1) supper-fast prepare thermoelectric material powder：Stoichiometric proportion according to each element in p-type thermoelectric compound prepares each unit
The simple substance powder body of element uniformly, is reacted by self-propagating combustion or thermal expousure as reactant, ground and mixed, obtains p-type heat
Electric material powder body；Stoichiometric proportion according to each element in N-shaped thermoelectric compound prepares the simple substance powder body of each element as reaction
Thing, ground and mixed uniformly, is reacted by self-propagating combustion or thermal expousure, obtains N-shaped thermoelectric material powder；
(2) supper-fast prepare thermo-electric device：The thermoelectric material powder that insulated substrate, electrode powder body and step (1) are obtained
Alternatively the raw material that sets out of property lf technique, prepares thermo-electric device by 3 D-printing.
2. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 1 is it is characterised in that institute
State electrode powder body and be selected from one or more of simple substance Ni, Cu, Ag, Al, Mo, W, Ti or NiAl alloy epitaxy by any
The mixture of ratio.
3. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 1 is it is characterised in that institute
State p-type thermoelectric compound and be selected from Bi2-xSbxTe3、SnSe、CeFe4Sb12、MnSi1.75、Zr0.5Hf0.5In CoSb and PbSe
A kind of；Described N-shaped thermoelectric compound is selected from Bi2Te3-xSex、SnTe、n-Co4Sb12-xTex、Mg2Si1-xSnx, ZrNiSn and
One of PbS.
4. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 1 is it is characterised in that walk
Suddenly the 3 D-printing described in (2) comprises the steps：
1) prepare raw material, including insulated substrate, electrode powder body, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder
Body；
2) according to required electrode pattern and thickness, electrode powder body is printed upon by the base that insulate using selective laser smelting process
On plate (), obtain being printed with the insulated substrate of electrode layer (one)；
3) the device thermoelectric arm size according to design and distribution, using selective laser smelting process respectively by p-type thermoelectricity chemical combination
Powder and N-shaped thermoelectric compound powder are in step 2) it is printed as p-type thermoelectric arm and N-shaped heat on the electrode layer () of gained
Electric arm；
4) according to required electrode pattern and thickness, electrode powder body is printed upon p-type heat using selective laser smelting process
In electric arm and N-shaped thermoelectric arm, form electrode layer (two), described electrode layer (two) is by p-type thermoelectric arm and N-shaped thermoelectric arm phase
Connect；
5) insulated substrate (two) in described electrode layer (two) surface cover, obtains thermo-electric device.
5. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 4 is it is characterised in that walk
In rapid 1), the Task-size Controlling of electrode powder body, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder is in 0.1～50 μm of model
Enclose.
6. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 4 is it is characterised in that walk
In rapid 1), electrode powder body, p-type thermoelectric compound powder and N-shaped thermoelectric compound powder are scattered in water or volatility respectively
Suspension is made for follow-up printing step, the solid concentration of suspension all controls 1～40% in solvent.
7. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 4 it is characterised in that
Described step 2) need if necessary to be repeated, until it reaches the thickness required for electrode layer ()；Described step 3) must
Will when need to be repeated, until it reaches the thickness required for p-type thermoelectric arm and N-shaped thermoelectric arm；Described step 4) if necessary
Needs are repeated, until it reaches the thickness required for electrode layer (two).
8. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 4 is it is characterised in that walk
Rapid 2), 3), 4) in selective laser smelting process in, the type of laser is continuous laser, and wavelength is 1060～1070
Nm, in 5～100W, in 10～500mm/s, control climate is 0.5～1 to laser scanning line rate controlled to the Power Control of laser
Atmospheric pressure inert atmosphere, monolayer powdering thickness is at 30～100 μm.
9. a kind of supper-fast method preparing thermoelectric material powder and device according to claim 1 is 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.
10. the thermo-electric device prepared by any one in claim 1-9.
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| CN110729391A (en) * | 2019-07-30 | 2020-01-24 | 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 |
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| 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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| 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 |
| CN110729391A (en) * | 2019-07-30 | 2020-01-24 | 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 |
| CN110783448A (en) * | 2019-07-30 | 2020-02-11 | 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 |
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| 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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