CN108461618A - The method that 3D printing technique manufactures thermo-electric device - Google Patents

The method that 3D printing technique manufactures thermo-electric device Download PDF

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Publication number
CN108461618A
CN108461618A CN201810225213.2A CN201810225213A CN108461618A CN 108461618 A CN108461618 A CN 108461618A CN 201810225213 A CN201810225213 A CN 201810225213A CN 108461618 A CN108461618 A CN 108461618A
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kinds
thermoelectric
electric device
printing technique
thermoelectric material
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CN201810225213.2A
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Chinese (zh)
Inventor
李勃
李甫
苏宁
郭帅
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Shenzhen Graduate School Tsinghua University
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Shenzhen Graduate School Tsinghua University
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Priority to CN201810225213.2A priority Critical patent/CN108461618A/en
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01Manufacture or treatment

Abstract

The present invention provides a kind of method of 3D printing technique manufacture thermo-electric device, elemental powders are synthesized to the compound of thermoelectric material needed for p-type and N-shaped including the use of ball-milling technology, binder and solvent is used uniformly to be mixed with certain proportion, forming two kinds of thermoelectric material mixed slurries makes it meet specific rheologic behavio(u)r, three-dimensional structure molding is carried out to thermoelectric material suspension using 3D printing technique, so that the thermoelectric material of be printed as two kinds of high length-diameter ratios is arranged alternately and is bonded on ceramic substrate;Thermoelectric material and ceramic substrate are sintered, remove the solvent and binder in thermoelectric material, ceramic substrate through-thickness is laminated and is accumulated, form p-type and the alternately arranged thermoelectric arm of N-shaped, complete the making of electrode so that all thermoelectric arms are together in series, and complete the encapsulation of upper and lower surface ceramic substrate, leading-out terminal is drawn, thermo-electric device is completed and makes.The making of high aspect ratio thermoelectric arm can be achieved in the present invention, can reach the larger temperature difference and output power.

Description

The method that 3D printing technique manufactures thermo-electric device
Technical field
The present invention relates to the sides that thermo-electric device preparing technical field more particularly to a kind of 3D printing technique manufacture thermo-electric device Method.
Background technology
Thermoelectric material refers to a kind of material that electric energy and thermal energy may be implemented and convert mutually.Thermoelectricity device prepared by thermoelectric material Part can be used for thermo-electric generation and refrigeration.The temperature difference, output power and the refrigerating efficiency of thermo-electric device are related with the aspect ratio of thermoelectric arm, Therefore it is urgent need to solve the problem to produce the thermo-electric device with high aspect ratio thermoelectric arm.Nowadays, with MEMS The problems such as growing rapidly, being controlled there are many energy supply and temperature urgent need solution, this makes the micromation of thermo-electric device also more next More receive significant attention.
The manufacturing process of Conventional thermoelectric device is to subtract material manufacturing process.It is synthesized first by ball-milled powder simple substance required Thermoelectricity material compound, then compound powder is put into mold and sinters thermoelectric material block into, then it is slotting embedding at multiple by cutting The thermoelectric pile of p-type and N-shaped thermoelectric arm is closed.This preparation process is not only complicated, made thermoelectric arm due to being limited by technique, Aspect ratio is extremely limited, thus cannot form the big temperature difference and output power, while will also result in the waste of raw material.
Invention content
In view of this, it is necessary to provide a kind of method that 3D printing technique manufactures thermo-electric device, Gao Zong can be prepared The horizontal thermo-electric device than thermoelectric material.
A kind of method of 3D printing technique manufacture thermo-electric device includes the following steps:
Elemental powders are synthesized to the compound powder of p-type and N-shaped thermoelectric material using ball-milling technology;
800 mesh sieve will be crossed respectively after the compound powder drying of two kinds of thermoelectric materials;
It is uniformly mixed with two kinds of Thermoelectricity material compound powders respectively using binder, forms two kinds of thermoelectric material slurries;
It is uniformly mixed with two kinds of thermoelectric material slurry in proportion respectively using solvent, forms two kinds of thermoelectric material mixing slurries Material, two kinds of thermoelectric material mixed slurries meet specific rheologic behavio(u)r;
Three-dimensional structure molding is carried out using two kinds of thermoelectric material mixed slurries of 3D printing technique pair, simultaneously using two syringe needles Two kinds of thermoelectric materials of p-type and N-shaped are printed, so that be printed as two kinds of thermoelectric materials is arranged alternately and is bonded on several ceramic substrates;
Two kinds of thermoelectric materials on several ceramic substrates and ceramic substrate are sintered, are removed in two kinds of thermoelectric materials Solvent, cure thermoelectric material, and remove two kinds of thermoelectric materials in binder;
Several ceramic substrate through-thickness are laminated and are accumulated, the gap among ceramic substrate is filled with epoxy resin, shape At two kinds of alternately arranged thermoelectric arms of thermoelectric material of p-type and N-shaped;
Complete the making of electrode so that all thermoelectric arms are together in series;
The encapsulation of several ceramic substrate upper and lower surfaces is completed, leading-out terminal is drawn.
Further, the rotating speed of the ball-milling technology is 450rpm, and the time is 4 hours.
Further, the grain size of described two thermoelectric material powders is no more than 10 μm, and 1 μm or more of particle accounts for sum 90%.
Further, in each thermoelectric material mixed slurry, the quality of the powder accounts for powder and the total matter of binder The 5~95% of amount, the quality of the solvent account for powder, binder and solvent gross mass 40~60%.
Further, the binder is polyvinyl alcohol, polyethylene glycol or dimethyl silica alkanol.
Further, the solvent is deionized water or absolute ethyl alcohol.
Further, the specific rheologic behavio(u)r is that elasticity modulus is more than loss modulus when not applying pressure, is applied Elasticity modulus is less than loss modulus when plus-pressure.
Further, the precision of the syringe needle is 50~100 μm.
Further, the sintering temperature is 400 degree, and the sintering time is 2 hours or 3 hours.
Further, the making of electrode is completed using magnetron sputtering.
The method of 3D printing technique manufacture thermo-electric device provided by the invention, can realize arbitrary shape under the path of setting The manufacture of shape material, prepares that speed is fast, and precision and efficient can prepare the thermo-electric device of high aspect ratio thermoelectric material.
Description of the drawings
Fig. 1 is the flow diagram for the method that 3D printing technique manufactures thermo-electric device in an embodiment of the present invention.
Following specific implementation mode will be further illustrated the present invention in conjunction with above-mentioned attached drawing.
Specific implementation mode
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other Embodiment shall fall within the protection scope of the present invention.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention The normally understood meaning of technical staff is identical.Used term is intended merely to description tool in the description of the invention herein The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein " and/or " include one or more phases Any and all combinations of the Listed Items of pass.
Referring to Fig. 1, Fig. 1 is the flow signal for the method that a kind of 3D printing technique provided by the invention manufactures thermo-electric device Figure, specifically includes following steps:
Elemental powders are synthesized the compound powder of p-type and N-shaped thermoelectric material using ball-milling technology by S11;
S12 will cross 800 mesh sieve respectively after the compound powder drying of two kinds of thermoelectric materials;
S13 is uniformly mixed with two kinds of Thermoelectricity material compound powders respectively using binder, forms two kinds of thermoelectric material slurries Material;
S14 is uniformly mixed with two kinds of thermoelectric material slurry in proportion respectively using solvent, forms two kinds of thermoelectric material mixing Slurry, two kinds of thermoelectric material mixed slurries meet specific rheologic behavio(u)r;
S15 carries out three-dimensional structure molding using two kinds of thermoelectric material mixed slurries of 3D printing technique pair, utilizes two syringe needles Two kinds of thermoelectric materials of p-type and N-shaped are printed simultaneously, so that be printed as two kinds of thermoelectric materials is arranged alternately and is bonded in several ceramic substrates On;
Two kinds of thermoelectric materials on several ceramic substrates and ceramic substrate are sintered by S16, remove two kinds of thermoelectricity materials Solvent in material cures thermoelectric material, and removes the binder in two kinds of thermoelectric materials;
Several ceramic substrate through-thickness are laminated and accumulate by S17, and the gap among ceramic substrate is filled out with epoxy resin It fills, forms two kinds of alternately arranged thermoelectric arms of thermoelectric material of p-type and N-shaped;
S18 completes the making of electrode so that all thermoelectric arms are together in series;
S19 completes the encapsulation of several ceramic substrate upper and lower surfaces, draws leading-out terminal.
In the present embodiment, the rotating speed of ball-milling technology is 450rpm in the step S11, and rotation time is 4 hours.
So that thermoelectricity diameter of particle is no more than 10 μm in the step S12, and 1 μm or more of particle accounts for the 90% of sum.
Binder is polyvinyl alcohol, polyethylene glycol or dimethiconol in the step S13.
In the step S14 in each thermoelectric material mixed slurry, the quality of powder accounts for the 5 of powder and binder gross mass ~95%, the quality of solvent account for powder, binder and solvent gross mass 40~60%, solvent is deionized water or anhydrous second Alcohol.It is uniformly mixed by a certain percentage with two kinds of thermoelectric material slurries respectively using solvent, formation meets specific rheologic behavio(u)r Two kinds of thermoelectric material mixed slurries, in the present embodiment, specific rheologic behavio(u)r be when not applying pressure springform Amount is more than loss modulus, and elasticity modulus is less than loss modulus when applying pressure.
In the present embodiment, in the step S15, the precision of syringe needle is 50~100 μm, it can print out a diameter of 50~ 100 μm, length is arbitrary and continuous thermoelectric material.
In the present embodiment, in the step S16, sintering temperature is 400 degree, and the sintering time is that 2 hours or 3 are small When.
In the present embodiment, in the step S18, the making of electrode is completed using magnetron sputtering.
The method that 3D printing technique manufactures thermo-electric device is explained below in conjunction with specific embodiment.
First embodiment of the invention provides a kind of 3D printing technique manufacture arbitrary aspect ratio Bi-Sb-Te base thermo-electric devices Method, include the following steps:
Using ball-milling technology by elemental powders Bi, Sb and Te according to specific stoichiometric reaction synthesis N-shaped Bi2Te3With P-type Sb2Te3, N-shaped Bi2Te3With p-type Sb2Te3Two kinds of raw materials of the thermoelectric arm as thermo-electric device.N-shaped Bi2Te3And p-type Sb2Te3Thermoelectricity powder body material milling parameters are:Ball milling 4h under 450rpm rotating speeds.
By two kinds of thermoelectricity powders respectively 800 mesh of mistake sieve so that obtained thermoelectricity diameter of particle be no more than 10 μm, and 1 μm with On particle account for sum 90%.
It is uniformly mixed with two kinds of Thermoelectricity material compound powder respectively using binder, forms two kinds of thermoelectric material slurries, Two kinds of thermoelectricity slurries are uniformly mixed with solvent in certain proportion respectively again, thermoelectric material mixed slurry are formed, in this implementation In example, the quality of solvent account for powder, binder, solvent gross mass 50%, the quality of powder accounts for powder and binder gross mass 90%, binder is polyvinyl alcohol, and solvent is deionized water, and two kinds of thermoelectric material mixed slurries meet specific rheological properties Can, when being not pressurized, elasticity modulus is more than loss modulus, and when there is pressure, elasticity modulus is less than loss modulus.
Using 3D printing technique respectively to N-shaped Bi2Te3With p-type Sb2Te3Thermoelectric material slurry carries out three-dimensional structure molding, P-type Sb is printed using two syringe needles simultaneously2Te3With N-shaped Bi2Te3Two kinds of thermoelectric materials make be printed as two kinds of thermoelectric materials hand over It is bonded on several ceramic substrates for arrangement.In the present embodiment, thermoelectric material printing precision is to be printed using 100 μm of syringe needle Go out a diameter of 100 μm, length is the thermoelectric arm of 1mm, and the aspect ratio of thermoelectric arm is 10:1.
Two kinds of thermoelectric materials on several ceramic substrates and ceramic substrate are sintered, are removed molten in thermoelectric material Agent.In the present embodiment, sintering temperature is 400 degree, sintering time 2h.Cure thermoelectric material at this temperature, and removes viscous Tie agent.
Several ceramic substrate through-thickness are laminated and are accumulated, the gap among several ceramic substrates is filled out with epoxy resin It fills, forms two kinds of alternately arranged thermoelectric arms of thermoelectric material of p-type and N-shaped.
Using magnetron sputtering, the making of electrode is completed under the covering of mask so that all thermoelectric arms are together in series.
The encapsulation of upper and lower surface ceramic substrate is completed, leading-out terminal is drawn, completes the making of thermo-electric device.
Second embodiment of the invention provides a kind of 3D printing technique manufacture arbitrary aspect ratio Bi-Sb-Te base thermo-electric devices Method, include the following steps:
Using ball-milling technology by elemental powders Bi, Sb and Te according to specific stoichiometric reaction synthesis N-shaped Bi2Te3With P-type Bi0.5Sb1.5Te3, N-shaped Bi2Te3With p-type Bi0.5Sb1.5Te3Two kinds of raw materials of the thermoelectric arm as thermo-electric device.N-shaped Bi2Te3With p-type Bi0.5Sb1.5Te3Thermoelectricity powder body material milling parameters are:Ball milling 4h under 450rpm rotating speeds.
By two kinds of thermoelectricity powders respectively 800 mesh of mistake sieve so that obtained thermoelectricity diameter of particle be no more than 10 μm, and 1 μm with On particle account for sum 90%.
It is uniformly mixed with two kinds of Thermoelectricity material compound powder respectively using binder, forms two kinds of thermoelectric material slurries, Two kinds of thermoelectricity slurries are uniformly mixed with solvent in certain proportion respectively again, thermoelectric material mixed slurry are formed, in this implementation In example, the quality of solvent account for powder, binder, solvent gross mass 70%, the quality of powder accounts for powder and binder gross mass 95%, binder is polyvinyl alcohol, and solvent is deionized water, and two kinds of thermoelectric material mixed slurries meet specific rheological properties Can, when being not pressurized, elasticity modulus is more than loss modulus, and when there is pressure, elasticity modulus is less than loss modulus.
Using 3D printing technique respectively to N-shaped Bi2Te3With p-type Bi0.5Sb1.5Te3Thermoelectric material slurry carries out three-dimensional structure Molding prints N-shaped Bi simultaneously using two syringe needles2Te3With p-type Bi0.5Sb1.5Te3Two kinds of thermoelectric materials make be printed as two kinds Thermoelectric material, which is arranged alternately, to be bonded on several ceramic substrates.In the present embodiment, thermoelectric material printing precision is to utilize 50 μm Syringe needle print a diameter of 50 μm, the aspect ratio of the thermoelectric arm that length is 500 μm, thermoelectric arm is 10:1.
Two kinds of thermoelectric materials on several ceramic substrates and ceramic substrate are sintered, are removed molten in thermoelectric material Agent.In the present embodiment, sintering temperature is 400 degree, sintering time 3h.Cure thermoelectric material at this temperature, and removes viscous Tie agent.
Several ceramic substrate through-thickness are laminated and are accumulated, the gap among several ceramic substrates is filled out with epoxy resin It fills, forms two kinds of alternately arranged thermoelectric arms of thermoelectric material of p-type and N-shaped.
Using magnetron sputtering, the making of electrode is completed under the covering of mask so that all thermoelectric arms are together in series.
The encapsulation of upper and lower surface ceramic substrate is completed, leading-out terminal is drawn, completes the making of thermo-electric device.
The method of 3D printing technique manufacture thermo-electric device provided by the invention, can realize arbitrary shape under the path of setting The manufacture of shape material, prepares that speed is fast, and precision and efficient can prepare the thermo-electric device of high aspect ratio thermoelectric material.
Those skilled in the art it should be appreciated that more than embodiment be intended merely to illustrate the present invention, And it is not used as making embodiment of above as long as in the spirit of the present invention for limitation of the invention Appropriate change and variation all fall in the scope of protection of present invention.

Claims (10)

1. a kind of method of 3D printing technique manufacture thermo-electric device, which is characterized in that the described method comprises the following steps:
Elemental powders are synthesized to the compound powder of p-type and N-shaped thermoelectric material using ball-milling technology;
800 mesh sieve will be crossed respectively after the compound powder drying of two kinds of thermoelectric materials;
It is uniformly mixed with two kinds of Thermoelectricity material compound powders respectively using binder, forms two kinds of thermoelectric material slurries;
It is uniformly mixed with two kinds of thermoelectric material slurry in proportion respectively using solvent, two kinds of thermoelectric material mixed slurries of formation, two Kind thermoelectric material mixed slurry meets specific rheologic behavio(u)r;
Three-dimensional structure molding is carried out using two kinds of thermoelectric material mixed slurries of 3D printing technique pair, is printed simultaneously using two syringe needles Two kinds of thermoelectric materials of p-type and N-shaped make be printed as two kinds of thermoelectric materials be arranged alternately and are bonded on several ceramic substrates;
Two kinds of thermoelectric materials on several ceramic substrates and ceramic substrate are sintered, are removed molten in two kinds of thermoelectric materials Agent cures thermoelectric material, and removes the binder in two kinds of thermoelectric materials;
Several ceramic substrate through-thickness are laminated and are accumulated, the gap among ceramic substrate is filled with epoxy resin, forms p-type With two kinds of alternately arranged thermoelectric arms of thermoelectric material of N-shaped;
Complete the making of electrode so that all thermoelectric arms are together in series;
The encapsulation of several ceramic substrate upper and lower surfaces is completed, leading-out terminal is drawn.
2. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:The ball-milling technology Rotating speed is 450rpm, and the time is 4 hours.
3. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:Described two thermoelectricity materials The grain size of feed powder body is no more than 10 μm, and 1 μm or more of particle accounts for the 90% of sum.
4. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:Each thermoelectricity material Expect in mixed slurry, the quality of the powder accounts for the 5~95% of powder and binder gross mass, and the quality of the solvent accounts for powder The 40~60% of body, binder and solvent gross mass.
5. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:The binder is poly- Vinyl alcohol, polyethylene glycol or dimethyl silica alkanol.
6. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:The solvent be go from Sub- water or absolute ethyl alcohol.
7. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:The specific rheology It is that elasticity modulus is more than loss modulus when not applying pressure to learn performance, and elasticity modulus is less than loss modulus when applying pressure.
8. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:The precision of the syringe needle It is 50~100 μm.
9. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:The sintering temperature is 400 degree, the sintering time is 2 hours or 3 hours.
10. the method for 3D printing technique manufacture thermo-electric device as described in claim 1, it is characterised in that:Using magnetron sputtering Complete the making of electrode.
CN201810225213.2A 2018-03-19 2018-03-19 The method that 3D printing technique manufactures thermo-electric device Pending CN108461618A (en)

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CN111446356A (en) * 2020-05-25 2020-07-24 长沙理工大学 Reel type transverse thermoelectric device and manufacturing method thereof

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Cited By (5)

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CN109545951A (en) * 2018-11-16 2019-03-29 清华大学深圳研究生院 A kind of organic thermo-electric device template and preparation method thereof and a kind of thermo-electric device
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CN111446356A (en) * 2020-05-25 2020-07-24 长沙理工大学 Reel type transverse thermoelectric device and manufacturing method thereof
CN111446356B (en) * 2020-05-25 2022-07-19 长沙理工大学 Reel type transverse thermoelectric device and manufacturing method thereof

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