CN105810810B - Annular-structure thermo-electric device with support frame and preparation method thereof - Google Patents
Annular-structure thermo-electric device with support frame and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to annular-structure thermo-electric device with support frame and preparation method thereof.The annular-structure thermo-electric device of the present invention, include the thermoelectric mechanism of two symmetrical semicirculars of minute surface；Each thermoelectric mechanism possesses：The thermoelectric element of the support frame of semicircular, the semicircular being arranged in the support frame；With the flow guiding electrode of the inside and outside ring surface of the connection thermoelectric element；Wherein, the thermoelectric element in minute surface symmetric position on the thermoelectric mechanism is connected in series.
Description
Technical field
The invention belongs to technical field of thermoelectric conversion, in particular it relates to a kind of annular-structure thermo-electric device and its preparation side
Method.
Background technology
As a kind of environment-friendly renewable sources of energy technology, thermoelectric generation technology received widely in the world in recent years
Attract attention.Thermoelectric power generation technology is the Seebeck effect using semi-conducting material, and the temperature difference is directly converted into the new technology of electric energy.Should
Technology has that reliability is high, pollution-free and noiseless advantage, more than the industry recycling of used heat and waste heat of automotive exhaust gas with
And the high-technology field such as Military Power will have a good application prospect.
One thermo-electric device is often made up of multiple n-types and p-type semiconductor thermoelectric element.It is defeated due to each thermoelectric element
Go out that voltage is very low, in order to obtain higher voltage in order to actually use, generally with metal or alloy electrode by a n-type heat
Electric device and a p-type thermoelectric element connect into thermoelectricity list idol, then that multiple thermoelectricity lists are occasionally in parallel by conductive series connection, heat conduction
Structure connects composition thermo-electric device.
Thermo-electric device main at present is configured to π shapes construction.In the structure shown here, n-type and p-type thermoelectric element with electrically coupled in series and
Hot form in parallel is integrated among the earthenware slab that two are electrically insulated and heat transfer is good, and this construction is primarily adapted for use in flat board
The environment of shape thermal source, i.e. direction of heat flow are perpendicular to two parallel ceramic wafers.
But when thermal source is non-planar base, this traditional π shapes construction thermo-electric device is just no longer applicable.Such as automobile
Exhaust emission pipeline, the thermoelectric generator to match with thermal source (such as patent text is such as manufactured using π shapes thermoelectric generation module
Offer：US8656710B2, US2005/0172993A1, US013/0160809A1), due to needing in electrothermal module surface applying power
Ensure the good contact between module and thermal source, so that the structure of electric organ becomes extremely complex, cost of manufacture is high, and
The performance and use reliability of electric organ are low.Especially for the small column thermal source as a diameter of about 1cm, this thermoelectric generator
It is integrated to become extremely difficult.But for this column thermal source, the collection of electric organ is allowed for using the thermo-electric device of circular structure
It is more excellent into relatively easy and performance.
In the thermo-electric device of circular structure, n-type and p-type annular hollow thermoelectric element are alternately coaxially arranged along column thermal source
Row, the material that filling heat and electricity insulate each other.This construction can maximally utilise what column thermal source was conducted
Heat, therefore the thermo-electric device that heating efficiency constructs relative to π shapes will increase substantially.Due to current many thermals source, such as vapour
Tail gas discharge tube belongs to non-planar base thermal source, and therefore, the thermo-electric device of circular structure is in actual applications with very big
Prospect.It needs to be emphasized that generated electricity for waste heat of automotive exhaust gas, it is ready-made on electric organ cold end cooling generally use automobile
Cooling water.Cylindrical by ring-shaped device is designed to hot junction, and inner circle is designed to cold end.Because the heat transfer between liquid and solid is excellent
Heat transfer between gas and solid, so can be with balancing device in hot and cold side using the area discrepancy of ring-shaped device inner and outer round surface
Heat-exchange capacity, this is another advantage of annular thermoelectric generator.United States Patent (USP) US2012/0174567A1 and China are special
Sharp CN201420052870.9 discloses the thermoelectric generator structure integrated with annular thermo-electric device, different according to design structure,
Thermal source can carry out heat exchange from radial and axial with thermoelectric element, compared with the electric organ that tradition is integrated by π types device, hence it is evident that
Improve heat exchanger effectiveness.
Although the concept of annular Thermoelectric Generator has been born many years, because the limitation of pyroelectric material performance is led
Cause the research report of the annular-structure thermo-electric device closely related with practical application in the world at present few.The western room in the U.S. in 1969
Electric company reports annular thermo-electric device concept earliest（Proc. 4th Intersoc Energy Couvers Eng.
Conf. Wahington DC, 1969, New York, 1969, 300-307）.Up to the present, it has been disclosed that or report
Annular thermo-electric device preparation method have it is following several：
（1）Annular thermoelectric material part is directly prepared using special die, then ring surfaces externally and internally metallizes, and finally uses
Element is connected into ring-shaped device by solder or diffusion welding (DW) by flow deflector.A. Schmitz is prepared for PbTe using special die
Annular thermoelectric material part, then with electroplating technology ring surface formed layer of Ni metal layer, finally use Ni for electrode with
Muscovite realizes the connection between element for insulating materials by diffusion welding (DW) at high temperature.（A. Schmitz,C. Stiewe
and E. Muller, Preparation of Ring-Shaped Thermoelectric Legs from PbTe
Powders for Tubular Thermoelectric Modules, J. Elec. Mater., 42 (2013) 1702-
1706）.Chinese patent CN201310443542.1 discloses a kind of method for directly preparing hollow structure, using this method from spy
The sample of sintering is taken out in molding jig, directly obtains the thermoelectric material part of hollow structure.
（2）Annular thermoelectric material part is processed from solid sample using cutting processing instrument, then to appearance in ring
Face is metallized, and element finally is connected into ring-shaped device by flow deflector using solder or diffusion welding (DW).Gao in 2007 et al. reports
Road is using spark cutting technique from Bi2Te3Annular element is processed in crystal prototype, surface metalation material is
Bi0.95Sb0.05, adjacent two ring connects to form Bi by the use of Cu as electrode2Te3Thermoelectric material annular thermo-electric device（M. Gao and
D.M. Rowe, Ring-structured Thermoelectric Module, Semicond. Sci. Technol. 22
(2007) 880-883）.
（3）Small material components are formed using various material preparation methods and local surfaces metallize, then will be some
Material widget is assembled into an annular hollow element, is finally connected into element by flow deflector using solder or diffusion welding (DW)
Ring-shaped device.Chinese patent CN201310549191.2 discloses three kinds and prepares abnormity（Including annular）The method of thermoelectric element.
Method A is directly to prepare a hollow structure from mould or model, then by its refine into accurate size（That is the above method
1）；Method B is to prepare a hollow structure from a solid block, is then cut into a hollow structure（That is the above method 2）；
Method C is the hollow structure that preliminary dimension and structure are formed by assembling multiple parts（That is this method 3）.This method includes：(a)
Substantial amounts of thermoelectric material widget is prepared, each widget has a predetermined shape；(b) by multiple material widget collection
The combination predetermined into one forms annular thermoelectric element；(c) a number of annular thermoelectric element is passed through into solder or diffusion
Weldering connects into the ring-shaped device of predetermined configuration with flow deflector.
（4）Material components preparation, surface metalation are realized using one-step technology and singly even device is integrated while completes, most
Single even device is connected into by ring-shaped device by flow deflector using solder or diffusion welding (DW) afterwards.Chinese patent
CN201410039382.9 discloses a kind of method that one-step method quickly prepares annular heat electrical component, according to the patented technology,
N-type and p-type thermoelectric material powder, surface metalation layer material and flow guiding electrode are placed in special die, by hot pressing or
Discharge plasma sintering technique realize annular material part and inner and outer round surface metallization and p-type and n-type list it is coupled connect it is same
When complete.
Up to the present, it has been disclosed that or the structure of the annular thermo-electric device of report have it is following several：
（1）It is monocyclic to contain some ring-shaped devices to sector ele-ment.United States Patent (USP) US4056406 discloses one kind within 1977
Annular thermoelectric element structure, each ring are made up of the n-type of identical quantity and the sector ele-ment of p-type, so as to effectively disappear
Except the thermal stress during thermoelectric element use influences.
（2）Monocyclic is complete annular thermoelectric element, and n-type and/or p-type annular thermoelectric element are in a manner of polycyclic alternate layout
Integrated device.Such as the disclosed Si that electrode is made of Cu of United States Patent (USP) US6096966 in 20000.8Ge0.2Annular thermo-electric device；
The Bi connected by the use of Cu as electrode of Gao in 2007 et al. reports2Te3Thermoelectric material annular thermo-electric device（M. Gao and
D.M. Rowe, Ring-structured Thermoelectric Module, Semicond. Sci. Technol. 22
(2007) 880-883）；A. Schmitz report with the PbTe annular thermo-electric devices that Ni is electrode.（A. Schmitz,C.
Stiewe and E. Muller, Preparation of Ring-Shaped Thermoelectric Legs from
PbTe Powders for Tubular Thermoelectric Modules, J. Elec. Mater., 42 (2013)
1702-1706）.
（3）Monocyclic is complete annular thermoelectric element, and cross sectional shape is polygon etc..From substantially saying, this structure is still
So belong to the second class.Such as Chinese patent CN201310549191.2 and CN201310443542.1 disclose several annular thermoelectricity
The shape and preparation method of material components.
But there are the following problems for existing annular thermoelectric element and device preparation method.First, existing annular thermoelectricity member
Part and device technology of preparing efficiency is low, cost is high；Secondly, the product quality of ring-shaped device（Such as ring-type element concentricity）It is difficult to
Ensure；3rd, ring-shaped device needs to reinforce some strength in interior outer ring surface in order to ensure use intensity（Thickness）Earthenware, drop
Low heat exchanger effectiveness between thermal source and thermoelectric element, while the stress release of ring-type element is also have impact on, cause annular heat
The damage of electric device；4th, it is restricted using the ring-shaped device temperature in use of solder connection ring-type element.Therefore, this area
There is an urgent need to develop a kind of brand-new annular heat electrical component technology of preparing for being suitable for batch production, produced using the new technology
Annular heat electrical component can significantly improve production efficiency and product quality, while reduce production cost, so as to promote annular structure
The real application of fabricate-heat electrical part.
The content of the invention
In view of the above, the technical problems to be solved by the invention be to provide it is a kind of it is rational in infrastructure, be advantageous to cost
A kind of new annular-structure thermo-electric device of control, performance optimization and mass production technique and preparation method thereof.
An aspect of of the present present invention, there is provided a kind of annular-structure thermo-electric device, include the heat of two symmetrical semicirculars of minute surface
Electric components；Each thermoelectric mechanism possesses：The thermoelectricity of the support frame of semicircular, the semicircular being arranged in the support frame
Element；With the flow guiding electrode of the inside and outside ring surface of the connection thermoelectric element；Wherein, it is in minute surface pair on the thermoelectric mechanism
The thermoelectric element of position is claimed to be connected in series.
According to the present invention, each thermoelectric element concentricity is high in annular-structure thermo-electric device, and the support frame of semicircular provides
Fundamental strength and as the partiting thermal insulation material between the thermoelectric element of adjacent semicircular, can partly substitute existing annular thermoelectricity
The advantages of ceramic outer pipe and inner tube in device, have that heat exchanger effectiveness is high, that is, generating efficiency is high.Using the annular of the present invention
Construction thermo-electric device can significantly improve the assembling quality and production efficiency of annular-structure thermo-electric device, reduce production cost, and
Stress release advantage caused by the design of the thermoelectric element of semicircular and support frame are carried using caused device strength
The service life of device can be significantly improved by rising, particularly the service life under the adverse circumstances such as vibrations.
Also, in the present invention or, the big frame part of each support frame including multiple semicirculars and multiple
The little framework part of semicircular, the radius of the big frame part are more than the radius of the little framework part, and the big frame
Part and the little framework part are axially alternately arranged with the big frame part and the small frame with certain spacing
The gap of semicircular is formed between frame part.
According to the present invention, the architectural feature of the big frame part and little framework part and being alternately arranged may insure adjacent
N-type and the effective of p-type thermoelectric element are connected in series.
Also, or, the thermoelectric material part of semicircular is set in the gap, and described in the present invention
Metallization and flow guiding electrode layer are formed on the inside and outside ring surface of thermoelectric material part.
According to the present invention, the thermoelectric material part of the previously prepared semicircular with suitable dimension is placed in semicircular
In gap, then semicircular support frame outer shroud and inner ring surface form certain thickness metallization and flow guiding electrode
Layer.I.e., the support frame of the previously prepared semicircular of the present invention, is then placed in prefabricated semi-ring by the thermoelectric material part of semicircular
In the support frame of shape, then metallization is formed on the inside and outside ring surface of support frame using suitable such as spraying technology and led
Electrode layer is flowed, so as to complete the preparation of thermoelectric element and thermo-electric device simultaneously, therefore production efficiency is high and production cost is low.
Also, or, the thermoelectric material part is handed over p-type and n-type semiconductor thermoelectric material part in the present invention
Be set in turn in for the form of arrangement in multiple gaps, and each adjacent thermoelectric material part by flow guiding electrode along footpath
It is connected in series to direction.
According to the present invention, when the thermoelectric material part of semicircular is placed in the gap of semicircular, p-type and n-type semiconductor
Thermoelectric material part is alternately arranged.P-type（Or n-type）Semiconductor material parts and left and right adjacent n form（Or p-type）Semiconductor material
Expect part by being connected on its outer shroud（Or inner ring）Surface and inner ring（Outer shroud）Surface alternately connects, and has necessarily so as to obtain
The electricity of output voltage.
Also, or, the height and thickness of the big frame part and the little framework part are homogeneous in the present invention
Together.
According to the present invention, the height and thickness all same of big frame part and little framework part cause the design of support frame
The manufacturing process of manufacturing process and material components is simply controllable.In addition, big frame part and little framework part depend highly on
The hot property of support frame material and the temperature in use of thermo-electric device.It is thick that the thickness of support frame depends on thermoelectric material part
Degree.And the radius of big frame part and little framework part depends on the radius of thermoelectric material part, big frame part and little framework
The outer ring surface of part（Or inner ring surface）Radial difference depends on the thickness of metallization and flow guiding electrode layer.The gap of support frame
Width depends on p-type and the height of n-type thermoelectric material part.
Also, or, the metallization and flow guiding electrode layer are located at the outer of the thermoelectric material part in the present invention
The thickness of ring surface and inner ring surface, the big frame part or the little framework part is the thickness of the thermoelectric material part
With the metallization and the thickness sum of flow guiding electrode layer.
According to the present invention, the thermoelectric material part can use the relatively larger thermoelectric material of resistivity, in addition, should
Kind structure, which can reduce the Interface Cracking caused by the hot expansion system difference of thermoelectric material part and support frame, to be influenceed.
Also, or, the metallization and flow guiding electrode layer are located at the side of the thermoelectric material part in the present invention
Face and the external annular surface or inner ring surface for extending to the big frame part or the little framework part, the thermoelectric material part
Thickness for the big frame part or the little framework part thickness and the thickness of the metallization and flow guiding electrode layer it
With.
According to the present invention, the thermoelectric material part can use the relatively smaller thermoelectric material of resistivity, in addition, this
Kind structure is particularly suitable for those using the material big compared with the resistivity of copper as guide layer and the situation of electrode layer material.
Also, or, the support frame is made up of ceramics, glass, resin or nylon in the present invention.
According to the present invention, made of ceramics, glass, resin or nylon are made etc. support frame possess excellent intensity and
Insulating properties, be advantageous to improve the service life of device.
Also, in the present invention or, the radial section of the support frame be formed as semi-annular shape, en ring-type,
Semi-hexagon shape ring-type or semiellipse ring-type.
According to the present invention, the radial cross-sectional shape of support frame is semi-annular shape, en ring-type, semi-hexagon shape ring-type or half
Oval ring-type can adapt to the requirement of different shape thermal source completely, it is ensured that the efficient utilization of the thermal source energy.
Another aspect of the present invention, there is provided a kind of preparation method of annular-structure thermo-electric device, including：Manufacture semicircular
Thermoelectric material part and support frame, the thermoelectric material part is embedded in the support frame；In the insertion thermoelectric material
The inner and outer ring surface spraying metallization of the support frame of part and flow guiding electrode layer, and be ground to form semicircular
Thermoelectric mechanism；The thermoelectric mechanism of two symmetrical semicirculars of minute surface is spliced into complete annular-structure thermo-electric device.
Compared with existing annular-structure thermo-electric device and preparation method thereof, the present invention has advantages below.
Each annular thermoelectric element in the annular-structure thermo-electric device with support frame of the present invention is because concentricity is high, heat
Electric device metallizes and flow guiding electrode layer is good with thermoelectric material component contact and thickness is uniform, so using produced by the present invention
Annular-structure thermo-electric device has the advantages of assembling quality height and good device performance.
Metallization and water conservancy diversion of the preparation method of the annular-structure thermo-electric device of the present invention due to annular thermoelectric material part
The connection of electrode layer is completed simultaneously, thus the preparation method has the advantages of production efficiency is high low with production cost.
One of function of support frame is that part substitutes existing annular heat electrical equipment in the annular-structure thermo-electric device of the present invention
Ceramic outer pipe and inner tube in part, thus the annular-structure thermo-electric device with support frame of the present invention is with heat exchanger effectiveness
Height, that is, the advantages of generating efficiency is high.
Support frame compares more existing annular heat electrical device structures significantly in the annular-structure thermo-electric device of the present invention
The intensity of device is improved, extends the service life of device, the particularly service life in frequent vibration environment.
The annular-structure thermo-electric device with support frame of the present invention forms metallization and water conservancy diversion electricity using spraying technology
Pole layer, the annular thermo-electric device that more existing part uses scolding tin to fix material for flow guiding electrode have temperature in use height and generating
The advantages of efficiency high.
According to following embodiments and refer to the attached drawing, the above of the present invention and other mesh are better understood with
, feature and advantage.
Brief description of the drawings
Fig. 1 shows the support of the annular-structure thermo-electric device with support frame of the embodiment according to the present invention
The structural representation of framework；
Fig. 2 shows the structural representation from the support frame in Fig. 1 of inner side viewing；
Fig. 3 shows another structural representation of the support frame in Fig. 1, and it illustrates the semicircle for being put into suitable dimension
The position in the semi-circular shape space of annular thermoelectric material part；
Fig. 4 shows the top view of the support frame in Fig. 3；
Fig. 5 shows the A-A sectional views of the support frame in Fig. 2 and Fig. 4；
Fig. 6 is shown is put into annular according to the support frame of the first embodiment of the present invention in Figure 5 by A type device architectures
The schematic diagram of thermoelectric material part；
Fig. 7 shows that the support frame in Fig. 4 is put into thermoelectric material part by A type device architectures, and is formed in ring surface
Metallization and the schematic diagram of flow guiding electrode layer；
Fig. 8 shows that the structure devices shown in Fig. 6 complete metallization and water conservancy diversion electricity by spraying technology in interior external annular surface
The sectional view of the A type annular-structure thermo-electric devices with support frame after the layer Joining Technology of pole；
Fig. 9 shows that support frame according to the second embodiment of the present invention in Figure 5 is put into annular by Type B device architecture
The schematic diagram of thermoelectric material part；
Figure 10 shows that the support frame in Fig. 4 is put into thermoelectric material part by Type B device architecture, and is formed in ring surface
Metallization and the schematic diagram of flow guiding electrode layer；
Figure 11 shows that the structure devices shown in Fig. 9 complete metallization and water conservancy diversion electricity by spraying technology in interior external annular surface
The sectional view of the Type B annular-structure thermo-electric device with support frame after the layer Joining Technology of pole；
Figure 12 shows the thermoelectric material part in Examples 1 and 2（Black）Radially sectional view.
Embodiment
Illustrate the progress of the substantive distinguishing features of the present invention and conspicuousness with reference to specific implementation form and accompanying drawing.Ying Li
Solution, these embodiments are only used for that the present invention is further described, it is impossible to are interpreted as limiting the scope of the invention.
An aspect of of the present present invention, there is provided a kind of annular-structure thermo-electric device, include the heat of two symmetrical semicirculars of minute surface
Electric components；Each thermoelectric mechanism possesses：The thermoelectricity of the support frame of semicircular, the semicircular being arranged in the support frame
Element；With the flow guiding electrode of the inside and outside ring surface of the connection thermoelectric element；Wherein, it is in minute surface pair on the thermoelectric mechanism
The thermoelectric element of position is claimed to be connected in series.
In the present invention, the radial section of support frame be formed as semi-annular shape, en ring-type, semi-hexagon shape ring-type or
Semiellipse ring-type.It is described in detail in the following explanation with reference to accompanying drawing exemplified by being formed as semi-annular shape, but the present invention is not
It is limited to this.
In illustrating below, semi-circular shape, arc and the trapezoidal thermoelectric material sample of preparation are referred to as thermoelectric material part, described
It is referred to as thermoelectric element after the metallization of part local surfaces, the thermoelectric element is integrated by flow guiding electrode material and support frame
Device be referred to as thermo-electric device.Radial distance between annular products inner and outer ring is referred to as the thickness of ring, annular products two sides it
Between vertical range be referred to as height.
In the embodiment of the present invention, there is provided a kind of new annular-structure thermo-electric device and preparation method thereof
（Referring to Figures 1 and 2）.Compared with prior art, novel part of the invention is previously prepared annular brace framework, then
Semi-circular shape thermoelectric material part is placed in prefabricated annular brace framework, thermoelectricity is completed using suitable spraying technology simultaneously
The preparation of element and device.
In the present invention,（Referring to Figures 1 and 2）Support frame is made up of the symmetrical two semi-circular shape portions of minute surface.Each half
The big part of semicircular ring that several radiuses are big is included in annular support frame（That is the big frame part of semicircular）1 and radius it is small
Semicircular ring widget（That is the little framework part of semicircular）2, the big part 1 of semicircular ring and semicircular ring widget 2 are between certain
Complete semi-circular shape support frame is formed by the connection of connecting portion 3 and 4 away from being axially alternately arranged.The big part 1 of semicircular ring
With the thickness of semicircular ring widget 2 and highly identical.
In the present invention, the big part 1 of semicircular ring and semicircular ring widget 2 with certain spaced apart so as to formed several half
The space of annular, such as 5,6,7,8 etc.（Reference picture 3,12 spaces are shared, but the invention is not restricted to this）.Prepare semicircular ring
Shape thermoelectric mechanism（HALF block devices）When, the previously prepared semi-circular shape thermoelectric material part with suitable dimension is placed in sky
In gap 5,6,7,8 etc., then certain thickness metallization and flow guiding electrode layer are formed in support frame outer shroud and inner ring surface.
In the present invention, two thermoelectric mechanisms with mirror symmetrical structure integrate a complete circular structure thermoelectricity device
Part, the thermoelectric element of opposite position passes through principle of connecting and connected in two thermoelectric mechanisms.
In the present invention, one of effect of support frame is to provide fundamental strength for annular thermo-electric device, and the two of effect is to make
For the partiting thermal insulation material between adjacent semi-circular shape thermoelectric element.
In the present invention, semicircle ring component 1,2 and connecting portion 3,4 four parts in support frame are made up of same material.
The material of support frame, which can be used for preparing, includes ceramics, glass, resin and nylon etc..
In the present invention,（Reference picture 4 is to Fig. 8）When semi-circular shape thermoelectric material part is placed in space, p-type and n-type half
Conductor thermoelectric material part is alternately arranged.For example, being put into p-type in gap 5, n-type is put into gap 6, p-type is put into gap 7,
N-type is put into gap 8, by that analogy.After metallization and the connection of flow guiding electrode layer, thermoelectric material part in gap 5 with
Thermoelectric material part in gap 6 connects in outer shroud position, the thermoelectric material part in gap 6 and the thermoelectric material in gap 7
Part connects in inner ring position, and the thermoelectric material part in gap 7 connects with the thermoelectric material part in gap 8 in outer shroud position
Connect, by that analogy.
In the present invention,（Reference picture 5）In each support frame, the height m2 of the big part 1 of semicircular ring and semicircular ring widget 2 takes
Certainly in the hot property of support frame material and the temperature in use of device.The thickness m1 of support frame depends on the annular thermoelectricity of design
The thickness of material components.The radius of the big part 1 of semicircular ring and semicircular ring widget 2 depends on the radius of thermoelectric material part, and
The outer ring surface of the big part 1 of semicircular ring and semicircular ring widget 2（Or inner ring surface）Radial difference depends on the metallization of design and led
Flow the thickness m5 of electrode layer.The gap width m3 and m4 of support frame depend on the height of annular thermoelectric material part, Ke Yixiang
Deng can also be unequal.Difference according to p-type and n-type pyroelectric material performance is so as to designing the p-type and n-type with different height
During annular material part, then correspondingly support frame adjacent segment width m3 and m4 are unequal.
In the present invention, the annular thermo-electric device of two kinds of structures can be formed using Fig. 1 and Fig. 2 support frame：A type devices
Structure and Type B device architecture.
In A type device architectures,（Reference picture 6 is to Fig. 8）Semicircular ring is big（It is small）Component thickness m1=annular thermoelectric material part is thick
Degree+metallization and flow guiding electrode thickness degree.The characteristic feature of this class formation is exactly the metallization of annular thermoelectric material part and led
Stream electrode connecting portion position is located at the external annular surface and inner ring surface of annular material part.
In Type B device architecture,（Reference picture 9 is to Figure 12）Annular thermoelectric material component thickness=semicircular ring is big（It is small）Part is thick
Spend m1+metal layer and flow guiding electrode thickness degree.The characteristic feature of this class formation is exactly the metallization of annular thermoelectric material part
It is located at the side of annular material part and close to annular material part external annular surface and inner ring surface with flow guiding electrode connecting portion.
In other embodiments of the present invention, the radial cross-sectional shape of semicircular ring support frame is not semicircle, and can be with
It is rectangular half, the half of hexagon or half elliptic etc..
Another aspect of the present invention, there is provided a kind of preparation method of annular-structure thermo-electric device, including：Manufacture semicircular
Thermoelectric material part and support frame, the thermoelectric material part is embedded in the support frame；In the insertion thermoelectric material
The inner and outer ring surface spraying metallization of the support frame of part and flow guiding electrode layer, and be ground to form semicircular
Thermoelectric mechanism；The thermoelectric mechanism of two symmetrical semicirculars of minute surface is spliced into complete annular-structure thermo-electric device.
Specifically, in the embodiment of the present invention, when preparing above-mentioned thermoelectric mechanism, can carry out according to the following steps：
The first step, the requirement according to the performance of thermoelectric material, support frame material property and device manufacture and design thermoelectric material portion
Part and support frame；Second step, one layer is formed using support frame external annular surface of the spraying technology in embedded thermoelectric material part
Or multiple-layer metallization layer and flow guiding electrode layer 10；3rd step, the support frame that external annular surface has been sprayed turn over, and pass through spraying
Technology carries out forming one layer or multiple-layer metallization layer and flow guiding electrode layer 11 in its inner ring surface；4th step, by inner and outer ring table
Face is coated with metal layer and the support frame of flow guiding electrode layer is ground with polisher lapper, is milled to its external annular surface just
The big part 1 of semicircular ring can completely be appeared, and inner ring surface can just completely appear semicircular ring widget 2；5th step, by two
The individual thermoelectric mechanism with mirror symmetrical structure is spliced into a complete annular-structure thermo-electric device, during splicing, positioned at same
The two semicircular ring material element of axial location point is according to series connection principle connection；6th, glued on interior anchor ring and cylindrical anchor ring
The insulation high-temperature-resistant of one layer of micron dimension thickness of knot and the layer material with certain corrosion resistance.
In the yet another aspect of the present invention, second step is the carriage in embedded thermoelectric material part using spraying technology
Frame inner ring surface forms one or more layers metal layer and flow guiding electrode layer 11；3rd step is the support for having sprayed inner ring surface
Framework turns over, and carries out forming one layer or multiple-layer metallization layer and flow guiding electrode layer in its external annular surface by spraying technology
10。
In the present invention, spraying technology may include flame-spraying, plasma spray coating, electric arc spraying, sensing heating spraying, electricity
Quick-fried spraying, laser spraying etc..
Annular-structure thermo-electric device of the present invention and preparation method thereof is further illustrated below by way of specific embodiment.
Embodiment 1
The present embodiment is to prepare annular bismuth telluride thermoelectric element and thermo-electric device according to the performance design of bismuth telluride material.This
The temperature in use of annular thermo-electric device is hot junction~523K, cold end~300K.
The bismuth telluride material used is (Bi2Te3)0.90(Sb2Te3)0.05(Sb2Se3)0.05（n-type）(Bi2Te3)0.25
(Sb2Te3)0.72(Sb2Se3)0.03（p-type）.Metallization and flow guiding electrode layer are double-layer structure, and internal layer is Mo layers, outer layer Al
Layer.
P-type and the structure of n-type semi-circular shape thermoelectric material part are as shown in figure 12.Wherein, outer shroud radius r2 is 8 mm, interior
Ring radius r1 is 5 mm, is highly 2 mm, and annular both ends of the surface clip the mm length of d=1.2.The metal of inner ring surface and external annular surface
Change and flow guiding electrode thickness degree m5 is 1 mm.
Using A type device architectures.Resin branch is prepared according to the size design of the bismuth telluride semi-circular shape material components of design
Support frame frame.Support frame can accommodate 6 pairs of semi-circular shape Bismuth Telluride elements.The big outer shroud radius of part 1 of semicircular ring is 9 mm, and inner ring is partly
Footpath is 5 mm, and the outer shroud radius of semicircular ring widget 2 is 8 mm, and inner ring radius is 4 mm.Semicircular ring is big（It is small）Component height m2
For 1 mm.Support frame gap width m3 and m4 are 2 mm.The thickness m6 of support frame parts 3 and 4 is 1.2 mm.
6 pairs of p-types for processing size and n-type semi-circular shape bismuth telluride material components are pre-processed.First surface is carried out
Blasting treatment, make its surface that there is certain roughness, to strengthen its adhesion between side metallization.Blasting treatment
During, blasting pressure can be 0.1 MPa, and blast time can be 30 seconds.
After the completion of blasting treatment, bismuth telluride material components are cleaned by ultrasonic to remove surface impurity.It is cleaned by ultrasonic institute
It is absolute ethyl alcohol with solvent, the time of ultrasonic cleaning is 2 minutes.
By the A types device architecture of design the p-type pre-processed and n are put into previously prepared semi-circular shape resinous framework
Type bismuth telluride material components.
Resinous framework external annular surface is faced to the nozzle of electric arc spraying equipment, in external annular surface successively Mo layers and Al in spraying
Layer.Mo layers thickness control is at 300~500 μm, and Al layers thickness control is at 600~800 μm.
The semi-circular shape support frame that external annular surface has sprayed is turned over, makes spray of its inner ring surface towards electric arc spraying
Mouth, one layer of Mo layer and Al layers are successively formed in inner ring surface using identical technological parameter.
The thermoelectric mechanism that inner and outer ring surface spraying there are AlMo layers is ground with polisher lapper, is milled in thermoelectric mechanism
External annular surface can just completely appear the big part 1 of semicircular ring, and inner ring surface can just completely appear semicircular ring widget
2。
Second bismuth telluride device is prepared according to technological parameter as before.Device architecture is still A type structures, still
P-type part n-type part is put into order in support frame gap and first bismuth telluride device on the contrary, i.e. first in material components
Individual bismuth telluride device and second bismuth telluride device have mirror symmetrical structure.
Two semi-circular shape bismuth telluride thermo-electric devices prepared by priority are spliced into a complete annular thermo-electric device.Spell
When connecing, the two semicircular ring material element positioned at same axial location point is according to series connection principle connection.The resistance to height in external annular surface both ends
Warm Teflon cloth is fixed.
In annular thermo-electric device both ends correct position welding current output end.
The insulation high-temperature-resistant of one layer of micron dimension thickness is bonded on interior anchor ring and cylindrical anchor ring and there is certain corrosion resistant
The layer material of erosion ability.
Embodiment 2
The present embodiment is to prepare annular skutterudite thermoelectric element and thermo-electric device according to the performance design of skutterudite material.This
The temperature in use of annular thermo-electric device is hot junction~823K, cold end~300K.
The skutterudite material used is Yb0.3Co4Sb12（n-type）And Ce0.9Fe4Sb12（p-type）.Metallization and water conservancy diversion
Electrode layer is double-layer structure, and internal layer is Mo layers, outer layer Cu0.5Mo0.5Mixed layer.
P-type and the structure of n-type semi-circular shape thermoelectric material part are as shown in figure 12.Wherein, outer shroud radius r2 is 10 mm,
Inner ring radius r1 is 5 mm, and annular both ends of the surface clip the mm length of d=1.5.The height of n-type material part is 3 mm, p-type material portion
The height of part is 3.5 mm.The metallization of inner ring surface and external annular surface and flow guiding electrode thickness degree m5 are 1 mm.
Using Type B device architecture.Cordierite is prepared according to the size design of the skutterudite semi-circular shape material components of design
Support frame.Support frame can accommodate 6 pairs of semi-circular shape skutterudite elements.The big outer shroud radius of part 1 of semicircular ring is 10 mm, interior
Ring radius is 6 mm, and the outer shroud radius of semicircular ring widget 2 is 9 mm, and inner ring radius is 5 mm.Semicircular ring is big（It is small）Component height
M2 is 1.5 mm.Support frame gap width m3 and m4 are 3 mm and 3.5 mm.The thickness m6 of support frame parts 3 and 4 is 1.5
mm。
6 pairs of p-types for processing size and n-type semi-circular shape skutterudite material components are pre-processed.First surface is carried out
Blasting treatment, make its surface that there is certain roughness, to strengthen its adhesion between side metallization.Blasting treatment
During, blasting pressure can be 0.1 MPa, and blast time can be 30 seconds.
After the completion of blasting treatment, bismuth telluride material components are cleaned by ultrasonic to remove surface impurity.It is cleaned by ultrasonic institute
It is absolute ethyl alcohol with solvent, the time of ultrasonic cleaning is 2 minutes.
The p-type pre-processed is put into previously prepared semi-circular shape cordierite framework by the Type B device architecture of design
With n-type skutterudite material components.
Cordierite framework external annular surface is faced to the nozzle of plasma-spraying device, in external annular surface successively Mo in spraying
Layer and Cu0.5Mo0.5Mixed layer.Mo layers thickness control is at 300~500 μm, Cu0.5Mo0.5Layer thickness control is 600~800
μm。
The support frame that external annular surface has been sprayed turns over, and makes its inner ring surface towards the nozzle of plasma spray coating,
One layer of Mo layer and one layer of Cu are successively formed in inner ring surface using identical technological parameter0.5Mo0.5Mixed layer.
By inner and outer ring surface spraying have Mo Cu0.5Mo0.5The thermoelectric mechanism of layer is ground with polisher lapper, is milled to heat
External annular surface can just completely appear the big part 1 of semicircular ring in electric components, and inner ring surface can just completely appear semicircle
Ring widget 2.
Second skutterudite device is prepared according to technological parameter as before.Device architecture is still Type B structure, still
P-type part n-type part is put into order in support frame gap and first skutterudite device on the contrary, i.e. first in material components
Individual skutterudite device and second skutterudite device have mirror symmetrical structure.
Two semi-circular shape skutterudite thermoelectric devices prepared by priority are spliced into a complete annular thermo-electric device.Spell
When connecing, the two semicircular ring material element positioned at same axial location point is according to series connection principle connection.The resistance to height in external annular surface both ends
Warm glass fabric is fixed.
In ring-shaped device both ends correct position welding current output end.
The aluminium nitride ceramics pipe that a thickness is 0.5mm on outer anchor ring set（Hot junction）, one is bonded on interior anchor ring
The insulation high-temperature-resistant of layer micron dimension thickness and the layer material with certain corrosion resistance.
Claims (11)
- A kind of 1. annular-structure thermo-electric device, it is characterised in thatInclude the thermoelectric mechanism of two symmetrical semicirculars of minute surface；Each thermoelectric mechanism possesses：The support frame of semicircular,The thermoelectric element for the semicircular being arranged in the support frame；WithConnect the flow guiding electrode of the inside and outside ring surface of the thermoelectric element；Wherein, the thermoelectric element in minute surface symmetric position on the thermoelectric mechanism is connected in series.
- 2. annular-structure thermo-electric device according to claim 1, it is characterised in that each support frame includes multiple half The big frame part of ring-type and the little framework part of multiple semicirculars, the radius of the big frame part are more than the little framework portion The radius of part, and the big frame part and the little framework part are axially alternately arranged with described with certain spacing The gap of semicircular is formed between big frame part and the little framework part.
- 3. annular-structure thermo-electric device according to claim 2, it is characterised in that semicircular is set in the gap Thermoelectric material part, and metallization and flow guiding electrode layer are formed on the inside and outside ring surface of the thermoelectric material part.
- 4. annular-structure thermo-electric device according to claim 3, it is characterised in that the thermoelectric material part is with p-type and n The form that type semi-conductor thermoelectric material part is alternately arranged is set in turn in multiple gaps, and each adjacent thermoelectric material Part is connected in series by flow guiding electrode along radial direction.
- 5. annular-structure thermo-electric device according to claim 3, it is characterised in that the big frame part and the small frame The height and thickness all same of frame part.
- 6. annular-structure thermo-electric device according to claim 5, it is characterised in that the metallization and flow guiding electrode layer position In the external annular surface and inner ring surface of the thermoelectric material part, the thickness of the big frame part or the little framework part is The thickness of the thermoelectric material part and the metallization and the thickness sum of flow guiding electrode layer.
- 7. annular-structure thermo-electric device according to claim 5, it is characterised in that the metallization and flow guiding electrode layer position In the side of the thermoelectric material part and extend to the big frame part or the little framework part external annular surface or Inner ring surface, the thickness of the thermoelectric material part is the thickness of the big frame part or the little framework part and the gold The thickness sum of categoryization and flow guiding electrode layer.
- 8. according to the annular-structure thermo-electric device any one of claim 1-7, it is characterised in that the support frame by Ceramics, glass, resin or nylon are made.
- 9. according to the annular-structure thermo-electric device any one of claim 1-7, it is characterised in that the support frame Radial section is formed as semi-annular shape, en ring-type, semi-hexagon shape ring-type or semiellipse ring-type.
- 10. annular-structure thermo-electric device according to claim 8, it is characterised in that the radial section of the support frame Be formed as semi-annular shape, en ring-type, semi-hexagon shape ring-type or semiellipse ring-type.
- A kind of 11. preparation method of annular-structure thermo-electric device, it is characterised in that including：The thermoelectric material part and support frame of semicircular are manufactured, the thermoelectric material part is embedded in the support frame；The metallization of inner and outer ring surface spraying and flow guiding electrode layer in the support frame of the insertion thermoelectric material part, and It is ground to form the thermoelectric mechanism of semicircular；The thermoelectric mechanism of two symmetrical semicirculars of minute surface is spliced into complete annular-structure thermo-electric device.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101409324A (en) * | 2008-07-24 | 2009-04-15 | 中国科学院上海硅酸盐研究所 | Bismuth-telluride-based thermoelectric electrification device and manufacturing method thereof |
| CN201523027U (en) * | 2009-11-10 | 2010-07-07 | 上海申和热磁电子有限公司 | Thermoelectric element location and electrical insulation frame |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20100229911A1 (en) * | 2008-12-19 | 2010-09-16 | Hi-Z Technology Inc. | High temperature, high efficiency thermoelectric module |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101409324A (en) * | 2008-07-24 | 2009-04-15 | 中国科学院上海硅酸盐研究所 | Bismuth-telluride-based thermoelectric electrification device and manufacturing method thereof |
| CN201523027U (en) * | 2009-11-10 | 2010-07-07 | 上海申和热磁电子有限公司 | Thermoelectric element location and electrical insulation frame |
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