CN110429172A - A kind of thermo-electric device and preparation method thereof - Google Patents
A kind of thermo-electric device and preparation method thereof Download PDFInfo
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- CN110429172A CN110429172A CN201910646400.2A CN201910646400A CN110429172A CN 110429172 A CN110429172 A CN 110429172A CN 201910646400 A CN201910646400 A CN 201910646400A CN 110429172 A CN110429172 A CN 110429172A
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- H—ELECTRICITY
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- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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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
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
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- H—ELECTRICITY
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Abstract
The present invention provides a kind of thermo-electric devices and preparation method thereof, can be realized temperature end flow deflector and directly contact with heat source.Thermo-electric device of the invention includes that cold end is covered with the insulating heat-conductive ceramic substrate of metal layer and at least one thermoelectricity pair being fixed on the insulating heat-conductive ceramic substrate；The thermoelectricity is to including: N-shaped thermoelectric element, p-type thermoelectric element and temperature end flow deflector, wherein the temperature end flow deflector is double-layer structure, the thermally conductive layer including directly contacting with the temperature end of N-shaped thermoelectric element, p-type thermoelectric element and the thermal insulation layer on the thermally conductive layer.
Description
Technical field
The present invention relates to a kind of thermo-electric devices and preparation method thereof, belong to thermoelectric material and device arts.
Background technique
The thermoelectric material hot and cold side temperature difference can be directly changed into electric energy using the Seebeck effect of thermoelectric material.Based on the original
The Thermoelectric Generator structure of reason is simple, compact layout, no rotation/transmission parts and work liquid, can long-term static work, In
Deep space exploration, special power supply and remaining waste-heat power generation field have broad application prospects.
The thermoelectricity capability of material indicates that high ZT peak value is the primary mesh of thermoelectric material research with dimensionless thermoelectric figure of merit ZT
Mark.ZT value usually varies with temperature, and is based on the corresponding temperature of ZT peak value, at present can the thermoelectric material system of practical application mainly have
Bi-Te(20~300 DEG C suitable for low-temperature space), the CoSb suitable for middle warm area3Base filled skutterudite (SKD, 400~600
DEG C), Pb-Te(400~800 DEG C), Half-Heusler(400~800 DEG C) and suitable for high-temperature region Si-Ge(600~
1000 DEG C) and oxide (600~1000 DEG C) etc..
When practical application, need to metallize thermoelectric material both ends of the surface, constitute thermoelectric element to be thermally connected needed for realizing and
Electrical connection.The basic function component of thermo-electric device is thermoelectricity pair, a typical π type thermoelectricity to by a N-shaped thermoelectric element and
One p-type thermoelectric element is arranged in parallel, and is formed by connecting in temperature end by flow deflector.Integrate a certain number of thermoelectricity to
Obtain thermo-electric device.In actual use, the thermoelectric element in thermo-electric device is usually fixed in a manner of electrically coupled in series and hot parallel connection
Between heat source and cold source.Cooling and Heat Source can be the diversified forms such as solid-state, liquid or gaseous state, but in the majority with solid-state.Therefore usual feelings
There is solid affixed touching under condition between Cooling and Heat Source and thermo-electric device low temperature and temperature end.It is usually led by electrically and thermally good on Cooling and Heat Source surface
Body, as nickel, copper, stainless steel and other metal materials are constituted.
Thermo-electric device integrates, i.e., the fixation and connection of multiple thermoelectricity pair are generally completed in low-temperature end.Support is covered with specific
The insulating heat-conductive ceramic substrate of metal pathway can be by the low temperature of different thermoelectricity pair by the low-temperature weldings technique such as simple soldering
End is fixed on insulating heat-conductive ceramic substrate, and required circuit connection is established between different thermoelectricity pair.
Thermo-electric device temperature end is there are mainly two types of structure at present, one is using thermoelectricity to flow deflector as thermo-electric device high temperature
End, second similar with low temperature end structure, i.e., is integrally connected thermoelectricity to flow deflector and metallized ceramic substrate by welding
It connects.
For the first structure, thermoelectricity is the metal simple-substance or alloy of single layer structure to temperature end flow deflector at present, this
Kind of flow deflector is in the direction (direction for being parallel to heat source Yu flow deflector contact surface) perpendicular to hot-fluid and is parallel to the direction of hot-fluid
Do not have insulation function on (perpendicular to the direction of heat source and flow deflector contact surface).When flow deflector and conductive heat source surface are straight
When contact, it will be shorted between different thermoelectricity pair.Therefore it when installing thermo-electric device, needs in thermoelectricity to flow deflector and heat source
Insulating heat-conductive ceramic substrate is additionally inserted between surface, is shorted to avoid between different flow deflectors by heat source surface.Often at present
Insulating heat-conductive ceramic substrate is Al2O3And AlN, thickness are generally not less than 100 μm.
Following problems will be brought to insulating heat-conductive ceramic substrate is inserted between flow deflector and heat source in thermoelectricity: 1. costs improve
(especially AlN substrate price is higher), simultaneity factor weight increase.2. additionally introducing two contact interfaces, i.e. heat source and ceramic base
Interface and ceramic substrate and thermoelectricity between plate is to the interface between flow deflector.Since above-mentioned interface is only able to achieve mechanical connection, no
It is able to achieve welded connecting, therefore interface contact heat resistance is big, this becomes an important factor for influencing thermo-electric device output performance.Its reason
It is that ceramic substrate material has excellent high-temperature stability and chemical inertness, under the limiting temperature that thermoelectric material is resistant to, according to
It is difficult to make to pass through between ceramic substrate and corresponding contact material (heat source surface or thermoelectricity are to flow deflector) by conventional mechanical contact
Atom diffusion and reaction, which are realized, to be welded to connect.3. ceramic substrate thickness is larger (generally at 100 μm or more), itself bring
Thermal resistance may interfere with further increasing for thermo-electric device output performance.
Second of structure realizes thermoelectricity and is welded to connect to flow deflector and metallized ceramic substrate, and is kept away by ceramic substrate
Exempt to be shorted between different flow deflectors by heat source surface.Compared with the first structured high temperature end structure, this structure is reduced
Temperature end interface resistance, but exist simultaneously problems: 1. further improve manufacturing cost.On the one hand, it adds additional
Temperature end metallized ceramic substrate, price are more more expensive than single ceramic substrate.On the other hand, need separately to develop flow deflector with
The Joining Technology of metallized ceramic substrate.2. equally existing system weight increase, ceramic substrate thickness brings greatly extra resistance etc.
Problem.3. usually there is larger difference between ceramic substrate and temperature end flow deflector thermal expansion coefficient, temperature end integration be will lead to
Temperature end each section (including interface and material internal) stress is sharply increased, impacts to device stability.
Summary of the invention
For this status, it is an object of that present invention to provide a kind of thermo-electric devices and preparation method thereof, can be realized height
Warm end flow deflector can directly be contacted with heat source.
Thermo-electric device of the invention includes that cold end is covered with the insulating heat-conductive ceramic substrate of metal layer and is fixed on the insulation and leads
At least one thermoelectricity pair on thermal Ceramics substrate；The thermoelectricity is to including: N-shaped thermoelectric element, p-type thermoelectric element and temperature end
Flow deflector, wherein the temperature end flow deflector is double-layer structure, including straight with the temperature end of N-shaped thermoelectric element, p-type thermoelectric element
The thermally conductive layer of contact and the thermal insulation layer on the thermally conductive layer.
By improving thermoelectricity to flow deflector structure, thermo-electric device temperature end provided by the invention is without welding additional metal
Change ceramic substrate, without insulating heat-conductive ceramic substrate is separately inserted between the flow deflector and heat source of thermo-electric device, that is, can avoid
It is shorted between different temperature end flow deflectors by heat source surface, to significantly reduce temperature end additional thermal resistance, is effectively improved
The output performance of thermo-electric device, while the variation of thermo-electric device manufacturing cost is less, and device stability is unaffected.
The thermally conductive layer directly contacted with thermoelectric element temperature end can be Ni, Cu, Al, Fe, Co, Cr, Mo etc.
One or more of common metal element or its alloy.Above-mentioned is common conductive and heat-conductive layer material, is worked in electrothermal module
Temperature range has enough mechanical strengths, lesser thermal resistance and resistance, while cost is relatively low, easy to process.
The thickness of the thermally conductive layer is preferably 5~3000 μm, and more preferably 200~500 μm, to take into account conductive and heat-conductive
Mechanical strength, thermal resistance/resistance and the cost/weight of layer.
The thermal insulation layer includes but is not limited to AlN, Al2O3And Si3N4Deng the insulating materials with Thermal conductivity
One or more of.Above-mentioned is common insulating heat-conductive layer material, in the common operating temperature of thermo-electric device and Current Voltage area
It is interior that there is ideal insulation effect and lesser thermal resistance.
The thickness of thermal insulation layer on heat-conducting layer is preferably 5nm~500 μm, and more preferably 1 ~ 5 μm.Thickness is greater than
The thermal insulation layer usually can realize insulation effect when 5nm, when thickness is not more than 500 μm, the system of the thermal insulation layer
It is standby that there is feasibility.In addition, under most of use condition, on the one hand, there is thermal insulation layer adequate thickness (to be not less than 1 μ
M), it is advantageously implemented reliable insulation effect；On the other hand, thermal insulation layer is without too thick (being no more than 5 μm), to avoid interface
Stress is excessive and preparation cost is excessively high.
The present invention additionally provides a kind of preparation method of above-mentioned thermo-electric device simultaneously, specifically in above-mentioned thermoelectricity pair
The method of conductive and heat-conductive layer surface deposition thermal insulation layer.
Above-mentioned thermal insulation layer is deposited using magnetron sputtering technique, includes the following steps: thermally conductive layer carrying out surface
Processing, and be placed in sputtering chamber.Sputtering chamber is evacuated to required background vacuum.Start heating device, sputtering chamber is carried out
Whole heating.It is passed through argon gas and pre-sputtering is carried out to Al target or Si target.It is passed through oxygen or nitrogen, by adjusting argon gas and oxygen, nitrogen
The ratio of gas carries out reactive sputtering to target.
Preferably, the air pressure of sputtering chamber base vacuum is lower than 3 × 10-3Pa.Thus it can avoid being mixed into impurity in deposition film, really
Protect the insulation heat-conducting property of film.
It is 180 ~ 350 DEG C that the sputtering sedimentation incipient stage, which sputters room temperature, and keeps the temperature 15 ~ 45 min.Therefore ensure that conduction is led
Thermosphere reaches required temperature, its surface is made to have certain activity, is conducive to the combination for improving thermal insulation layer and thermally conductive layer
Intensity.
120 ~ 300 min are sputtered to Al target or Si target with the power of 150 ~ 500 W in sputter deposition process.It therefore ensures that
Thermal insulation layer has suitable deposition rate.
The argon gas of chamber and the flow-rate ratio of oxygen are passed through in sputter deposition process between 2:1 ~ 2:3, argon gas and nitrogen
Flow-rate ratio is between 2:1 ~ 2:3, and chamber pressure is between 0.1 ~ 0.8Pa.Thus the thermal insulation layer for obtaining deposition has institute
The stoicheiometry needed, it is ensured that it insulate and heating conduction.
Specifically, the thermo-electric device of an implementation form provided by the invention, thermoelectricity have bilayer to temperature end flow deflector
Structure: the side towards N-shaped and p-type thermoelectric element temperature end is thermally conductive layer, by with excellent conductivity and thermal conductivity
Material, such as Cu, Ni, Al, Fe, Mo or its composition of alloy, with a thickness of 5~3000 μm, preferred thickness is 200~500 μm.Upper
Stating on thermally conductive layer is thermal insulation layer, by the insulating materials with excellent thermal conductivity, such as AlN, Al2O3Or Si3N4Etc. groups
At with a thickness of 0.005 ~ 500 μm, preferred thickness is 1 ~ 5 μm.
The present invention deposits thermal insulation layer to flow deflector surface in thermoelectricity, and preparation method can use physical vapour deposition (PVD)
Method, such as magnetron sputtering, electric arc spraying or thermal spraying can also use chemical vapour deposition technique.
It is in the Ni piece surface depositing Al as thermoelectricity to flow deflector below by taking magnetron sputtering as an example2O3Thermal insulation layer
Preparation method: by Ni piece surface polishing, and it is cleaned by ultrasonic with alcohol, dries and be placed on sputtering chamber sample stage.Sputtering chamber is taken out true
Sky to air pressure is lower than 3 × 10-3Start heating device after Pa, whole heating is carried out to sputtering chamber, and reach 180 in sputtering room temperature
15 ~ 45 min are kept the temperature after ~ 350 DEG C.Argon gas is passed through after heat preservation, throughput is 50 ~ 200 sccm, and with 150 ~ 500 W
Dc power to 5 ~ 15 min of aluminium target pre-sputtering, be subsequently passed oxygen, throughput is 30 ~ 200 sccm, and chamber pressure is
0.1 ~ 0.8 Pa sputters 120 ~ 300 min to aluminium target with the dc power of 150 ~ 500 W by adjusting argon gas and oxygen proportion.
Finally deposit to obtain the Al of insulating heat-conductive on Ni piece surface2O3Coating.Thermoelectricity for depositing coating is to water conservancy diversion sheet material, ruler
The very little final size that can be flow deflector, after the completion of deposition can by subsequent technique with N-type and p-type thermoelectric element are integrated obtains
Corresponding thermoelectricity pair；It is also possible to big sheet, to obtain multiple final sizes by suitably cutting means after deposition is complete
Flow deflector.It using magnetron sputtering, is had the advantages that relative to other sedimentations: firstly, magnetron sputtering is laboratory and work
Common film deposition equipment, acquisition cost can receive in industry production；Secondly, the film deposition rate of magnetron sputtering is suitble to use
In preparing micron-sized Al2O3, AlN or Si3N4Equal thermal insulation layers, preparation cost can also receive；Again, it is splashed by magnetic control
The optimization of technological parameter is penetrated, it can be achieved that Al2O3, AlN or Si3N4Equal thermal insulation layers stablize preparation.
(thermally conductive layer+thermal insulation layer) is designed by the double-layer structure of temperature end flow deflector, heat provided by the invention
Electrical part has a clear superiority compared with existing thermo-electric device:
1. reducing device preparation cost and system weight, while simplifying device architecture, be conducive to device reliability into one
Step improves.This is because by thermal insulation layer, without welding additional metallized ceramic substrate on the flow deflector of temperature end,
Without being separately inserted into insulating heat-conductive ceramic substrate between flow deflector and heat source, thermo-electric device temperature end flow deflector and heat can be realized
The direct contact in source；
2. reducing interface resistance, is conducive to device and obtains more high output performance.This is because by magnetron sputtering, ion plating or
Thermal insulation layer is deposited on conductive and heat-conductive layer surface by the method for manufacturing thin film such as spraying, can realize close connection between the two,
Achieve the effect that similar welding contact.Compared with the situation for being separately inserted into insulating heat-conductive ceramic substrate between flow deflector and heat source,
The former interface contact heat resistance substantially reduces, and thus can effectively reduce temperature end temperature difference loss, improves device output performance；With lead
Additional metallized ceramic substrate (thickness is usually at 100 μm or more) is welded in flow to compare, and passes through currently used film system
Standby technique, (preferred thickness is 1 ~ 5 μm) can be greatly reduced in thermal insulation layer thickness of the present invention, and temperature end is not necessarily to solder
Layer, therefore the temperature end thermal resistance introduced by thermal insulation layer and solder layer itself can be further decreased, this is equally beneficial for device
The further improvement of output performance；
3. compared with the situation for welding additional metallized ceramic substrate on flow deflector, thermo-electric device temperature end provided by the invention
Stress is smaller, is conducive to the improvement of device reliability.This is because the thermal expansion coefficient of metallized ceramic substrate is substantially less than normal
The temperature ends water conservancy diversion sheet material such as Cu, Ni, Al.The metallized ceramic substrate of hundred micron thickness as a whole, with thermo-electric device
Temperature end flow deflector will introduce a large amount of thermal stress at interface and respective material region when integrally molded, seriously affect the structure of device
Stability.And thermal insulation layer thickness of the present invention is only micron order, and is not intended as whole appearance in thermo-electric device, and
It is dispersed on the thermally conductive layer of mutually independent each thermoelectricity pair, therefore caused by the deposition of above-mentioned thermal insulation layer
Thermal stress varies less, the also very little of the influence to device architecture stability.
Detailed description of the invention
Fig. 1 is contained heat in a kind of thermo-electric device that temperature end directly can be contacted and be electrically insulated with heat source provided by the invention
The structural schematic diagram of electricity pair；
Fig. 2 is to be deposited on Mo-Cu flow deflector in the preparation method using an implementation form of the invention using magnetically controlled sputter method
Al2O3The stereoscan photograph of coating；
Fig. 3 is the output performance of device A and device B at a temperature of different temperature ends in embodiment 1.Wherein, (a) current-voltage
Curve；(b) current versus output power curve；(c) electric current-conversion efficiency curve；
Fig. 4 is the output performance of device C and device D at a temperature of different temperature ends in embodiment 2.Wherein, (a) current-voltage
Curve；(b) current versus output power curve；(c) electric current-conversion efficiency curve.
Appended drawing reference:
1:n type thermoelectric element；
2:p type thermoelectric element；
3: thermally conductive layer；
4: thermal insulation layer.
Specific embodiment
The present invention is further illustrated below by way of specific embodiment, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
A kind of thermo-electric device that temperature end flow deflector can directly be contacted with heat source, the insulation for being covered with metal layer including cold end are led
Thermal Ceramics substrate and fixed at least one thermoelectricity pair on the substrate, Fig. 1 show the structural schematic diagram of thermoelectricity pair.Thermoelectricity pair
Including 1, p-type thermoelectric element 2 of a N-shaped thermoelectric element and one piece of temperature end flow deflector.The temperature end flow deflector is
Double-layer structure, including the thermally conductive layer 3 that is directly contacted with thermoelectric element temperature end and exhausted on thermally conductive layer
Edge heat-conducting layer 4.That is, thermally conductive layer 3, thermal insulation layer 4 are respectively positioned on the temperature end of thermoelectricity pair.
(thermally conductive layer 3+ thermal insulation layer 4) is designed by the double-layer structure of temperature end flow deflector, it is provided by the invention
Thermo-electric device has a clear superiority compared with existing thermo-electric device: by thermal insulation layer 4, without another between flow deflector and heat source
Row insertion insulating heat-conductive ceramic substrate can be realized thermo-electric device temperature end flow deflector and contact with the direct of heat source, therefore reduces
Device preparation cost and system weight, while device architecture is simplified, be conducive to further increasing for device reliability.
Further, which is the sedimentary for being deposited on thermally conductive layer.Interface resistance is reduced as a result,
Be conducive to device and obtain more high output performance.This is because the common film such as magnetron sputtering, ion plating or spraying can be passed through
Thermal insulation layer 4 is deposited on 3 surface of thermally conductive layer by preparation method, can be realized close connection between the two, be reached similar
Weld the effect of contact.Compared with the situation for being separately inserted into insulating heat-conductive ceramic substrate between flow deflector and heat source, the former boundary
Face contact thermal resistance substantially reduces, and thus can effectively reduce temperature end temperature difference loss, improves device output performance.
Embodiment 1
Being sintered diameter respectively by one-step method sintering process is 50 mm, and with a thickness of 8 mm, both ends all have barrier layer and electrode
N-shaped and p-type filled skutterudite sample, structure are respectively Ni/Ti-Al/Yb0.3Co4Sb12/ Ti-Al/Ni and Ni/Ti-Al/
CeFe4Sb12/ Ti-Al/Ni, wherein Ni is electrode, and about 120 μm of thickness, Ti-Al is barrier layer, about 100 μm of thickness.Wire cutting
Corresponding thermoelectric element is obtained, having a size of 4 × 4 × 8 mm3.Then by soldering processes, by Cu-Ag solder, in vacuum chamber
By the temperature end of single N-shaped thermoelectric element and single p-type thermoelectric element respectively and having a size of 5 × 12 × 0.5 mm in room3 Mo-
The connection of Cu guide layer, obtains corresponding π type thermoelectricity pair.
Design is by 8 thermoelectricity to the envelope being composed in series having a size of 30 × 30 × 9.3 mm3Thermo-electric device, thereby determine that
Thermo-electric device low-temperature end circuit connecting mode, and select accordingly with a thickness of the deposited copper Al of 0.6 mm2O3Ceramic substrate.
8 thermoelectricity pair are taken out at random, are thrown using Mo-Cu water conservancy diversion layer surface of the 5000# sand paper to above-mentioned π type thermoelectricity pair
Light, then ultrasonic cleaning obtains clean surface in dehydrated alcohol, after natural drying by above-mentioned thermoelectricity to being placed in sputtering chamber sample
On product pedestal, and make Mo-Cu water conservancy diversion layer surface in face of sputtering target material.Chamber evacuation to background vacuum reaches 8*10-4 Pa, after
Continuous pumping, starts simultaneously at heating, and keep the temperature half an hour after temperature reaches 250 DEG C.Then pass to high-purity Ar, flow velocity 80
Sccm sputters 10 min of Al target with the dc power of 200 W, is then passed through high-purity Ar and high-purity O simultaneously2, flow velocity is respectively 60
Sccm and 80 sccm, chamber pressure are 0.6 Pa, 180 min of Al target are sputtered with 200 W power, on Mo-Cu flow deflector surface
Deposit the Al of insulating heat-conductive2O3Layer.Finally terminate whole preparation process.Sample furnace cooling, chamber temp are opened after being lower than 50 DEG C
Sample is taken out in cabin.
The cold end of above-mentioned thermoelectricity pair and deposited copper ceramic substrate dehydrated alcohol are cleaned by ultrasonic and are dried.
Deposited copper ceramic base plate surface is placed on heating platform, applies copper face upward.In substrate copper-clad (300 μm of thickness) table
Face, which corresponds at the position of N-shaped thermoelectric element and p-type thermoelectric element low-temperature end, places having a size of 4 × 4 × 0.2 mm3Sn foil,
Thermoelectric element low-temperature end is placed on corresponding Sn foil, 0.3 MPa pressure is applied to thermoelectric element low-temperature end and is kept.It opens and adds
Hot platform makes it be to slowly warm up to 260 DEG C, keeps the temperature 5min.It is then shut off heating platform, platform surface temperature to be heated is down to 50
DEG C when remove low temperature end pressure, obtain by 8 pairs of π type thermoelectricity to the temperature end being composed in series have thermal insulation layer thermoelectricity device
Part is indicated with device A.
As a comparison, then at random 8 thermoelectricity pair are taken out, its cold end and deposited copper ceramic substrate are cleaned by ultrasonic with dehydrated alcohol
And it dries.Thermoelectricity is then fixed on deposited copper ceramic substrate (process flow and the same device of parameter by soldering process to cold end
A), corresponding thermo-electric device is obtained, is indicated with device B.
Device A thermoelectricity is tested to the surface insulation performance of temperature end flow deflector with multimeter first, is tested in positive and negative anodes
The temperature end flow deflector surface that 8 thermoelectricity pair are measured in the case of 5 mm of needle spacing, 100 V of voltage remains electrically isolated from state.
The room temperature internal resistance of device is then tested, it is found that the room temperature internal resistance of device A and device B is essentially identical, is respectively
40.5 m Ω and 40.4 m Ω show that the quality of above-mentioned thermo-electric device has good consistency.
Device A and device B are then placed in by the hot persistence testing platform vacuum chamber of thermo-electric device by machanical fastener respectively
In room.The low-temperature end of device A applies copper ceramic substrate and is close to test platform low-temperature end Cu electrode, temperature end thermal insulation layer and test
Platform temperature end Ni heating electrode directly contacts.The low-temperature end of device B applies copper ceramic substrate and is close to test platform low-temperature end Cu electricity
Pole, the Al that temperature end thermally conductive layer is close to a thickness of 200 μm2O3Insulating heat-conductive ceramic substrate, the ceramic substrate other side are tight
It pastes test platform temperature end Ni and heats electrode.The pressure that the temperature end flow deflector of thermo-electric device A and B are born in test process is equal
For 5MPa.
Thermo-electric device after the installation is completed vacuumizes test chamber, and temperature end heating is opened when chamber pressure is lower than 2 Pa
Switch and low-temperature end cooling water switch, temperature end Ni heating electrode temperature reaches 350 DEG C after 4 hours.When test platform high/low temperature
Termination electrode temperature is stable in 350 DEG C and 35 DEG C respectively, and chamber pressure stabilization keeps above-mentioned 20 min of state after 5Pa, surveys later
Try thermo-electric device output performance.It is completed rear low-temperature end and is kept for 35 DEG C, temperature end continues slowly heating, is reaching 400 respectively
DEG C, 450 DEG C, 500 DEG C and at 550 DEG C, chamber pressure is stablized in 5Pa, and keep above-mentioned 20 min of state, then test is corresponding
Thermo-electric device output performance at temperature spot.
Test result is as shown such as (a)-(c) in Fig. 3, when discovery high/low temperature termination electrode temperature is respectively 550 DEG C and 35 DEG C, device
Part A open-circuit voltage is 1.099 V, compared with device B(1.045 V) promote 5.6%；Device A peak power output is 3.81 V, compared with
Device B(3.45 V) promote 6.8%；Device A maximum conversion efficiency is 7.63%, promotes 4.5% compared with device B(7.30%).Such as preceding institute
It states, the main reason is that device B relative device A reduces the additional thermal resistance of temperature end, thus under equal conditions, present invention heat
The output power of electrical part A has compared with the output performance of the thermo-electric device B of traditional structure to be obviously improved.
Embodiment 2
Being sintered diameter respectively by one-step method sintering process is 50 mm, and with a thickness of 8 mm, both ends all have barrier layer and electrode
N-shaped and p-type filled skutterudite sample, structure are respectively Ni/Ti-Al/Yb0.3Co4Sb12/ Ti-Al/Ni and Ni/Ti-Al/
CeFe3CoSb12/ Ti-Al/Ni, wherein Ni is electrode, and about 120 μm of thickness, Ti-Al is barrier layer, about 100 μm of thickness.Line is cut
It cuts to obtain corresponding thermoelectric element, having a size of 4 × 4 × 8 mm3.Then by soldering processes in vacuum chamber, by Cu-Ag
Solder, by the temperature end of single N-shaped thermoelectric element and single p-type thermoelectric element respectively and having a size of 5 × 12 × 0.5 mm3 's
The connection of Mo-Cu guide layer, obtains corresponding π type thermoelectricity pair.
Design is by 8 thermoelectricity to the envelope being composed in series having a size of 30 × 30 × 9.3 mm3Thermo-electric device, thereby determine that
Thermo-electric device temperature end and low-temperature end circuit connecting mode, and select to apply accordingly with a thickness of the temperature end and low-temperature end of 0.6 mm
Copper Al2O3Ceramic substrate.
8 thermoelectricity pair are taken out at random, are thrown using Mo-Cu water conservancy diversion layer surface of the 5000# sand paper to above-mentioned π type thermoelectricity pair
Light, then ultrasonic cleaning obtains clean surface in dehydrated alcohol, after natural drying by above-mentioned thermoelectricity to being placed in sputtering chamber sample
On product pedestal, and make Mo-Cu water conservancy diversion layer surface in face of sputtering target material.Chamber evacuation to background vacuum reaches 8*10-4 Pa, after
Continuous pumping, starts simultaneously at heating, and keep the temperature half an hour after temperature reaches 250 DEG C.Then pass to high-purity Ar, flow velocity 80
Sccm sputters 10 min of Al target with the dc power of 200 W, is then passed through high-purity Ar and high-purity O simultaneously2, flow velocity is respectively 60
Sccm and 80 sccm, chamber pressure are 0.6 Pa, 180 min of Al target are sputtered with 200 W power, on Mo-Cu flow deflector surface
Deposit the Al of insulating heat-conductive2O3Layer.Finally terminate whole preparation process.Sample furnace cooling, chamber temp are opened after being lower than 50 DEG C
Sample is taken out in cabin.
The cold end of above-mentioned thermoelectricity pair and deposited copper ceramic substrate dehydrated alcohol are cleaned by ultrasonic and are dried.
Deposited copper ceramic base plate surface is placed on heating platform, applies copper face upward.In substrate copper-clad (300 μm of thickness) table
Face, which corresponds at the position of N-shaped thermoelectric element and p-type thermoelectric element low-temperature end, places having a size of 4 × 4 × 0.2 mm3Sn foil,
Thermoelectric element low-temperature end is placed on corresponding Sn foil, 0.3 MPa pressure is applied to thermoelectric element low-temperature end and is kept.It opens and adds
Hot platform makes it be to slowly warm up to 260 DEG C, keeps the temperature 5min.It is then shut off heating platform, platform surface temperature to be heated is down to 50
DEG C when remove low temperature end pressure, obtain by 8 pairs of π type thermoelectricity to the temperature end being composed in series have thermal insulation layer thermoelectricity device
Part is indicated with device C.
As a comparison, then at random 8 thermoelectricity pair are taken out, using 5000# sand paper to the Mo-Cu guide layer table of above-mentioned thermoelectricity pair
Face is polished, and itself and the deposited copper ceramic base plate surface dehydrated alcohol of temperature end are cleaned by ultrasonic and are dried.Then in vacuum
By soldering processes in chamber, by Cu-Ag solder, the temperature end flow deflector of 8 thermoelectricity pair and temperature end are applied into copper ceramic base
Plate carries out integrated connection by designed thermo-electric device temperature end connection type.Thermoelectricity is then applied into copper pottery to cold end and low-temperature end
Porcelain substrate dehydrated alcohol is cleaned by ultrasonic and dries, and thermoelectricity is fixed on low-temperature end by soldering process to cold end and applies copper ceramics
(process flow and parameter are obtained corresponding thermo-electric device, are indicated with device D with device A) on substrate.
Device C thermoelectricity is tested to the surface insulation performance of temperature end flow deflector with multimeter first, is tested in positive and negative anodes
The temperature end flow deflector surface that 8 thermoelectricity pair are measured in the case of 5 mm of needle spacing, 100 V of voltage remains electrically isolated from state.
The room temperature internal resistance of device is then tested, it is found that the room temperature internal resistance of device C and device D is essentially identical, is respectively
37.8 m Ω and 37.7 m Ω show that the quality of above-mentioned thermo-electric device has good consistency.
Device C and device D are then placed in by the hot persistence testing platform vacuum chamber of thermo-electric device by machanical fastener respectively
In room.The low-temperature end ceramic substrate of device C is close to test platform low-temperature end Cu electrode, temperature end thermal insulation layer and test platform
Temperature end Ni heating electrode directly contacts.The low-temperature end of device D applies copper ceramic substrate and is close to test platform low-temperature end Cu electrode, high
Warm end applies copper ceramic substrate and is close to test platform temperature end Ni heating electrode.The temperature end of thermo-electric device C and D are led in test process
The pressure that flow is born is 5MPa.
Thermo-electric device after the installation is completed vacuumizes test chamber, and temperature end heating is opened when chamber pressure is lower than 2 Pa
Switch and low-temperature end cooling water switch, temperature end Ni heating electrode temperature reaches 350 DEG C after 4 hours.When test platform high/low temperature
Termination electrode temperature is stable in 350 DEG C and 35 DEG C respectively, and chamber pressure stabilization keeps above-mentioned 20 min of state after 5Pa, surveys later
Try thermo-electric device output performance.It is completed rear low-temperature end and is kept for 35 DEG C, temperature end continues slowly heating, is reaching 400 respectively
DEG C, 450 DEG C, 500 DEG C and at 550 DEG C, chamber pressure is stablized in 5Pa, and keep above-mentioned 20 min of state, then test is corresponding
Thermo-electric device output performance at temperature spot.
Test result is as shown such as (a)-(c) in Fig. 4, when discovery high/low temperature termination electrode temperature is respectively 550 DEG C and 35 DEG C, device
The open-circuit voltage (1.168 V:1.167 V) of part C and device D, peak power output (4.305 W:4.299 W), maximum conversion
Efficiency is substantially quite (8.048%:8.041%).In view of device C-structure is simple, preparation cost is low, and internal stress is small, reliability
Height, therefore still have a clear superiority compared with Conventional thermoelectric device D.
The thermo-electric device and preparation method thereof that temperature end flow deflector provided by the invention can directly be contacted with heat source, by changing
Into thermoelectricity to temperature end flow deflector structure, a thermal insulation layer, heat provided by the invention are deposited in the thermally conductive layer surface of conventional conductive
Electrical part need to only be such that its temperature end flow deflector directly contacts with heat source when working normally, without in temperature end flow deflector and heat source
Between be inserted into additional insulating heat-conductive ceramic substrate, or in temperature end flow deflector surface separately welding metal ceramic substrate.With
It is inserted into additional insulating heat-conductive ceramic substrate between temperature end flow deflector and heat source to compare, thermo-electric device provided by the invention is significant
Temperature end additional thermal resistance is reduced, the output performance of thermo-electric device is effectively improved；It is separately welded on temperature end flow deflector surface
It connects metallized ceramic substrate to compare, thermo-electric device provided by the invention has comparable output performance, while significantly reducing system
This is caused, and the stress for avoiding higher device temperature end increases.
According to the above description, the more improvement of the present invention and other implementation forms are illustrated in those skilled in the art.Therefore, on
It states bright only as example for illustrating, is to implement optimal modality of the invention as mesh to instruct to those skilled in the art
And offer.Purport that as long as it does not depart from the spirit of the invention can substantially be changed to other structures and/or function.
Claims (10)
1. a kind of thermo-electric device, which is characterized in that
The thermo-electric device includes that cold end is covered with the insulating heat-conductive ceramic substrate of metal layer and is fixed on the insulating heat-conductive ceramic base
At least one thermoelectricity pair on plate；
The thermoelectricity is to including: N-shaped thermoelectric element, p-type thermoelectric element and temperature end flow deflector, wherein the temperature end water conservancy diversion
Piece is double-layer structure, the thermally conductive layer including directly contacting with the temperature end of N-shaped thermoelectric element, p-type thermoelectric element and position
Thermal insulation layer on the thermally conductive layer.
2. thermo-electric device according to claim 1, which is characterized in that
The thermally conductive layer is one or more of Ni, Cu, Al, Fe, Co, Cr, Mo or its alloy.
3. according to claim 1 or thermo-electric device described in 2, which is characterized in that
The thermally conductive layer with a thickness of 5 μm~3000 μm.
4. thermo-electric device described in any one of -3 according to claim 1, which is characterized in that
The thermal insulation layer includes AlN, Al2O3And Si3N4One or more of.
5. thermo-electric device described in any one of -4 according to claim 1, which is characterized in that
The thermal insulation layer with a thickness of 5nm~500 μm.
6. the preparation method of thermo-electric device described in a kind of any one of claim 1-5, which is characterized in that
Thermal insulation layer is deposited using magnetron sputtering technique, is included the following steps:
Thermally conductive layer is surface-treated, and is placed in sputtering chamber；
Sputtering chamber is evacuated to required background vacuum；
Start heating device, whole heating is carried out to sputtering chamber；
It is passed through argon gas and pre-sputtering is carried out to Al target or Si target；
It is passed through oxygen or nitrogen, by adjusting argon gas and oxygen, the ratio of nitrogen carries out reactive sputtering to target.
7. the preparation method of thermo-electric device according to claim 6, which is characterized in that
Sputtering chamber base vacuum air pressure is lower than 3 × 10-3Pa。
8. the preparation method of thermo-electric device according to claim 6, which is characterized in that
It is 180 ~ 350 DEG C that the sputtering sedimentation incipient stage, which sputters room temperature, and keeps the temperature 15 ~ 45 min.
9. the preparation method of thermo-electric device according to claim 6, which is characterized in that
120 ~ 300 min are sputtered to Al target or Si target with the power of 150 ~ 500 W in sputter deposition process.
10. the preparation method of thermo-electric device according to claim 6, which is characterized in that
The argon gas of chamber and the flow-rate ratio of oxygen are passed through in sputter deposition process between 2:1 ~ 2:3, the flow of argon gas and nitrogen
Than between 2:1 ~ 2:3, chamber pressure is between 0.1 ~ 0.8Pa.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113594343A (en) * | 2021-07-07 | 2021-11-02 | 西安交通大学 | Thermoelectric device, mold for manufacturing same, and method for manufacturing same |
| CN114497335A (en) * | 2022-01-20 | 2022-05-13 | 济南大学 | Skutterudite thermoelectric material electrode and connection method of skutterudite thermoelectric material and electrode |
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| CN103560203A (en) * | 2013-10-23 | 2014-02-05 | 合肥工业大学 | Simple and efficient film thermobattery structure and manufacturing method thereof |
| CN108550688A (en) * | 2018-05-24 | 2018-09-18 | 中国科学院上海硅酸盐研究所 | A kind of thermo-electric device with adaptive connection layer |
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| CN101894904A (en) * | 2010-07-15 | 2010-11-24 | 电子科技大学 | Metal-base film thermocouple and preparation method thereof |
| CN103560203A (en) * | 2013-10-23 | 2014-02-05 | 合肥工业大学 | Simple and efficient film thermobattery structure and manufacturing method thereof |
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| CN113594343A (en) * | 2021-07-07 | 2021-11-02 | 西安交通大学 | Thermoelectric device, mold for manufacturing same, and method for manufacturing same |
| CN114497335A (en) * | 2022-01-20 | 2022-05-13 | 济南大学 | Skutterudite thermoelectric material electrode and connection method of skutterudite thermoelectric material and electrode |
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Application publication date: 20191108 |