CN207529976U - Thermo-electric device and its electrode - Google Patents
Thermo-electric device and its electrode Download PDFInfo
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- CN207529976U CN207529976U CN201720979310.1U CN201720979310U CN207529976U CN 207529976 U CN207529976 U CN 207529976U CN 201720979310 U CN201720979310 U CN 201720979310U CN 207529976 U CN207529976 U CN 207529976U
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Abstract
The utility model discloses a kind of thermo-electric device and its electrodes.The utility model thermo-electric device electrode includes half Heusler hypothallus, solder layer and electrode layer that combination is laminated with this, is also laminated between the half Heusler hypothallus and solder layer and is combined with barrier layer, and the barrier layer is Ti-Ni alloy layer.Ti-Ni alloy layer structure contained by the utility model thermo-electric device electrode enables to have good thermal expansion matching between electrode layer and half Heusler hypothallus contact interfaces, and the thickness of diffusion layer formed between interface is small, interface contact resistance is small, and thickness of diffusion layer can be kept stablizing with the extension of active time, so that interface stability is high, so as to assign utility model thermo-electric device high conversion efficiency of thermoelectric.
Description
Technical field
The utility model belongs to technical field of thermoelectric conversion, relates particularly to a kind of thermo-electric device electrode and thermoelectricity device
Part.
Background technology
Thermoelectric power generation is that the temperature difference (thermal energy) at material both ends is converted to the complete of electric energy using semiconductor thermoelectric transition material
Static electricity-generating method is a kind of environmentally friendly green energy resource technology, current growing non-renewable for alleviating
Energy consumption pressure and pollution problem have great significance.The electricity generation system has dependable performance, compact-sized, without motion portion
Part, noiseless, No leakage, without abrasion, mobility it is strong etc. the characteristics of, suitable for the recycling of waste heat of automotive exhaust gas and industrial waste heat etc.
It utilizes.
Half-Heusler base thermoelectricity materials are the high temperatures (600~800 that one kind has excellent thermoelectricity capability (ZT~1)
One of DEG C) thermoelectric material, component has both the features such as cheap, proportion is small and environmental-friendly, is sent out suitable for high temperature thermoelectricity
The fields such as electricity and Waste Heat Recovery, research people have carried out a large amount of research to the raising of the ZT values of half-Heusler thermoelectric materials.
In recent years, phon scattering is enhanced to form nano-second-phase, using quality fluctuating or energy filtering effect by doped and substituted
To reduce thermal conductivity, raising thermoelectricity capability.Up to the present, this system N-type ZrNiSn and p-type FeNbSb are in high temperature section
(600-800 DEG C) ZT value highests respectively reach 1.2 and 1.5.The continuous improvement of HH alloy ZT values, the application for HH thermo-electric devices are established
Basis is determined.
The main problem that efficient half-Heusler thermoelectric conversion elements cannot manufacture on a large scale at present is electrode
Design with prepare and device overall package.Electrode is for connection to n, p-type thermoelectric material both ends, forms electric current transmission circuit
Important component.Half-heusler high temperature thermo-electric devices are usually operated at 600~800 DEG C, therefore, electrode material
And the stabilization of its linkage interface with thermoelectric material, the matching of coefficient of thermal expansion, interface resistance and thermal resistance etc. all will be to devices
Performance And Reliability generate very important influence.Joshi G are directly connected to Ag electrodes, Ag/Incusil solders using hot pressing
With P-type Hf0.5Zr0.5CoSn0.2Sb0.8、 N-type Ti0.6Hf0.4NiSn, the linkage interface reaction obtained is serious, Ag
And the diffusion depth of Incusil solders is about 4 μm, 40 μm, contact resistivity is more than 50 μ Ω cm2, the research think interface connect
The serious diffusion reaction in the place of connecing is the main reason for contact resistivity is caused to rise.In order to solve this problem, someone utilizes hot pressing
Method realizes Ti and P-Hf0.5Zr0.5CoSb0.8Sn0.2、N-Ti0.6Hf0.4The connection of NiSn.Thickness is spread at this linkage interface
Degree<100 μm, the μ Ω cm of contact resistivity~12, junction intensity~50MPa.Ti and half-Heusler bases are thought in the research
Thermoelectric material have well it is thermally matched, meanwhile, formed diffusion layer the performance of HH is not had an impact simultaneously again improve company
The intensity that connects and the further diffusion for preventing Ti elements, but the research does not analyze diffusion layer structure and ingredient,
Also the thermal stability of the connection is not examined further, only single tests the output performance of device.It finds, uses by test
Ti is connect with half-Heusler base thermoelectricity materials, although in initial stage diffusion phenomena unobvious of being on active service, with active time
Extension, Ti and half-Heusler linkage interface diffusion phenomena are serious, thickness of diffusion layer increase, lead to interface contact resistance
Rate increases, and causes thermo-electric device performance unstable.
Utility model content
The purpose of the utility model is to overcome the above-mentioned deficiencies of the prior art, provide a kind of thermo-electric device electrode, with solution
Certainly existing thermo-electric device electrode causes the thickness of diffusion layer to increase therewith with the extension of active time, and causes interfacial contact electric
The increase of resistance reduces the technical issues of pyroelectric material performance causes thermo-electric device stability to decline.
The another object of the utility model is to provide a kind of thermo-electric device, during solving existing thermo-electric device with being on active service
Between extension, hot junction stability decline the technical issues of.
In order to realize above-mentioned purpose of utility model, the one side of the utility model provides a kind of thermo-electric device electrode.Institute
It states thermo-electric device electrode and includes half-Heusler hypothallus, solder layer and electrode layer that combination is laminated with this, in the half-
It is also laminated between Heusler hypothallus and solder layer and is combined with barrier layer, the barrier layer is Ti-Ni alloy layer.
Preferably, the thickness of the Ti-Ni alloy layer is 0.1-0.6mm.
It is further preferred that the thickness 5-20mm of the half-Heusler hypothallus.
It is further preferred that the thickness of the solder layer is 0.01-0.1mm.
It is further preferred that the thickness of the electrode layer is 0.5-2mm.
It is further preferred that the electrode layer is copper electrode.
Specifically, the stacking is combined into sintering.
The another aspect of the utility model provides a kind of thermo-electric device.The thermo-electric device includes electrode, and the electricity
The thermo-electric device that extremely prepared by the utility model thermo-electric device electrode or the utility model preparation method.
Compared with prior art, above-mentioned thermo-electric device electrode is used and is increased between half-Heusler hypothallus and solder layer
If Ti-Ni alloy layer structure, on the one hand enable to have between electrode layer and half-Heusler hypothallus contact interfaces good
Thermal expansion matching, effectively improve the structural stability of linkage interface；On the other hand the thickness of diffusion layer formed between interface
Small, interface contact resistance is small, and thickness of diffusion layer can be kept stablizing with the extension of active time so that interface stability is high.
Above-mentioned thermo-electric device electrode is above-mentioned the utility model thermo-electric device electrode, therefore, the utility model thermo-electric device
Electrode interface contact resistance is small, and interface thermal expansion matches, and assigns above-mentioned the utility model thermo-electric device high heat to electricity conversion effect
Rate, and can stablize with the extension property retention of active time.
Description of the drawings
Fig. 1 is the structure diagram that the utility model implements thermo-electric device electrode；
Fig. 2 is that the Electronic Speculum of production diffusion layer in the thermo-electric device electrode that the utility model embodiment 1 is provided with comparative example 2 is swept
Trace designs piece；Wherein, Fig. 2 a are electrode interface electron-microscope scanning picture in embodiment 1, and Fig. 2 b are that electrode interface Electronic Speculum is swept in comparative example 2
Trace designs piece.
Specific embodiment
In order to which the technical problems to be solved in the utility model, technical solution and advantageous effect is more clearly understood, below
In conjunction with the embodiments with attached drawing, the present invention is further described in detail.It should be appreciated that specific implementation described herein
Example is only used to explain the utility model, is not used to limit the utility model.
On the one hand, the utility model embodiment provides a kind of thermo-electric device electrode, and structure is as shown in Figure 1, it includes
Half-Heusler hypothallus 1, by the direction of extension of 1 center of half-Heusler hypothallus to a surface, described
It is stacked gradually on 1 surface of half-Heusler hypothallus and is combined with barrier layer 2, solder layer 3 and electrode layer 4.
Wherein, half-Heusler hypothallus 1 is used as heat to electricity conversion functional layer and the carrier layer as electrode layer 4.
In one embodiment, half-Heusler thermoelectric materials contained in the half-Heusler hypothallus 1 are n
Type HfxZr1-xNiSn1-ySby, p-type FeNb1-mHfmOne or both of Sb, wherein, x 0.1-0.7, y 0.01-0.05,
M is 0.1-0.3.The thermoelectric material has excellent thermoelectricity capability, with high temperature pyroelecthc properties, but also with proportion
The advantages that small, environmental-friendly and at low cost, can improve the thermoelectrical efficiency and stability of thermo-electric device.Certainly, the half-
The material of Heusler hypothallus 1 can also be other thermoelectric materials.
In another embodiment, the thickness of half-Heusler hypothallus 1 can with but not only control in 5-20mm.
Above-mentioned solder layer 3 realizes welding electrode layer 4 and half-Heusler hypothallus 1.In one embodiment, the solder layer
3 can select Ag-Cu-Zn solder layer, can also select other solders used in thermo-electric device electrode certainly.In another embodiment
In, the thickness of above-mentioned solder layer 3 is 0.01-0.1mm.The specific can be that but not just for 0.05mm.
The barrier layer 2 being incorporated between above-mentioned solder layer 3 and half-Heusler hypothallus 1, which is laminated, can play blocking
Effect, specifically, the barrier layer 2 is Ti-Ni alloy layer.In this way, on the one hand the Ti-Ni alloy layer is obstructed in titanium and solder layer 3
Such as silver, copper metallic element are spread into half-Heusler hypothallus 1, so as to ensure half-Heusler thermoelectric material thermoelectricity
The stabilization of performance, and so that the thickness of diffusion layer formed is small, and as the time lengthening that thermo-electric device is on active service ensures diffusion thickness
The stabilization of degree in other words, ensures that the diffusion layer to be formed will not be thickening with the extension of thermo-electric device active time, so as to protect
The stabilization of thickness of diffusion layer is demonstrate,proved, and so that interface contact resistance is small；On the other hand, which has and half-
The coefficient of thermal expansion that Heusler hypothallus 1 matches, this ensure that half-Heusler hypothallus 1 and solder layer 3 and electricity
The stability of structure between pole layer 4.Therefore, which has the heat to match with 1 material of half-Heusler hypothallus
The coefficient of expansion, and with titanium a degree of chemical reaction can occur for nickel, form intermetallic compound, reduce interface junction
Thickness of diffusion layer effectively reduces contact resistance, which also effectively inhibits solder layer 3 and electrode material to half-
The diffusion of Heusler hypothallus 1.In addition, the addition of nickel also improves the inoxidizability of titanium at high temperature, so as to improve thermoelectricity
The output performance and stability of device also increase the service life of device.
In one embodiment, above-mentioned Ti-Ni alloy layer 2 is to form powder by titanium valve, the mixture of nickel powder or Ti-Ni alloy powder
Layer is formed through sintering processes.In a further embodiment, the temperature of the sintering processes is 650-850 DEG C, pressure 30-
45MPa, wherein, under conditions of the sintering processes, sintering time should be sufficient, such as be sintered 15-30min.
On the basis of the various embodiments described above, in an embodiment, above-mentioned Ti-Ni alloy layer is contained in barrier layer 2
Ti/Ni=n, the n take 4-9, preferably 7-9, are further 8-9.Wherein, n values are the molar ratios of value Ti and Ni.
In another embodiment, the thickness control on above-mentioned barrier layer 2 is further 0.4-0.6mm or 0.1-0.5mm in 0.1-0.6mm.
By optimizing the content that Ti-Ni alloy layer is generation type in barrier layer 2, formation condition, titanium elements and nickel element
Than the control with layer structural thickness, it is above-mentioned to realize that optimization barrier layer 2 has the function of, further improves above-mentioned thermo-electric device electrode
Performance.
Above-mentioned 4 material of electrode layer can be the common electrode material of thermo-electric device electrode, such as in a particular embodiment, the electricity
The material of pole layer 4 is any one in copper, Ag, Mo, Co, W, Nb, Ni.In one embodiment, the thickness of above-mentioned electrode layer is
0.5-2mm, specifically can be with but not just for 0.8mm.
In addition, on the basis of the various embodiments described above, combination between each layer can with but be not only that sinter bonded can be used,
Other modes can also be used to combine, such as each layer is sequentially prepared using sputtering sedimentation so that each layer structure is combined as a whole.
Therefore, above-mentioned thermo-electric device electrode is closed using titanium nickel is added between half-Heusler hypothallus 1 and solder layer 3
Layer gold structure, that is, barrier layer 2, not only so that having between 1 contact interface of electrode layer 4 and half-Heusler hypothallus good
Thermal expansion matching, and the thickness of diffusion layer formed between interface is small, and thickness of diffusion layer can be with the extension of active time
It keeps stablizing so that interface resistance is small, and interface stability is high.
Correspondingly, the utility model embodiment additionally provides a kind of preparation method of thermo-electric device electrode described above.It should
Preparation method includes the following steps：
S01. it is laid with Ti-Ni alloy barrier layer powder layer, solder layer 3 and electrode successively in half-Heusler stromal surfaces
Layer 4；
S02. it is sintered again.
Specifically, the half-Heusler matrix in above-mentioned steps S01 and solder layer 3 and electrode layer 4 as described above,
In order to save length, details are not described herein.Wherein, solder layer 3 can be solder paillon, specifically Ag-Cu-Zn solder foil in this way
Piece, 600~800 DEG C of fusing point.Electrode layer 4 can be but not just for copper sheet.
In step S01, for barrier layer powder layer after sintering processes, powder sintering forms thermo-electric device electricity described above
Extremely contained barrier layer 2.In one embodiment, which is titanium valve, nickel powder or peptide-nickel alloy powder are laid with
It is formed, in specific embodiment, the grain size of the powder is but not just for 200 mesh.Each mixed body hybrid mode can with but not just for
Ultrasonic vibration, mechanical ball mill in mixed process, can add in blending agent, which is advisable volatile media, such as pure
Spend AR or ethyl alcohol etc..Howsoever hybrid mode, in one embodiment, as described above, the resistance formed after sintering processes
In barrier, Ti/Ni=n, n take 4-9, preferably 7-9, are further 8-9, the thickness 0.1-0.6mm on barrier layer 2, further for
0.4-0.6mm or 0.1-0.5mm.
In addition, the half-Heusler matrix in step S01 can be prepared as follows to be formed：
S011. each raw metal is measured according to the molar ratio of the metallic element contained by half-Heusler thermoelectric materials；
S012. by except the Sb raw metals of measurement, remaining raw metal of measurement is subjected to vacuum melting processing, is formed
First ingot casting；
S013. the first ingot casting together with the Sb raw metals of measurement is ground processing, forms mixture powder；
S014. by the mixture powder in vacuum melting again handle, after made annealing treatment, obtain the second ingot casting；
S015. it after second ingot casting being ground processing, is sintered.
In above-mentioned steps S011, the half-Heusler thermoelectric materials of half-Heusler thermoelectric materials as described above.
Electric arc melting processing may be used in vacuum melting processing in above-mentioned steps S012.Grinding in above-mentioned steps S013 can adopt
With conventional lapping mode milled processed, the diameter of particle of milled processed can be 200 mesh.In above-mentioned steps S014 at vacuum melting
The temperature for managing melting processing is 1000-1100 DEG C, and the time is 24-96 hours, specific such as 72 hours, specifically can be in vacuum
It is carried out in quartz ampoule.The temperature of annealing in step S014 is 800-900 DEG C, and specific such as 850 DEG C, the time is 24-96
Hour, it is specific such as 48 hours.In above-mentioned steps S015, regrinding processing can be such as the grinding in above-mentioned steps S013 at
Reason, the diameter of particle of milled processed are but not just for 200 mesh.In addition, the temperature of sintering processes is 650- in step S015
1100 DEG C, be further 850-1100 DEG C, and sintering pressure is 35-75MPa, is further 50-75MPa.Specifically, the step
Sintering processes can be to carry out in SPS or hot pressing powder metallurgical equipment in S015, and the condition of the sintering processes can be according to hereafter real
Step d conditions in example 1 are applied to carry out.
In above-mentioned steps S02, after sintering processes, as described above, barrier layer powder layer is sintered to form barrier layer 2, and each layer
It is sintered and is combined as a whole, form thermo-electric device electrode shown in FIG. 1 as described above.In one embodiment, at the sintering
The temperature of reason is 650-900 DEG C, is further 650-850 DEG C, pressure 20-50Mpa is further 30-45MPa.The condition
Under sintering should be sufficient, such as sintering time 15-30min.Equally, the sintering processes in this step can be with SPS or hot pressing
It is carried out in powder metallurgical equipment.
Therefore, above-mentioned thermo-electric device electrode preparation method is sintered after each layer is laminated and is integrated, and sound construction makes
The transition zone that must be formed between Ti-Ni alloy barrier layer and half-Heusler matrix is thin, and interface contact resistance is small, and causes
Thickness of diffusion layer can be kept stablizing with the extension of active time, ensure that interface stability is high, and thermal expansion matching between interface,
Improve the stability of connection interface structure.In addition, above-mentioned preparation method process conditions are easily-controllable, the thermoelectricity device for preparing and being formed ensure that
The stability of part electrode performance, and production efficiency is high, reduces the cost of production.
On the basis of thermo-electric device electrode extremely preparation method described above, the utility model embodiment also provides
A kind of thermo-electric device.The thermo-electric device includes at least conventional necessary component, such as electrod assembly.Wherein, the electrod assembly
For the thermo-electric device electrode shown in FIG. 1 described in the utility model embodiment above.In this way, due to above-mentioned heat as described above
Electrical part electrode interface contact resistance is small, and interface thermal expansion matches, so as to assign the utility model embodiment thermo-electric device height
Conversion efficiency of thermoelectric, and can stablize with the extension property retention of active time.
In conjunction with specific example, to structure of the utility model embodiment composite polycrystal-diamond and preparation method thereof into
Row is further described.
Embodiment 1
The present embodiment provides a kind of thermo-electric device electrodes and preparation method thereof.Thermo-electric device electrode structure such as Fig. 1 institutes
Show, including half-Heusler hypothallus 1 and the barrier layer 2, the solder layer that are layered in 1 surface of half-Heusler hypothallus
3rd, copper electrode layer 4.Wherein, 2 thickness of barrier layer is 0.5mm, and the thickness of solder paillon is 0.05mm.The thickness of copper electrode is
0.8mm。
The preparation method of the present embodiment thermo-electric device electrode is as follows：
The preparation of S11half-Heusler thermoelectric material blocks：
A proportionings weigh simple substance element used, electric arc melting are carried out to the element except Sb, by the obtained casting after melting
Ingot proportioning weighs the amount of required Sb, and the powder that processing is mixed is ground to above two material；Electric arc melting electric current
For 150A, vacuum degree 10-3Pa, smelting time 2min；
Above-mentioned powder is put into vitreosil pipe and carries out high melt by b；The temperature of vacuum high-temperature melting is 1050 DEG C,
Time is 48h, and the vacuum degree of vitreosil pipe is 10-3Pa；
C by above-mentioned melting to block re-grind to 200 mesh；
D is by the methods of SPS hot pressed sinterings, by above-mentioned powder sintering into block；The temperature of SPS hot pressing is 650 DEG C of (p
Type), sintering pressure 35MPa, maximum sintering temperature is held time as 10min~15min, and cooling time is more than 25min, adopts
It is 15mm, the long 40mm of die sleeve, graphite pressure head outer diameter 14.6mm with internal diameter, the graphite jig of length 25mm；
E polishes above-mentioned block with sand paper, ultrasonic clean surface；
S12 is packed into copper electrode piece, solder paillon, barrier material mixed powder, step S11 into graphite jig successively
After the half-Heusler thermoelectric material blocks of preparation, above-mentioned different materials are sintered one by the method for SPS hot pressed sinterings
It rises；Wherein,
Barrier material mixed powder is titanium valve, nickel powder or peptide-nickel alloy powder (200 mesh), medium for purity AR and
It is mixed, and Ti/Ni=9 using ultrasonic vibration mode in the presence of the volatile mediums such as more than alcohol；
The condition of sintering：P-HH/ barrier material sintering temperatures are selected in 700-800 DEG C, and sintering time is 10-
20min, pressure 20-50MPa；Carry out Isothermal sinter；
S13 will be sintered the sample body formed, by diamond wire saw, cuts into length as defined in device, is using sand paper
Polishing forms the high temperature electrode of half-Heusler thermo-electric devices.
Embodiment 2
The present embodiment provides a kind of thermo-electric device electrodes and preparation method thereof.The thermo-electric device electrode structure and embodiment
1 is identical.
The preparation method of the present embodiment thermo-electric device electrode is as follows：
The preparation of S21half-Heusler thermoelectric material blocks is with reference to the S11 of embodiment 1；Wherein, material half-
Heusler be N-shaped half-Heusler, and the temperature of SPS hot pressing be 850 DEG C (N-shapeds), sintering pressure 35MPa, highest sintering
Temperature is held time as 10min~15min, and cooling time is more than 25min, uses internal diameter as 15mm, the long 40mm of die sleeve, graphite
Pressure head outer diameter 14.6mm, the graphite jig of length 25mm；
Step S12 in S22 parameters embodiment 1, wherein,
The condition of sintering：The sintering temperature of N-HH/ barrier materials is selected in 750-900 DEG C, and sintering time is 10-
20min, pressure 20-50MPa；Carry out Isothermal sinter；
Step S13 in S23 parameters embodiment 1.
Embodiment 3
The present embodiment provides a kind of thermo-electric device electrodes and preparation method thereof.The thermo-electric device electrode structure and embodiment
1 is identical.Wherein, 2 thickness of barrier layer is 0.6mm, and the thickness of solder paillon is 0.1mm.The thickness of copper electrode is 0.5mm.
The preparation method of the present embodiment thermo-electric device electrode is as follows：
The preparation of S31half-Heusler thermoelectric material blocks is with reference to the S11 of embodiment 1；Wherein, material half-
Heusler be N-shaped half-Heusler, and the temperature of SPS hot pressing be 850 DEG C (N-shapeds), sintering pressure 35MPa, highest sintering
Temperature is held time as 10min~15min, and cooling time is more than 25min, uses internal diameter as 15mm, the long 40mm of die sleeve, graphite
Pressure head outer diameter 14.6mm, the graphite jig of length 25mm；
Step S12 in S32 parameters embodiment 1, wherein, the Ti/Ni=6 in barrier material；
Step S13 in S33 parameters embodiment 1.
Embodiment 4
The present embodiment provides a kind of thermo-electric device electrodes and preparation method thereof.The thermo-electric device electrode structure and embodiment
1 is identical.Wherein, 2 thickness of barrier layer is 0.1mm, and the thickness of solder paillon is 0.07mm.The thickness of copper electrode is 1mm.
The preparation method of the present embodiment thermo-electric device electrode is as follows：
The preparation of S41half-Heusler thermoelectric material blocks is with reference to the S11 of embodiment 1；Wherein, material half-
Heusler be N-shaped half-Heusler, and the temperature of SPS hot pressing be 850 DEG C (N-shapeds), sintering pressure 35MPa, most high fever
Junction temperature is held time as 10min~15min, and cooling time is more than 25min, uses internal diameter as 15mm, the long 40mm of die sleeve, stone
Black pressure head outer diameter 14.6mm, the graphite jig of length 25mm；
Step S12 in S42 parameters embodiment 1, wherein, the Ti/Ni=5 in barrier material；
Step S13 in S43 parameters embodiment 1.
Comparative example 1
Thermo-electric device electrode is conventional silver (CTE at a temperature of 300KTi=19.5m-1m-1K-1) electrode material and half-
Heusler base thermoelectricity materials (CTE at a temperature of 300Khalf-Heusler=10.5um-1m-1K-1) directly in conjunction with.
Comparative example 2
With reference to thermo-electric device electrode in embodiment 1, difference is, barrier layer is pure titanium (CTE at a temperature of 300KTi=
10.9um-1m-1K-1)。
Correlated performance is tested
1. interface stability
Interface stability is measured after thermo-electric device electrode in embodiment 1-4 and comparative example is carried out high-temperature service respectively.Through
It measures, the interface between the electrode layer 4 of thermo-electric device electrode and half-Heusler hypothallus that the present embodiment 1-4 is provided is steady
It is fixed, it is flawless, wherein, electrode interface as shown in Figure 2 a, further carries out interface analysis, substantially to embodiment 2-4 in embodiment 1
Identical with Fig. 2 a, interface is stablized, flawless.2 electrode interface of comparative example is also horizontal without apparent row, as shown in Figure 2 b, but compares
There is apparent slight crack with half-Heusler hypothallus in the silver electrode material of 1 electrode of example, that is to say the sector electrode of comparative example 1
Face stability is deteriorated during service.2 electrode of comparative example is due to the presence of titanium layer, with half-Heusler hypothallus thermoelectricity materials
The thermal expansion of material more matches, more secured with the connection of half-Heusler thermoelectric materials, and therefore, interface stability is good.
The present embodiment 1-4 provide thermo-electric device electrode due to the variation there are its coefficient of thermal expansion on Ti-Ni alloy barrier layer 3 it is smaller,
There is preferable thermal expansion matching, and the presence of titanium elements additionally aids the welding of solder with half-Heusler thermoelectric materials,
Therefore the thermo-electric device electrode interface stability relative contrast example 1,2 that the present embodiment 1-4 is provided is more excellent.
The thickness of 2 interface diffusion layers
The embodiment 1-4 thickness of diffusion layer generated with thermo-electric device electrode interface in comparative example is measured.This implementation
Example 1-4 electrode interfaces thickness of diffusion layer is significantly lower than the thickness of diffusion layer produced by comparative example 1,2 electrode interfaces.And with clothes
The time lengthening of labour, comparative example 1,2 interface diffusion layer thickness can be thickened with the extension of active time, this is because comparative example
Although titanium elements material is more matched with the thermal expansion of half-Heusler thermoelectric materials, with half-Heusler thermoelectric materials
Connection is more secured, but titanium has higher reactivity, is formed at high temperature with the linkage interface of thermoelectric material
Diffusion layer is thicker and as time thickness of diffusion layer increases comparatively fast, has both increased the contact resistance at linkage interface, following article table 1
It is shown, so as to reduce the stability of the military service of the performance of thermoelectric material and device.And contained by the electrode in the present embodiment 1-4
Barrier layer 3 in contain nickel so that the variation of Ti-Ni alloy layer coefficient of thermal expansion is smaller, with half-Heusler thermoelectric materials
There is preferable thermal expansion matching, while metallic element in titanium and solder can be significantly reduced again and entered in half-Heusler
Degree reduces the thickness of diffusion layer, and titanium additionally aids the welding of solder, so that the electrode that the present embodiment 1-4 is provided is in warm
It gets a promotion in terms of the stability of expansion, contact resistance and linkage interface.Wherein, the electrode that the present embodiment 1 is provided with
The electrode provided in comparative example 2 carries out electron-microscope scanning, and electron-microscope scanning picture is as shown in Figure 2.From Figure 2 it can be seen that the utility model
Each interfacial contact including barrier layer 2 of thermo-electric device electrode is good and clear, without apparent crackle and crack, and spreads
The thickness of layer is thin, as shown in Figure 2 a；And the electrode diffusion layer thickness in comparative example 2 is significantly greater than the thickness of diffusion layer of Fig. 2 a, such as
Shown in Fig. 2 b.After tested, the electron-microscope scanning figure of embodiment 2-4 is substantially the same manner as Example 1.
The measure that 2 interface diffusion layer thickness and contact resistance change in military service
By embodiment 1-4 with thermo-electric device electrode in comparative example after 500 DEG C are on active service, each electrode interface diffusion layer and contact
Resistivity in active time variation be measured.Wherein, electrode test result such as the following table 1 institute in embodiment 1 and comparative example 2
Show.After tested, the electrode test result of embodiment 2-4 and embodiment 1 are very close.
From figure 1 it appears that Ti layers in comparative example 2 in half-Heusler linkage interfaces and the present embodiment 1
Ti/Ni barrier layers and the contact resistivity of half-Heusler linkage interfaces are close at the beginning, with active time
Extend, Ti layers serious with half-Heusler linkage interface diffusion phenomena, and thickness of diffusion layer increases, this is the connection contact resistance
The main reason for rate increases compares the interface diffusion layer rate of rise of two kinds of connections, Ti layers and half-Heusler linkage interfaces
Diffusion layer balanced growth rate is significantly greater than Ti/Ni barrier layers and the diffusion layer balanced growth speed of half-Heusler linkage interfaces
Rate.The contact resistivity of Ti/Ni barrier layers and half-Heusler linkage interfaces is with active time with being increased slightly, but change
Smaller, thickness of diffusion layer growth is slower, and to improving diffusion layer structure, reducing thickness of diffusion layer has obvious effect for the addition of Ni.
On the basis of this, 1 electrode interface contact resistance of embodiment is increased slowly, and significantly lower than 2 median surface of comparative example contact electricity
Resistance.
Table 1
The above is only the preferred embodiment of the utility model only, is not intended to limit the utility model, all at this
All any modification, equivalent and improvement made within the spirit and principle of utility model etc., should be included in the utility model
Protection domain within.
Claims (8)
1. a kind of thermo-electric device electrode, half-Heusler hypothallus, solder layer and electrode layer including combination is laminated with this,
It is characterized in that：It is also laminated between the half-Heusler hypothallus and solder layer and is combined with barrier layer, the barrier layer is
Ti-Ni alloy layer.
2. thermo-electric device electrode according to claim 1, it is characterised in that：The thickness of the Ti-Ni alloy layer is 0.1-
0.6mm。
3. according to any thermo-electric device electrodes of claim 1-2, it is characterised in that：The half-Heusler hypothallus
Thickness 5-20mm.
4. according to any thermo-electric device electrodes of claim 1-2, it is characterised in that：The thickness of the solder layer is
0.01-0.1mm。
5. according to any thermo-electric device electrodes of claim 1-2, it is characterised in that：The thickness of the electrode layer is 0.5-
2mm。
6. thermo-electric device electrode according to claim 5, it is characterised in that：The electrode layer is copper electrode.
7. according to any thermo-electric device electrodes of claim 1-2, it is characterised in that：The stacking is combined into sintering.
8. a kind of thermo-electric device, including electrode, it is characterised in that：The electrode is any thermoelectricity devices of claim 1-7
Part electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107665943A (en) * | 2017-08-04 | 2018-02-06 | 深圳大学 | Thermo-electric device electrode and preparation method thereof and thermo-electric device |
| CN111211214A (en) * | 2020-01-09 | 2020-05-29 | 中国科学院上海硅酸盐研究所 | Interface barrier layer for half-heusler alloy thermoelectric material |
-
2017
- 2017-08-04 CN CN201720979310.1U patent/CN207529976U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107665943A (en) * | 2017-08-04 | 2018-02-06 | 深圳大学 | Thermo-electric device electrode and preparation method thereof and thermo-electric device |
| CN111211214A (en) * | 2020-01-09 | 2020-05-29 | 中国科学院上海硅酸盐研究所 | Interface barrier layer for half-heusler alloy thermoelectric material |
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