CN104347788B - Skutterudite-based thermoelectric element equipment and preparation method thereof - Google Patents
Skutterudite-based thermoelectric element equipment and preparation method thereof Download PDFInfo
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Abstract
The invention relates to skutterudite-based thermoelectric element equipment and a preparation method thereof, and provides skutterudite-based thermoelectric element equipment. The skutterudite-based thermoelectric element equipment comprises a thermoelectric element and at least one electrode, wherein the thermoelectric element is provided with a surface and is made of thermoelectric element material, the electrode is coupled to the surface of the thermoelectric element and is used for carrying current to the thermoelectric element or from the thermoelectric element, each electrode comprises an electrode layer, each electrode layer is made of at least two metals, is used for covering at least one part of the surface of the thermoelectric element, and is directly or indirectly connected with at least one part of the surface of the thermoelectric element, each electrode layer comprises at least one of (i) alloy of at least two metals; (ii) a multi-layer structure, and each layer comprises at least one of two metals. The invention also provides the preparation method of the skutterudite-based thermoelectric element equipment.
Description
Technical field
The invention belongs to thermoelectricity components and parts technical field, it is related to a kind of skutterudite-base thermoelectrical component equipment and its preparation side
Method, more particularly, it relates to a kind of alloy electrode of skutterudite-base thermoelectrical element and preparation method thereof.
Background technology
Thermoelectric power generation is by heat energy using semiconductor thermoelectric transition material（The temperature difference）It is converted into the entirely static of electric energy directly to send out
Electrically, it is the green energy resource technology meeting environmental protection, dirty for the currently growing Pressure on Energy of alleviation and solution and environment
Dye is significant.Thermoelectric heat generation system have compact conformation, dependable performance, run when noiseless, no abrasion, No leakage,
The features such as mobility is got well and is applied to low energy densities and recycles, is particularly suitable for industrial exhaust heat and waste heat of automotive exhaust gas etc.
Recycle.Currently, with respect to the suitable maturation of the bismuth telluride-based thermoelectric refrigeration device of cryogenic refrigeration and be widely used
The components and parts of the preparations such as thermoelectric material such as PbTe and SiGe generating electricity in commodity production, high temperature are at present in the prosperity such as America and Europe state
Family also begins to be applied to space field, and substantial amounts of research has been done to the oxide pyroelectric material generating electricity and device by Japan.Square cobalt
The thermoelectricity capability of ore deposit base thermoelectricity material Yin Qigao and its factor such as other cost and controllable standby technology are considered as to have most
The middle temperature electricity generation material of future, the p-type of doping or filling, its thermoelectric figure of merit of skutterudite-base thermoelectrical material of N-shaped（ZT）All
Reach more than 1.0（Shi Xun;Yang Jiong;Salvador James R et al., Multiple-Filled
Skutterudites:High Thermoelectric Figure of Merit through Separately
Optimizing Electrical and Thermal Transports（The skutterudite of many fillings：By separately optimizing electricity and
The hyperpyrexia quality factor of Heat transmission）,JACS,2011(133)7837-7846;Chen Lidong, Liu Ruiheng, Chou Pengfei, a kind of " hyperpyrexia
The p-type of electrical property is combined skutterudite material and preparation method thereof ", CN201010259433.0）But, the preparation skill of its components and parts
Art is still far from perfect, and particularly the connectivity problem of electrode, intermediate layer and skutterudite-base thermoelectrical material is it is important to will adopt suitably
Technology of preparing is reducing the generation of the mismatch of thermal coefficient of expansion and serious diffusion reaction each other.
In general, the electrode of thermoelectricity components and parts selects mainly to follow following principle：Using electrode in temperature range
The phase counterdiffusion no serious with corresponding thermoelectric material and its intermediate layer or reaction, thus ensure thermoelectric material self performance not
Impacted；There are higher electrical conductivity and thermal conductivity to reduce energy loss；Using having certain antioxidation in temperature range
Property is to ensure reliability and the service life of device；The thermal coefficient of expansion of electrode material and corresponding thermoelectric material mate to prevent
Crack thus affecting thermoelectric transport properties and heat stability.
Low temperature thermoelectric unit part, due to not high using temperature, typically can select Cu and Al etc. as electrode, such as patent documentation
Bi in JP100129352Te3Thermoelement selects Al as electrode material.But for high temperature thermoelectricity components and parts, due to temperature
Degree range spans are larger, and the long-term work of thermo-electric device hot junction is under the high temperature conditions, and thermoelectric material is with electrode material because heat is swollen
The difference of swollen coefficient and easily crack in interface, the therefore selection of centering high temperature thermoelectric components and parts electrode and Joining Technology
There is higher requirement.In patent documentation JP11274580 and JP2000100751, PbTe and SiGe thermo-electric device is all adopted
With Cu electrode.Research for skutterudite-base thermoelectrical device is still in laboratory stage at present, and some researcheres are to skutterudite
The electrode of base thermo-electric device also uses Ni metal as electrode, such as patent documentation JP2004063585.And in fact Cu with
CoSb3Thermal expansion coefficient difference excessive（During 373K, Ni metal and skutterudite material thermal expansion coefficient are respectively 18 × 10-6K-1With
10×10-6K-1）, when using under hot conditionss, easily cause electrode material and thermoelectric material Interface Cracking.U.S.'s jet power
Test chamber（Jet propulsion Laboratory）Once in the 20th International Conference on
Thermoelectrics（Thermoelectricity world conference）Metal Ti was employed as electrode when reporting single pair of antimony cobalt base thermoelectric power generation
（D.J.Yao, C.J.Kim, G.Chen, J.L.Liu, K.L.Wang, J.Snyder and J.P.Fleurial, " MEMS
thermoelectric microcooler（MEMS thermoelectricity micro-cooler）"Proceedings（Procceedingss）
ICT2001.20International Conference on Thermoelectrics(Cat.No.01TH8589),
pp.401-404,2001）.But the shortcoming as electrode for the metal Ti is electrical conductivity and thermal conductivity is relatively low, and energy consumption is larger, and
And non-oxidizability is poor, therefore it is also not suitable for the electrode material as skutterudite-base thermoelectrical power generating device.Chinese Academy of Sciences's Shanghai silicon
Hydrochlorate institute has done substantial amounts of work on the preparation research of skutterudite-base thermoelectrical device, particular for the selection of electrode material
And skutterudite-base thermoelectrical material has done substantial amounts of research with the connection reliability of electrode material.In patent documentation CN1585145
In, Fan etc. adopts metal Mo as electrode material, using metal Ti as boundary layer, is sintered with discharge plasma（SPS）Side
Method achieves the connection of electrode, intermediate layer and thermoelectric material, but the thermal coefficient of expansion due to Mo is differed very with skutterudite material
Greatly（During 373K, metal Mo and skutterudite material thermal expansion coefficient are respectively 5.4 × 10-6K-1With 10 × 10-6K-1）, and the conductance of Mo
Rate is relatively low, and Mo is not as suitable as the electrode material of skutterudite device；In patent documentation CN101101955A and
In CN100552999C, Zhao etc. to substitute single Ni metal or Mo electrode using alloy material Mo-W and Mo-Cu as electrode,
Using metal Ti as intermediate layer material, achieve the connection of electrode, intermediate layer and thermoelectric material with the method for SPS.But use
The method of SPS realizing the connection of electrode, intermediate layer and thermoelectric material, high cost, complex operation and be not suitable for producing in batches, and
The temperature end that the electrode layer of excessive densification is easily caused thermoelement still easily ftractures.
Therefore, in the urgent need to developing, a kind of process is simple, good reliability, preparation cost be low and suitable scale for this area
The alloy electrode preparation method of the skutterudite-base thermoelectrical element producing, to be obtained, consistency is low, reduce electrode material and interface
Negative effect that the difference of layer material thermal coefficient of expansion is brought, intermediate layer Ti alloy electrical contact performance be good and electrode and its heat
The durability of electric device and thermal-shock resistance alloy electrode of good performance.
Content of the invention
The invention provides a kind of novel skutterudite-base thermoelectrical component equipment and preparation method thereof, thus solving existing
Problem present in technology.The invention provides one kind is by least two metals（Preferably Ni metal and metal Mo）The alloy of composition
Electrode, and electrode is realized using a kind of low cost, simple to operate and beneficial to a large amount of preparation method-sprayings producing method
The good combination of material, intermediate layer and thermoelectric material.
It is an object of the invention to provide a kind of alloy electrode for skutterudite-base thermoelectrical components and parts and preparation method thereof,
That is, the present invention provide a kind of with skutterudite-base thermoelectrical material thermally matched good by least two metals（Preferably Ni metal and gold
Belong to Mo）The alloy electrode of composition and the connection work of electrode and Ti alloy substrates in intermediate layer used by skutterudite-base thermoelectrical components and parts
Skill.The process is simple of the present invention, the skutterudite-base thermoelectrical device interface prepared is functional, interface reliability high.
On the one hand, the invention provides a kind of skutterudite-base thermoelectrical component equipment, including：
The thermoelement being formed by the skutterudite-base material with surface；And
The surface being coupled to described thermoelement is for carrying electricity to described thermoelement or from described thermoelement
Carry at least one electrode of electricity, at least one electrode described includes the electrode layer being formed by least two metals, described electrode layer
Cover at least a portion on the surface of described thermoelement, and directly or indirectly at least with the surface of described thermoelement
Divide and connect, wherein, described electrode layer includes one below：（i）The alloy of at least two metals；And（ii）Multiple structure, its
In each layer include one of described at least two metals.
In one preferred embodiment, described at least two metals are selected from：Cu, Mo, Ni, Ti, W, Co and Nb.
Another preferred embodiment in, described at least two metals are one below：（i）Cu and Mo；And
（ii）Ni and Mo.
Another preferred embodiment in, described multiple structure includes at least four subgrades, wherein adjacent subgrade
It is the different situations of described at least two metals.
Another preferred embodiment in, this equipment meets following at least one performance：
The gross thickness of described electrode layer is one below：（i）0.02-20.0mm；（ii）0.05-10.0mm；And（iii）
0.1-1.5mm；And
The thickness of each subgrade of described multiple structure is one below：（i）0.01-2.0mm；（ii）0.01-1.0mm；
And（iii）0.05-0.5mm.
Another preferred embodiment in, this equipment also includes：
The boundary layer being formed by titanium or its alloy, described boundary layer covers at least of the surface of described thermoelement
Point, and be directly or indirectly connected with least a portion on the surface of described thermoelement,
Wherein, described electrode layer covers at least a portion of described boundary layer, and direct or indirect and described boundary layer
At least a portion connects.
Another preferred embodiment in, described boundary layer directly with the skutterudite-base material of described thermoelement
Surface connects, and described boundary layer is inserted between described thermoelement and electrode layer, and described electrode layer directly with described interface
Layer connects.
Another preferred embodiment in, described titanium alloy contains titanium and aluminum.
Another preferred embodiment in, the gross thickness of described boundary layer is one below：（i）0.001-1mm；
（ii）0.005-0.5mm；And（iii）0.01-0.1mm.
On the other hand, the invention provides a kind of method preparing skutterudite-base thermoelectrical component equipment, the method includes：
The thermoelement being formed by the skutterudite-base material with least one surface is provided；And
In at least a portion on the surface at least one electrode layer being directly or indirectly placed on described thermoelement, and cover
Cover at least a portion on the surface of described thermoelement, wherein, at least one electrode layer described is formed by least two metals, makes
Obtain described electrode layer and include one below：（i）The alloy of at least two metals；And（ii）Multiple structure, wherein each layer includes
One of described at least two metals.
In one preferred embodiment, at least one electrode layer is placed on the step on the surface of described thermoelement
Suddenly include described electrode layer is directly or indirectly sprayed on the surface of described thermoelement.
Another preferred embodiment in, described electrode layer is directly or indirectly sprayed on the table of described thermoelement
Step on face includes one below：
（i）One or more layers alloy-layer of described at least two metals is directly or indirectly sprayed on described thermoelement
On surface；And
（ii）The ground floor of described at least two metals is directly or indirectly sprayed on the surface of described thermoelement, connects
And the succeeding layer of described at least two metals is sprayed on front layer, be consequently formed different subgrades so that adjacent Asia
Layer is the different situations of described at least two metals.
Another preferred embodiment in, described at least two metals are selected from：Cu, Mo, Ni, Ti, W, Co and Nb.
Another preferred embodiment in, described at least two metals are one below：（i）Cu and Mo；And
（ii）Ni and Mo.
Another preferred embodiment in, the method meets following at least one performance：
The gross thickness of described electrode layer is one below：（i）0.02-20.0mm；（ii）0.05-10.0mm；And（iii）
0.1-1.5mm；And
The thickness of each subgrade of described multiple structure is one below：（i）0.01-2.0mm；（ii）0.01-1.0mm；
And（iii）0.05-0.5mm.
Another preferred embodiment in, the method also includes：The boundary layer being formed by titanium or its alloy is placed
In at least a portion on the surface of described thermoelement, and directly connect with least a portion on the surface of described thermoelement
Connect so that described boundary layer is inserted between surface and the electrode layer of described thermoelement, and make described electrode layer directly and institute
State boundary layer contact.
Another preferred embodiment in, the method meets following at least one performance：
Described boundary layer is formed by titanium；
Described boundary layer is formed by titanium alloy；And
Described boundary layer is formed by the titanium alloy containing titanium and aluminum.
Another preferred embodiment in, the gross thickness of described boundary layer is one below：（i）0.001-1mm；
（ii）0.005-0.5mm；And（iii）0.01-0.1mm.
Brief description
The structural representation that a kind of alloy electrode of stacking that Fig. 1 provides for the present invention is connected with intermediate layer Ti alloy substrates
Figure, as shown in figure 1, Ni metal layer 2 is placed on intermediate layer Ti alloy 1, metal Mo layer 3 is placed on Ni metal layer 2, more above successively
Setting Ni metal layer and metal Mo layer.
Fig. 2 is Ni metal and the metal Mo stacking of embodiment 1 preparation（Mo and substrate contact）Alloy electrode and metal Ti
The scanning electron microscope (SEM) photograph of alloy substrates.
Fig. 3 is Ni metal and the metal Mo stacking of embodiment 1 preparation（Mo and substrate contact）Alloy electrode and metal Ti
The contact resistance variation relation schematic diagram at alloy substrates interface.
Fig. 4 is Ni metal and the metal Mo stacking of embodiment 1 preparation（Mo and substrate contact）Alloy electrode and metal Ti
Alloy substrates are in 550 DEG C -0 DEG C scanning electron microscope (SEM) photograph after 10 thermal shocks.
Fig. 5 is Ni metal and the metal Mo stacking of embodiment 2 preparation（Cu and substrate contact）Alloy electrode and metal Ti
The scanning electron microscope (SEM) photograph of alloy substrates.
Fig. 6 is Ni metal and the metal Mo stacking of embodiment 2 preparation（Cu and substrate contact）Alloy electrode and metal Ti
The contact resistance variation relation schematic diagram at alloy substrates interface.
Fig. 7 is Ni metal and the metal Mo stacking of embodiment 2 preparation（Cu and substrate contact）Alloy electrode and metal Ti
Alloy substrates are in 550 DEG C -0 DEG C scanning electron microscope (SEM) photograph after 10 thermal shocks.
Fig. 8 is Ni metal and the alloy electrode that is uniformly mixed of metal Mo and the intermediate layer Ti alloy of embodiment 3 preparation
The scanning electron microscope (SEM) photograph that substrate combines.
Fig. 9 is Ni metal and the alloy electrode that is uniformly mixed of metal Mo and the intermediate layer Ti alloy of embodiment 3 preparation
The contact resistance variation relation schematic diagram at interface.
Figure 10 be the Ni metal of embodiment 3 preparation and the alloy electrode that is uniformly mixed of metal Mo with substrate through 10 heat
Scanning electron microscope (SEM) photograph after shake.
Specific embodiment
The present inventor have passed through extensively and finds after in-depth study, by least two metals（Preferably Ni metal
With metal Mo）Component alloy electrode, using the intermediate layer Ti alloy of skutterudite-base thermoelectrical element as substrate, using the method for spraying
Realize the connection of described at least two metals and intermediate layer Ti alloy substrates, can obtain being combined with intermediate layer Ti alloy substrates good
Good, interface resistance is low, and interface there are no crackle and obvious diffusing phenomenon exist, can stand long thermal shock test and
The alloy electrode of the skutterudite-base thermoelectrical element of degradation.Based on above-mentioned discovery, the present invention is accomplished.
The technology design of the present invention is as follows：
From at least two metals（Preferably Ni metal and metal Mo）As alloy electrode material, the method using spraying is come
Realize alloy electrode and the connection of Ti alloy substrates in intermediate layer used by skutterudite-base thermoelectrical components and parts.
In the present invention, the version of described alloy electrode material can be at least two metals（Preferably Ni metal and
Metal Mo）It is laminated or at least two metals（Preferably Ni metal and metal Mo）It is uniformly mixed.
In the present invention, the spraying method being adopted is electric arc spraying, flame-spraying or plasma spraying.It is preferably electric arc
The method of spraying.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The alloy electrode being laminated,
Its total thickness is 0.02-20.0mm, preferably 0.05-10.0mm, more preferably 0.1-1.5mm.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The alloy electrode being laminated,
Its every layer thickness is 0.01-2.0mm, preferably 0.01-1.0mm, more preferably 0.05-0.5mm.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The alloy electrode being laminated,
Can be that Ni metal and metal Mo are respectively one layer, can be to be respectively two-layer or be respectively N（N>2）Layer.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The alloy electrode being laminated,
Can be that Ni metal is connected with substrate as alloy electrode ground floor or metal Mo is as alloy electrode ground floor and base
Bottom connects.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The alloy electricity being uniformly mixed
Pole, the ratio of itself Cu and Mo can regulate and control.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The alloy electricity being uniformly mixed
Pole, Cu:Mo is 100:1 to 1:100, preferably 10:1 to 1:10.
In the present invention, described intermediate layer Ti alloy substrates, can be pure metal Ti or Ti and other gold
Belong to the alloy being formed.
In the present invention, described by least two metals（Preferably Ni metal and metal Mo）The preparation of the alloy electrode of composition
Method comprises the steps：Weigh a certain amount of metal Ti powder, load in graphite jig, then carry out hot pressing burning in a vacuum
Knot, obtains the metal Ti block of densification；Again to sinter the metal Ti of gained as substrate, the method using spraying is prepared by least
Two kinds of metals（Preferably Ni metal and metal Mo）It is laminated or by least two metals（Preferably Ni metal and metal Mo）
The alloy electrode being uniformly mixed.
Main advantages of the present invention are：
Compared with prior art, the present invention provide using spraying method preparation by least two metals（Preferably gold
Belong to Cu and metal Mo）The alloy electrode of composition, the Mo-Cu conjunction of the Mo-Cu piece that its consistency is bought compared with market and sintering gained
Gold is lower slightly, on the premise of not affecting its alloy electrode electrical property itself and interface electrical property, reduces electrode material and boundary
The negative effect that the difference of surface material thermal coefficient of expansion is brought.The present invention has been obtained good with intermediate layer Ti alloy electrical contact performance
Good alloy electrode, the durability of electrode and its thermoelement and thermal-shock resistance are functional.The skutterudite that the present invention provides
The alloy electrode of base thermoelement is well combined with intermediate layer Ti alloy substrates, and interface resistance is low.Interface there are no crackle and
Significantly diffusing phenomenon exist, and can stand long thermal shock test and degradation.In addition, the preparation method of the present invention is also
There is the low and suitable large-scale production of process is simple, good reliability, preparation cost.
Embodiment
The present invention is expanded on further with reference to specific embodiment.It should be appreciated, however, that these embodiments are only used for
The bright present invention and be not meant to limit the scope of the invention.The test method of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer.Unless otherwise stated, all of percentage ratio and number be by weight
Meter.
Embodiment 1
The preparation of Ti alloy substrates：Weigh in the graphite jig that about 1.8g metal Ti powder loads a diameter of 10mm, Ran Hou
Carry out discharge plasma sintering under vacuum：Vacuum is 10Pa, and sintering pressure is 60MPa, and heating rate is 100 DEG C/min,
Sintering temperature is 600 DEG C, and temperature retention time is 8min；Last furnace cooling, to room temperature, obtains required intermediate layer Ti alloy substrates.
The preparation of alloy electrode：First above-mentioned prepared Ti alloy substrates are fixed on the fixture on electric arc spraying sample stage
On, according to the technological parameter of the spray metal Mo having optimized（Spraying current 180A, voltage 35V, atomization air pressure 60-50psi）Enter
Row spraying, obtains the metal Mo layer that thickness is about 100 μm, according still further to the technological parameter of the spray metal Cu having optimized（Spraying electricity
Stream 160A, voltage 28V, atomization air pressure 50-40psi）Sprayed, obtained the Ni metal layer that thickness is about 250 μm, circulated 3 times,
Obtain the alloy electrode that Ni metal of the present invention and metal Mo are laminated, its structural representation is as shown in Figure 1.?
After carry out thermal shock experiment, thermal shock experiment carries out condition and is：The alloy electrode preparing sample is loaded quartz ampoule, is placed in after tube sealing
Temperature is to be incubated ten minutes in 550 DEG C of Muffle furnace, further takes out and puts into chilling in frozen water, so circulation 10 times.
Fig. 2 is Ni metal manufactured in the present embodiment and metal Mo stacking（Mo and substrate contact）Alloy electrode with
The scanning electron microscope (SEM) photograph that interbed Ti alloy substrates combine.As seen from Figure 2：Alloy electrode manufactured in the present embodiment combines between layers
Well, and keep good contact between substrate.
Using four termination electrode methods, interface resistance is measured, Fig. 3 is Ni metal manufactured in the present embodiment and metal Mo layer
Folded（Mo and substrate contact）Alloy electrode and intermediate layer Ti alloy interface contact resistance variation relation schematic diagram.By scheming
3 is visible, and the interface resistance at each interface, between 10-30 μ Ω, compared with overall resistance, is almost negligible.
Fig. 4 is Ni metal manufactured in the present embodiment and metal Mo stacking（Mo and substrate contact）Alloy electrode with
Scanning electron microscope (SEM) photograph after 10 thermal shocks for the interbed Ti alloy substrates.From fig. 4, it can be seen that passing through thermal shock 10 times at a temperature of 550 DEG C,
Alloy electrode is good with intermediate layer Ti alloy substrates interface cohesion, there are no crackle and exists, and is also not observed in interface
Diffusing phenomenon exist.
Embodiment 2
The preparation of intermediate layer Ti alloy substrates is carried out according to described in embodiment 1.
The preparation of alloy electrode：First above-mentioned prepared substrate is fixed on the fixture on electric arc spraying sample stage, presses
Technological parameter according to the spray metal Cu having optimized（Spraying current 160A, voltage 28V, atomization air pressure 50-40psi）Sprayed
Apply, obtain the Ni metal layer that thickness is about 250 μm, according still further to the technological parameter of the spray metal Mo having optimized（Spraying current
180A, voltage 35V, atomization air pressure 60-50psi）Sprayed, obtained the metal Mo layer that thickness is about 100 μm, so circulated 3
Secondary, that is, obtain the alloy electrode that Ni metal of the present invention and metal Mo are laminated.Finally carry out thermal shock experiment, thermal shock
Experiment condition is identical with described in embodiment 1.
Fig. 5 is Ni metal manufactured in the present embodiment and metal Mo stacking（Cu and substrate contact）Alloy electrode with
The scanning electron microscope (SEM) photograph that interbed Ti alloy substrates combine.As seen from Figure 5, alloy electrode manufactured in the present embodiment combines between layers
Well, and keep good contact between substrate.
Using four termination electrode methods, interface resistance is measured, Fig. 6 is Ni metal manufactured in the present embodiment and metal Mo layer
Folded（Cu and substrate contact）Alloy electrode and intermediate layer Ti alloy interface contact resistance variation relation schematic diagram.By scheming
6 is visible, and the interface resistance at each interface, between 10-30 μ Ω, compared with overall resistance, is almost negligible.
Fig. 7 is Ni metal and the metal Mo stacking of embodiment 2 preparation（Cu and substrate contact）Alloy electrode and base
Scanning electron microscope (SEM) photograph after 10 thermal shocks for the bottom.As seen from Figure 7, pass through thermal shock 10 times at a temperature of 550 DEG C, alloy electrode with
Interbed Ti alloy substrates interface cohesion is good, there are no crackle and exists, and diffusing phenomenon presence is also not observed in interface.
Embodiment 3
The preparation of intermediate layer Ti alloy substrates is carried out according to described in embodiment 1.
The preparation of alloy electrode：First above-mentioned prepared substrate is fixed on the fixture on electric arc spraying sample stage, presses
According to the spraying parameter having optimized（Spraying current 180A, voltage 30V, atomization air pressure 50-40psi）Sprayed, obtained thickness
Degree is about 500 μm of the uniform mixed layer of metal Mo- Ni metal, that is, obtained Ni metal of the present invention and metal Mo uniformly mixes
The alloy electrode closing.Finally carry out thermal shock experiment, thermal shock experiment condition is identical with described in embodiment 1.
The alloy electrode that Fig. 8 is Ni metal manufactured in the present embodiment and metal Mo is uniformly mixed and intermediate layer Ti alloy
The scanning electron microscope (SEM) photograph that substrate combines.As seen from Figure 8, alloy electrode manufactured in the present embodiment is well combined between layers, and
Good contact is kept between substrate.
Using four termination electrode methods, interface resistance is measured, Fig. 9 is Ni metal manufactured in the present embodiment and metal Mo is equal
The even alloy electrode mixing and the contact resistance variation relation schematic diagram of intermediate layer Ti alloy interface.As seen from Figure 9, interface
Resistance about in 10 μ Ω, compared with overall resistance, is almost negligible.
The alloy electrode that Figure 10 is Ni metal manufactured in the present embodiment and metal Mo is uniformly mixed and substrate are through 10 times
Scanning electron microscope (SEM) photograph after thermal shock.As seen from Figure 10, thermal shock 10 times at a temperature of 550 DEG C, alloy electrode and intermediate layer Ti are passed through
Alloy substrates interface cohesion is good, there are no crackle and exists, and diffusing phenomenon presence is also not observed in interface.
The all documents referring in the present invention are all incorporated as reference in this application, independent just as each document
It is incorporated as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, those skilled in the art can
To make various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (13)
1. a kind of skutterudite-base thermoelectrical component equipment, including：
The thermoelement being formed by the skutterudite-base material with surface；And
The surface being coupled to described thermoelement is for carrying to described thermoelement by electricity or carrying electricity from described thermoelement
At least one electrode, at least one electrode described includes the electrode layer being formed by least two metals, and described electrode layer covers
At least a portion on the surface of described thermoelement, and by the direct or indirect surface with described thermoelement of spraying at least
A part connects, and wherein, described electrode layer includes：Multiple structure, wherein each layer includes one of described at least two metals, its
In, described at least two metals are Cu and Mo.
2. equipment as claimed in claim 1 is it is characterised in that described multiple structure includes at least four subgrades, wherein adjacent
Subgrade be described at least two metals different situations.
3. equipment as claimed in claim 1 is it is characterised in that this equipment meets following performance：
The thickness of each subgrade of described multiple structure is one below：(i)0.01-2.0mm；(ii)0.01-1.0mm；And
(iii)0.05-0.5mm.
4. equipment as claimed in claim 1 is it is characterised in that this equipment also includes：
The boundary layer being formed by titanium or its alloy, described boundary layer covers at least a portion on the surface of described thermoelement, and
Directly or indirectly it is connected with least a portion on the surface of described thermoelement,
Wherein, described electrode layer covers at least a portion of described boundary layer, and directly or indirectly with described boundary layer at least
A part connects.
5. equipment as claimed in claim 4 is it is characterised in that the described boundary layer directly skutterudite-base with described thermoelement
The surface of material connects, and described boundary layer is inserted between described thermoelement and electrode layer, and described electrode layer is directly and institute
State boundary layer to connect.
6. equipment as claimed in claim 4 is it is characterised in that described titanium alloy contains titanium and aluminum.
7. equipment as claimed in claim 4 is it is characterised in that the gross thickness of described boundary layer is one below：(i)0.001-
1mm；(ii)0.005-0.5mm；And (iii) 0.01-0.1mm.
8. a kind of method preparing skutterudite-base thermoelectrical component equipment, the method includes：
The thermoelement being formed by the skutterudite-base material with least one surface is provided；And
In at least a portion on the surface at least one electrode layer being directly or indirectly placed on described thermoelement, and cover institute
State at least a portion on the surface of thermoelement, wherein, at least one electrode layer described is formed by least two metals so that institute
State electrode layer to include：Multiple structure, wherein each layer includes one of described at least two metals,
Wherein, the step at least one electrode layer being placed on the surface of described thermoelement includes will be direct for described electrode layer
Or be indirectly sprayed on the surface of described thermoelement；Described at least two metals are Cu and Mo.
9. method as claimed in claim 8 is it is characterised in that be directly or indirectly sprayed on described thermoelectricity unit by described electrode layer
Step on the surface of part includes：
The ground floor of described at least two metals is directly or indirectly sprayed on the surface of described thermoelement, then will be described
The succeeding layer of at least two metals is sprayed on front layer, is consequently formed different subgrades so that adjacent subgrade is described
The different situations of at least two metals.
10. method as claimed in claim 8 is it is characterised in that the method meets following performance：
The thickness of each subgrade of described multiple structure is one below：(i)0.01-2.0mm；(ii)0.01-1.0mm；And
(iii)0.05-0.5mm.
11. methods as claimed in claim 8 are it is characterised in that the method also includes：The interface that will be formed by titanium or its alloy
In at least a portion on surface that layer is placed on described thermoelement, and directly at least with the surface of described thermoelement
Divide and connect so that described boundary layer is inserted between surface and the electrode layer of described thermoelement, and make described electrode layer direct
Contact with described boundary layer.
12. methods as claimed in claim 11 are it is characterised in that the method meets following at least one performance：
Described boundary layer is formed by titanium；
Described boundary layer is formed by titanium alloy；And
Described boundary layer is formed by the titanium alloy containing titanium and aluminum.
13. methods as claimed in claim 11 are it is characterised in that the gross thickness of described boundary layer is one below：(i)
0.001-1mm；(ii)0.005-0.5mm；And (iii) 0.01-0.1mm.
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| CN106299099B (en) * | 2015-05-19 | 2019-01-29 | 中国科学院上海硅酸盐研究所 | A kind of alloy electrode and preparation method thereof for skutterudite thermoelectric element |
| CN113020736B (en) * | 2021-03-25 | 2022-08-30 | 哈尔滨工业大学 | Brazing connection method for skutterudite thermoelectric material and copper electrode |
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Inventor after: Chen Lidong Inventor after: Li Fei Inventor after: Huang Xiangyang Inventor after: Gu Ming Inventor after: Li Xiaoya Inventor after: Xia Xugui Inventor after: Tang Yunshan Inventor after: He Lin Inventor after: Zhuang Chenggang Inventor before: Chen Lidong Inventor before: Li Fei Inventor before: Huang Xiangyang Inventor before: Gu Ming Inventor before: Li Xiaoya Inventor before: Xia Xugui Inventor before: Tang Yunshan Inventor before: He Lin Inventor before: Zhuang Chenggang |