CN104347788A - Skutterudite-based thermoelectric element equipment and preparation method thereof - Google Patents
Skutterudite-based thermoelectric element equipment and preparation method thereof Download PDFInfo
- Publication number
- CN104347788A CN104347788A CN201310338239.5A CN201310338239A CN104347788A CN 104347788 A CN104347788 A CN 104347788A CN 201310338239 A CN201310338239 A CN 201310338239A CN 104347788 A CN104347788 A CN 104347788A
- Authority
- CN
- China
- Prior art keywords
- thermoelectric element
- metals
- kinds
- alloy
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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, relate to a kind of skutterudite-base thermoelectrical component equipment and preparation method thereof, more particularly, relate to alloy electrode of a kind of skutterudite-base thermoelectrical element and preparation method thereof.
Background technology
Thermoelectric power generation is the complete static direct generation of electricity mode utilizing semiconductor thermoelectric transition material heat energy (temperature difference) to be converted into electric energy, the green energy resource technology meeting environmental protection, for alleviation with solve current growing Pressure on Energy and environmental pollution is significant.Noiseless when thermoelectric heat generation system has compact conformation, dependable performance, an operation, get well without wearing and tearing, No leakage, mobility and be applicable to the features such as low energy densities recycling, being particularly suitable for the recycling of industrial exhaust heat and waste heat of automotive exhaust gas etc.At present, the maturation suitable about the bismuth telluride-based thermoelectric refrigeration device of cryogenic refrigeration and be widely used in commodity production, the components and parts that the thermoelectric material of middle high-temperature power generation is prepared as PbTe and SiGe etc. also start to be applied to space field in developed countries such as America and Europes at present, and large quantifier elimination has done to the oxide pyroelectric material of generating and device in Japan.The thermoelectricity capability of skutterudite-base thermoelectrical material Yin Qigao and other such as factor such as cost and controlled synthesis technology thereof are considered to the most promising middle temperature electricity generation material, and the p-type of doping or filling, its thermoelectric figure of merit of skutterudite-base thermoelectrical material (ZT) of N-shaped have all reached more than 1.0 (Shi Xun; Yang Jiong; The people such as Salvador James R; the skutterudite of the many fillings of Multiple-Filled Skutterudites:High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports(: by separately optimizing electricity and the hot quality factor of height of Heat transmission); JACS, 2011 (133) 7837-7846; Chen Lidong, Liu Ruiheng, Chou Pengfei, " p-type composite square cobalt ore material of a kind of high thermoelectricity capability and preparation method thereof ", CN201010259433.0), but the technology of preparing of its components and parts is still far from perfect, the particularly connectivity problem of electrode, intermediate layer and skutterudite-base thermoelectrical material, key is the generation that will adopt suitable technology of preparing to reduce the mismatch of the thermally coefficient of expansion and serious diffusion reaction.
Generally speaking, the electrode of thermoelectricity components and parts is selected mainly to follow following principle: within the scope of serviceability temperature, electrode and corresponding thermoelectric material and intermediate layer thereof are without serious phase counterdiffusion or reaction, thus ensure that thermoelectric material self performance is unaffected; There are higher conductivity and thermal conductivity to reduce energy loss; There is certain non-oxidizability to ensure reliability and the useful life of device within the scope of serviceability temperature; The thermal coefficient of expansion of electrode material and corresponding thermoelectric material coupling are to prevent from cracking thus to affect thermoelectric transport properties and thermal stability.
Low temperature thermoelectric unit part is not high due to serviceability temperature, Cu and Al etc. generally can be selected as electrode, as Bi in patent documentation JP10012935
2te
3thermoelectric element selects Al as electrode material.But for middle high temperature thermoelectric components and parts, because temperature range span is larger, and the long-term work of thermoelectric device hot junction under the high temperature conditions, thermoelectric material and electrode material very easily crack in interface due to the difference of thermal coefficient of expansion, and therefore the selection of centering high temperature thermoelectric components and parts electrode and Joining Technology have higher requirement.In patent documentation JP11274580 and JP2000100751, PbTe and SiGe thermoelectric device is all have employed Cu electrode.Research at present for skutterudite-base thermoelectrical device is still in laboratory stage, and the electrode of some researchers to skutterudite-base thermoelectric device also uses Ni metal as electrode, as patent documentation JP2004063585.And in fact Cu and CoSb
3thermal expansion coefficient difference excessive (during 373K, Ni metal and skutterudite material thermal expansion coefficient are respectively 18 × 10
-6k
-1with 10 × 10
-6k
-1), be easy to when using under hot conditions cause electrode material and thermoelectric material Interface Cracking.Jet power laboratory of the U.S. (Jet propulsion Laboratory) is once in the international conference of the 20th International Conference on Thermoelectrics(thermoelectricity) reported that list have employed metal Ti as electrode (D.J.Yao to during the thermoelectric power generation of antimony cobalt-based, 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(procceedings) ICT2001.20International Conference on Thermoelectrics (Cat.No.01TH8589), pp.401-404, 2001).But metal Ti is that conductivity and thermal conductivity are relatively low as the shortcoming of electrode, energy consumption is comparatively large, and non-oxidizability is poor, is therefore also not suitable as the electrode material of skutterudite-base thermoelectrical power generating device.A large amount of work has been done on the preparation research of skutterudite-base thermoelectrical device by Shanghai Silicate Inst., Chinese Academy of Sciences, has done large quantifier elimination especially for the selection of electrode material and the connection reliability of skutterudite-base thermoelectrical material and electrode material.In patent documentation CN1585145, Fan etc. adopt metal M o as electrode material, using metal Ti as boundary layer, with discharge plasma sintering (SPS) method achieves electrode, intermediate layer is connected with thermoelectric material, but because the thermal coefficient of expansion of Mo and skutterudite material differ greatly, (during 373K, metal M o and skutterudite material thermal expansion coefficient are respectively 5.4 × 10
-6k
-1with 10 × 10
-6k
-1), and the conductivity of Mo is lower, Mo the electrode material be not suitable for as skutterudite device; In patent documentation CN101101955A and CN100552999C, Zhao etc. adopt alloy material Mo-W and Mo-Cu to come alternative single Ni metal or Mo electrode as electrode, using metal Ti as intermediate layer material, with the method for SPS achieve electrode, intermediate layer is connected with thermoelectric material.But use the method for SPS to realize the connection of electrode, intermediate layer and thermoelectric material, cost is high, complicated operation and be not suitable for producing in batches, and the electrode layer of excessive densification easily causes the temperature end of thermoelectric element still easily to ftracture.
Therefore; in the urgent need to developing, a kind of technique is simple, good reliability, preparation cost are low and the alloy electrode preparation method of the skutterudite-base thermoelectrical element of applicable large-scale production in this area, difference that is low with obtained density, that reduce electrode material and interlayer materials thermal coefficient of expansion bring negative effect, intermediate layer Ti alloy electrical contact performance well and the durability of electrode and thermoelectric element thereof and thermal-shock resistance alloy electrode of good performance.
Summary of the invention
Skutterudite-base thermoelectrical component equipment that the invention provides a kind of novelty and preparation method thereof, thus solve problems of the prior art.The invention provides a kind of alloy electrode be made up of at least two kinds of metals (preferable alloy Cu and metal M o), and adopt a kind of cost low, simple to operate and the method being beneficial to mass-produced preparation method-spraying to realize the good combination of electrode material, intermediate layer and thermoelectric material.
The object of the present invention is to provide a kind of alloy electrode for skutterudite-base thermoelectrical components and parts and preparation method thereof, that is, the invention provides a kind of with skutterudite-base thermoelectrical material heat mate the good alloy electrode be made up of at least two kinds of metals (preferable alloy Cu and metal M o) and the Joining Technology of electrode and skutterudite-base thermoelectrical components and parts intermediate layer used Ti alloy substrates.Technique of the present invention is simple, and the skutterudite-base thermoelectrical device interface prepared is functional, interface reliability is high.
On the one hand, the invention provides a kind of skutterudite-base thermoelectrical component equipment, comprising:
The thermoelectric element formed by the skutterudite-base material with surface; And
Be coupled to the surface of described thermoelectric element for being carried by electricity to described thermoelectric element or at least one electrode from described thermoelectric element live, at least one electrode described comprises the electrode layer formed by least two kinds of metals, described electrode layer covers the surface of described thermoelectric element at least partially, and directly or indirectly with being connected at least partially of the surface of described thermoelectric element, wherein, described electrode layer comprises one of following: (i) the alloy of at least two kinds of metals; And (ii) sandwich construction, wherein each layer comprise described in one of at least two kinds of metals.
In one preferred embodiment, described at least two kinds of metals are selected from: Cu, Mo, Ni, Ti, W, Co and Nb.
Another preferred embodiment in, described at least two kinds of metals are one of following: (i) Cu and Mo; And (ii) Ni and Mo.
Another preferred embodiment in, described sandwich construction comprises at least four subgrades, and wherein adjacent subgrade is the different situations of described at least two kinds of metals.
Another preferred embodiment in, this equipment meets following at least one performance:
The gross thickness of described electrode layer is one of following: (i) 0.02-20.0mm; (ii) 0.05-10.0mm; And (iii) 0.1-1.5mm; And
The thickness of each subgrade of described sandwich construction is one of following: (i) 0.01-2.0mm; (ii) 0.01-1.0mm; And (iii) 0.05-0.5mm.
Another preferred embodiment in, this equipment also comprises:
The boundary layer formed by titanium or its alloy, described boundary layer covers the surface of described thermoelectric element at least partially, and directly or indirectly with being connected at least partially of the surface of described thermoelectric element,
Wherein, described electrode layer covers described boundary layer at least partially, and directly or indirectly with being connected at least partially of described boundary layer.
Another preferred embodiment in, described boundary layer is directly connected with the surface of the skutterudite-base material of described thermoelectric element, and described boundary layer is inserted between described thermoelectric element and electrode layer, and described electrode layer is directly connected with described boundary layer.
Another preferred embodiment in, described titanium alloy contains titanium and aluminium.
Another preferred embodiment in, the gross thickness of described boundary layer is one of following: (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 comprises:
The thermoelectric element formed by the skutterudite-base material with at least one surface is provided; And
At least one electrode layer is directly or indirectly placed on going up at least partially of the surface of described thermoelectric element, and the surface covering described thermoelectric element at least partially, wherein, at least one electrode layer described is formed by least two kinds of metals, described electrode layer is comprised one of following: (i) the alloy of at least two kinds of metals; And (ii) sandwich construction, wherein each layer comprise described in one of at least two kinds of metals.
In one preferred embodiment, the step be placed on by least one electrode layer on the surface of described thermoelectric element comprises and being directly or indirectly sprayed on the surface of described thermoelectric element by described electrode layer.
Another preferred embodiment in, the step be directly or indirectly sprayed on by described electrode layer on the surface of described thermoelectric element comprises one of following:
(i) one or more layers alloy-layer of described at least two kinds of metals is directly or indirectly sprayed on the surface of described thermoelectric element; And
(ii) the ground floor of described at least two kinds of metals is directly or indirectly sprayed on the surface of described thermoelectric element, then the succeeding layer of described at least two kinds of metals is sprayed on front layer, form different subgrades thus, make adjacent subgrade be the different situations of described at least two kinds of metals.
Another preferred embodiment in, described at least two kinds of metals are selected from: Cu, Mo, Ni, Ti, W, Co and Nb.
Another preferred embodiment in, described at least two kinds of metals are one of following: (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 of following: (i) 0.02-20.0mm; (ii) 0.05-10.0mm; And (iii) 0.1-1.5mm; And
The thickness of each subgrade of described sandwich construction is one of following: (i) 0.01-2.0mm; (ii) 0.01-1.0mm; And (iii) 0.05-0.5mm.
Another preferred embodiment in, the method also comprises: the boundary layer formed by titanium or its alloy is placed on going up at least partially of the surface of described thermoelectric element, and directly with being connected at least partially of the surface of described thermoelectric element, between the surface making described boundary layer be inserted in described thermoelectric element and electrode layer, and described electrode layer is directly contacted with described boundary layer.
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 aluminium.
Another preferred embodiment in, the gross thickness of described boundary layer is one of following: (i) 0.001-1mm; (ii) 0.005-0.5mm; And (iii) 0.01-0.1mm.
Accompanying drawing explanation
Fig. 1 is the structural representation that a kind of stacked alloy electrode provided by the invention is connected with intermediate layer Ti alloy substrates, as shown in Figure 1, Ni metal layer 2 is placed on intermediate layer Ti alloy 1, and metal M o layer 3 is placed on Ni metal layer 2, then sets gradually Ni metal layer and metal M o layer above.
Fig. 2 is the Ni metal prepared of embodiment 1 and the stacked alloy electrode of (Mo and substrate contact) of metal M o and the scanning electron microscope (SEM) photograph of metal Ti alloy substrates.
Fig. 3 is the Ni metal prepared of embodiment 1 and the alloy electrode of metal M o stacked (Mo and substrate contact) and the contact resistance variation relation schematic diagram at metal Ti alloy substrates interface.
Fig. 4 is the Ni metal prepared of embodiment 1 and the alloy electrode of metal M o stacked (Mo and substrate contact) and metal Ti alloy substrates at 550 DEG C-0 DEG C scanning electron microscope (SEM) photograph after 10 thermal shocks.
Fig. 5 is the Ni metal prepared of embodiment 2 and the stacked alloy electrode of (Cu and substrate contact) of metal M o and the scanning electron microscope (SEM) photograph of metal Ti alloy substrates.
Fig. 6 is the Ni metal prepared of embodiment 2 and the alloy electrode of metal M o stacked (Cu and substrate contact) and the contact resistance variation relation schematic diagram at metal Ti alloy substrates interface.
Fig. 7 is the Ni metal prepared of embodiment 2 and the alloy electrode of metal M o stacked (Cu and substrate contact) and metal Ti alloy substrates at 550 DEG C-0 DEG C scanning electron microscope (SEM) photograph after 10 thermal shocks.
Fig. 8 is the scanning electron microscope (SEM) photograph that the Ni metal of embodiment 3 preparation and the alloy electrode of metal M o Homogeneous phase mixing are combined with intermediate layer Ti alloy substrates.
Fig. 9 is the Ni metal prepared of embodiment 3 and the alloy electrode of metal M o Homogeneous phase mixing and the contact resistance variation relation schematic diagram of intermediate layer Ti alloy interface.
Figure 10 is the Ni metal prepared of embodiment 3 and the alloy electrode of metal M o Homogeneous phase mixing and the scanning electron microscope (SEM) photograph of substrate after 10 thermal shocks.
Embodiment
The present inventor finds after have passed through extensive and deep research, by at least two kinds of metals (preferable alloy Cu and metal M o) component alloy electrode, using the intermediate layer Ti alloy of skutterudite-base thermoelectrical element as substrate, the connection of at least two kinds of metals and intermediate layer Ti alloy substrates described in the method realization of utilization spraying, can obtain being combined well with intermediate layer Ti alloy substrates, interface resistance is low, interface exists there are no crackle and obvious diffusion phenomena, can stand the alloy electrode of the skutterudite-base thermoelectrical element of long thermal shock test and ageing test.Based on above-mentioned discovery, the present invention is accomplished.
Technical conceive of the present invention is as follows:
Select at least two kinds of metals (preferable alloy Cu and metal M o) as alloy electrode material, adopt the method for spraying to realize the connection of alloy electrode and skutterudite-base thermoelectrical components and parts intermediate layer used Ti alloy substrates.
In the present invention, the version of described alloy electrode material can be laminated at least two kinds of metals (preferable alloy Cu and metal M o), also can form at least two kinds of metal (preferable alloy Cu and metal M o) Homogeneous phase mixing.
In the present invention, the spraying method adopted is electric arc spraying, flame-spraying or plasma spraying.Be preferably the method for electric arc spraying.
In the present invention, the described alloy electrode be laminated by least two kinds of metals (preferable alloy Cu and metal M o), its total thickness is 0.02-20.0mm, is preferably 0.05-10.0mm, is more preferably 0.1-1.5mm.
In the present invention, the described alloy electrode be laminated by least two kinds of metals (preferable alloy Cu and metal M o), its thickness of every layer is 0.01-2.0mm, is preferably 0.01-1.0mm, is more preferably 0.05-0.5mm.
In the present invention, the described alloy electrode be laminated by least two kinds of metals (preferable alloy Cu and metal M o) can be Ni metal and metal M o is respectively one deck, can be respectively for two-layer, also can be respectively N(N>2) layer.
In the present invention, the described alloy electrode be laminated by least two kinds of metals (preferable alloy Cu and metal M o) can be that Ni metal is connected with substrate as alloy electrode ground floor, also can be that metal M o is connected with substrate as alloy electrode ground floor.
In the present invention, the described alloy electrode by least two kinds of metals (preferable alloy Cu and metal M o) Homogeneous phase mixing, the ratio of its Cu and Mo can regulate and control.
In the present invention, the described alloy electrode by least two kinds of metals (preferable alloy Cu and metal M o) Homogeneous phase mixing, Cu:Mo is 100:1 to 1:100, is preferably 10:1 to 1:10.
In the present invention, described intermediate layer Ti alloy substrates can be pure metal Ti, also can be the alloy that Ti and other metals are formed.
In the present invention, the preparation method of the described alloy electrode be made up of at least two kinds of metals (preferable alloy Cu and metal M o) comprises the steps: to take a certain amount of metal Ti powder, load in graphite jig, then carry out hot pressed sintering in a vacuum, obtain fine and close metal Ti block; Again to sinter the metal Ti of gained as substrate, the preparation of the method for spraying is utilized to be laminated by least two kinds of metals (preferable alloy Cu and metal M o) or by the alloy electrode of at least two kinds of metals (preferable alloy Cu and metal M o) Homogeneous phase mixing.
Major advantage of the present invention is:
Compared with prior art, the alloy electrode be made up of at least two kinds of metals (preferable alloy Cu and metal M o) adopting the method for spraying to prepare provided by the invention, the Mo-Cu alloy of the Mo-Cu sheet that its density is bought compared with market and sintering gained is lower slightly, under the prerequisite not affecting the electrical property of its alloy electrode own and interface electrical property, the negative effect that the difference reducing electrode material and interlayer materials thermal coefficient of expansion is brought.The present invention has obtained the alloy electrode good with intermediate layer Ti alloy electrical contact performance, and durability and the thermal-shock resistance of electrode and thermoelectric element thereof are functional.The alloy electrode of skutterudite-base thermoelectrical element provided by the invention is combined well with intermediate layer Ti alloy substrates, and interface resistance is low.Interface exists there are no crackle and obvious diffusion phenomena, can stand long thermal shock test and ageing test.In addition, preparation method of the present invention also has that technique is simple, good reliability, preparation cost are low and the advantage such as applicable large-scale production.
Embodiment
The present invention is set forth further below in conjunction with specific embodiment.But, should be understood that these embodiments only do not form limitation of the scope of the invention for illustration of the present invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Except as otherwise noted, all percentage and number are by weight.
Embodiment 1
The preparation of Ti alloy substrates: taking about 1.8g metal Ti powder loading diameter is in the graphite jig of 10mm, then carry out discharge plasma sintering under vacuo: vacuum degree is 10Pa, 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 with stove cool to room temperature, obtain required intermediate layer Ti alloy substrates.
The preparation of alloy electrode: first above-mentioned obtained Ti alloy substrates is fixed on the fixture on electric arc spraying sample stage, according to technological parameter (the spraying current 180A of the spray metal Mo optimized, voltage 35V, atomization air pressure 60-50psi) spray, obtain the metal M o layer that thickness is about 100 μm, again according to technological parameter (the spraying current 160A of the spray metal Cu optimized, voltage 28V, atomization air pressure 50-40psi) spray, obtain the Ni metal layer that thickness is about 250 μm, circulate 3 times, namely the alloy electrode that Ni metal of the present invention and metal M o are laminated is obtained, its structural representation as shown in Figure 1.Finally carry out thermal shock experiment, the thermal shock experiment condition of carrying out is: the alloy electrode sample prepared is loaded quartz ampoule, and it is be incubated ten minutes in the Muffle furnace of 550 DEG C that tube sealing is placed on temperature, then frozen water chilling is put in taking-up, so circulation 10 times.
Fig. 2 is the scanning electron microscope (SEM) photograph that the alloy electrode of the Ni metal prepared of the present embodiment and metal M o stacked (Mo and substrate contact) is combined with intermediate layer Ti alloy substrates.As seen from Figure 2: alloy electrode prepared by the present embodiment combines well between layers, and and substrate between keep good contact.
Adopt four termination electrode methods to measure interface resistance, Fig. 3 is the Ni metal prepared of the present embodiment and the alloy electrode of metal M o stacked (Mo and substrate contact) and the contact resistance variation relation schematic diagram of intermediate layer Ti alloy interface.As seen from Figure 3, the interface resistance at each interface is between 10-30 μ Ω, compared with overall resistance, almost negligible.
Fig. 4 is alloy electrode and the scanning electron microscope (SEM) photograph of intermediate layer Ti alloy substrates after 10 thermal shocks of the Ni metal prepared of the present embodiment and metal M o stacked (Mo and substrate contact).As seen from Figure 4, through thermal shock at the temperature of 550 DEG C 10 times, alloy electrode and intermediate layer Ti alloy substrates interface cohesion well, exist there are no crackle, and also do not observe diffusion phenomena in interface.
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 obtained substrate is fixed on the fixture on electric arc spraying sample stage, according to technological parameter (the spraying current 160A of the spray metal Cu optimized, voltage 28V, atomization air pressure 50-40psi) spray, obtain the Ni metal layer that thickness is about 250 μm, again according to technological parameter (the spraying current 180A of the spray metal Mo optimized, voltage 35V, atomization air pressure 60-50psi) spray, obtain the metal M o layer that thickness is about 100 μm, such circulation 3 times, namely the alloy electrode that Ni metal of the present invention and metal M o are laminated is obtained.Finally carry out thermal shock experiment, thermal shock experiment condition is identical with described in embodiment 1.
Fig. 5 is the scanning electron microscope (SEM) photograph that the alloy electrode of the Ni metal prepared of the present embodiment and metal M o stacked (Cu and substrate contact) is combined with intermediate layer Ti alloy substrates.As seen from Figure 5, alloy electrode prepared by the present embodiment combines well between layers, and and substrate between keep good contact.
Adopt four termination electrode methods to measure interface resistance, Fig. 6 is the Ni metal prepared of the present embodiment and the alloy electrode of metal M o stacked (Cu and substrate contact) and the contact resistance variation relation schematic diagram of intermediate layer Ti alloy interface.As seen from Figure 6, the interface resistance at each interface is between 10-30 μ Ω, compared with overall resistance, almost negligible.
Fig. 7 is the Ni metal prepared of embodiment 2 and the alloy electrode of metal M o stacked (Cu and substrate contact) and the scanning electron microscope (SEM) photograph of substrate after 10 thermal shocks.As seen from Figure 7, through thermal shock at the temperature of 550 DEG C 10 times, alloy electrode and intermediate layer Ti alloy substrates interface cohesion well, exist there are no crackle, and also do not observe diffusion phenomena 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 obtained substrate is fixed on the fixture on electric arc spraying sample stage, according to the spraying parameter optimized (spraying current 180A, voltage 30V, atomization air pressure 50-40psi) spray, obtain the metal M o-Ni metal Homogeneous phase mixing layer that thickness is about 500 μm, namely obtain the alloy electrode of Ni metal of the present invention and metal M o Homogeneous phase mixing.Finally carry out thermal shock experiment, thermal shock experiment condition is identical with described in embodiment 1.
Fig. 8 is the scanning electron microscope (SEM) photograph that the alloy electrode of the Ni metal prepared of the present embodiment and metal M o Homogeneous phase mixing is combined with intermediate layer Ti alloy substrates.As seen from Figure 8, alloy electrode prepared by the present embodiment combines well between layers, and and substrate between keep good contact.
Adopt four termination electrode methods to measure interface resistance, Fig. 9 is the Ni metal prepared of the present embodiment and the alloy electrode of metal M o Homogeneous phase mixing and the contact resistance variation relation schematic diagram of intermediate layer Ti alloy interface.As seen from Figure 9, interface resistance is about 10 μ Ω, compared with overall resistance, almost negligible.
Figure 10 is alloy electrode and the scanning electron microscope (SEM) photograph of substrate after 10 thermal shocks of the Ni metal prepared of the present embodiment and metal M o Homogeneous phase mixing.As seen from Figure 10, through thermal shock at the temperature of 550 DEG C 10 times, alloy electrode and intermediate layer Ti alloy substrates interface cohesion well, exist there are no crackle, and also do not observe diffusion phenomena in interface.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (18)
1. a skutterudite-base thermoelectrical component equipment, comprising:
The thermoelectric element formed by the skutterudite-base material with surface; And
Be coupled to the surface of described thermoelectric element for being carried by electricity to described thermoelectric element or at least one electrode from described thermoelectric element live, at least one electrode described comprises the electrode layer formed by least two kinds of metals, described electrode layer covers the surface of described thermoelectric element at least partially, and directly or indirectly with being connected at least partially of the surface of described thermoelectric element, wherein, described electrode layer comprises one of following: (i) the alloy of at least two kinds of metals; And (ii) sandwich construction, wherein each layer comprise described in one of at least two kinds of metals.
2. equipment as claimed in claim 1, it is characterized in that, described at least two kinds of metals are selected from: Cu, Mo, Ni, Ti, W, Co and Nb.
3. equipment as claimed in claim 1, is characterized in that, described at least two kinds of metals are one of following: (i) Cu and Mo; And (ii) Ni and Mo.
4. equipment as claimed in claim 1, it is characterized in that, described sandwich construction comprises at least four subgrades, and wherein adjacent subgrade is the different situations of described at least two kinds of metals.
5. equipment as claimed in claim 1, it is characterized in that, this equipment meets following at least one performance:
The gross thickness of described electrode layer is one of following: (i) 0.02-20.0mm; (ii) 0.05-10.0mm; And (iii) 0.1-1.5mm; And
The thickness of each subgrade of described sandwich construction is one of following: (i) 0.01-2.0mm; (ii) 0.01-1.0mm; And (iii) 0.05-0.5mm.
6. equipment as claimed in claim 1, it is characterized in that, this equipment also comprises:
The boundary layer formed by titanium or its alloy, described boundary layer covers the surface of described thermoelectric element at least partially, and directly or indirectly with being connected at least partially of the surface of described thermoelectric element,
Wherein, described electrode layer covers described boundary layer at least partially, and directly or indirectly with being connected at least partially of described boundary layer.
7. equipment as claimed in claim 6, it is characterized in that, described boundary layer is directly connected with the surface of the skutterudite-base material of described thermoelectric element, and described boundary layer is inserted between described thermoelectric element and electrode layer, and described electrode layer is directly connected with described boundary layer.
8. equipment as claimed in claim 6, it is characterized in that, described titanium alloy contains titanium and aluminium.
9. equipment as claimed in claim 6, is characterized in that, the gross thickness of described boundary layer is one of following: (i) 0.001-1mm; (ii) 0.005-0.5mm; And (iii) 0.01-0.1mm.
10. prepare a method for skutterudite-base thermoelectrical component equipment, the method comprises:
The thermoelectric element formed by the skutterudite-base material with at least one surface is provided; And
At least one electrode layer is directly or indirectly placed on going up at least partially of the surface of described thermoelectric element, and the surface covering described thermoelectric element at least partially, wherein, at least one electrode layer described is formed by least two kinds of metals, described electrode layer is comprised one of following: (i) the alloy of at least two kinds of metals; And (ii) sandwich construction, wherein each layer comprise described in one of at least two kinds of metals.
11. methods as claimed in claim 10, is characterized in that, the step be placed on by least one electrode layer on the surface of described thermoelectric element comprises and being directly or indirectly sprayed on the surface of described thermoelectric element by described electrode layer.
12. methods as claimed in claim 11, is characterized in that, the step be directly or indirectly sprayed on by described electrode layer on the surface of described thermoelectric element comprises one of following:
(i) one or more layers alloy-layer of described at least two kinds of metals is directly or indirectly sprayed on the surface of described thermoelectric element; And
(ii) the ground floor of described at least two kinds of metals is directly or indirectly sprayed on the surface of described thermoelectric element, then the succeeding layer of described at least two kinds of metals is sprayed on front layer, form different subgrades thus, make adjacent subgrade be the different situations of described at least two kinds of metals.
13. methods as claimed in claim 10, it is characterized in that, described at least two kinds of metals are selected from: Cu, Mo, Ni, Ti, W, Co and Nb.
14. methods as claimed in claim 10, is characterized in that, described at least two kinds of metals are one of following: (i) Cu and Mo; And (ii) Ni and Mo.
15. methods as claimed in claim 10, it is characterized in that, the method meets following at least one performance:
The gross thickness of described electrode layer is one of following: (i) 0.02-20.0mm; (ii) 0.05-10.0mm; And (iii) 0.1-1.5mm; And
The thickness of each subgrade of described sandwich construction is one of following: (i) 0.01-2.0mm; (ii) 0.01-1.0mm; And (iii) 0.05-0.5mm.
16. methods as claimed in claim 10, it is characterized in that, the method also comprises: the boundary layer formed by titanium or its alloy is placed on going up at least partially of the surface of described thermoelectric element, and directly with being connected at least partially of the surface of described thermoelectric element, between the surface making described boundary layer be inserted in described thermoelectric element and electrode layer, and described electrode layer is directly contacted with described boundary layer.
17. methods as claimed in claim 16, it is characterized 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 aluminium.
18. methods as claimed in claim 16, is characterized in that, the gross thickness of described boundary layer is one of following: (i) 0.001-1mm; (ii) 0.005-0.5mm; And (iii) 0.01-0.1mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310338239.5A CN104347788B (en) | 2013-08-05 | 2013-08-05 | Skutterudite-based thermoelectric element equipment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310338239.5A CN104347788B (en) | 2013-08-05 | 2013-08-05 | Skutterudite-based thermoelectric element equipment and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104347788A true CN104347788A (en) | 2015-02-11 |
| CN104347788B CN104347788B (en) | 2017-02-15 |
Family
ID=52502960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310338239.5A Active CN104347788B (en) | 2013-08-05 | 2013-08-05 | Skutterudite-based thermoelectric element equipment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104347788B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299099A (en) * | 2015-05-19 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | A kind of alloy electrode for skutterudite thermoelectric element and preparation method thereof |
| CN113020736A (en) * | 2021-03-25 | 2021-06-25 | 哈尔滨工业大学 | Brazing connection method for skutterudite thermoelectric material and copper electrode |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585145A (en) * | 2004-05-28 | 2005-02-23 | 中国科学院上海硅酸盐研究所 | Electrode material of cobalt base antimonide pyroelectric material and preparing process thereof |
| CN101022149A (en) * | 2007-03-02 | 2007-08-22 | 中国科学院上海硅酸盐研究所 | Alloy electrod matched with cobalt antimonide thermoelectric component and one-step process connecting technology |
| CN101101955A (en) * | 2007-07-03 | 2008-01-09 | 中国科学院上海硅酸盐研究所 | Alloy pole for cobalt antimonides-based thermal electrical part and part making method |
| CN101114692A (en) * | 2007-08-10 | 2008-01-30 | 中国科学院上海硅酸盐研究所 | Method for manufacturing cobalt stibium antimonide based thermoelectric device |
| CN101136450A (en) * | 2007-10-16 | 2008-03-05 | 中国科学院上海硅酸盐研究所 | Pi type CoSb3 based thermoelectric converting device and method for producing the same |
| US20100096357A1 (en) * | 2005-02-15 | 2010-04-22 | Yamaha Corporation | Thermoelectric module and manufacturing method for same |
| CN101828278A (en) * | 2007-10-15 | 2010-09-08 | 住友化学株式会社 | Thermoelectric conversion module |
| CN101847686A (en) * | 2009-03-26 | 2010-09-29 | 中国科学院上海硅酸盐研究所 | Thermoelectric device, electrode material and manufacturing method thereof |
| CN102412366A (en) * | 2011-09-30 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Bismuth-telluride-based thermoelectric element and preparation method thereof |
-
2013
- 2013-08-05 CN CN201310338239.5A patent/CN104347788B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585145A (en) * | 2004-05-28 | 2005-02-23 | 中国科学院上海硅酸盐研究所 | Electrode material of cobalt base antimonide pyroelectric material and preparing process thereof |
| US20100096357A1 (en) * | 2005-02-15 | 2010-04-22 | Yamaha Corporation | Thermoelectric module and manufacturing method for same |
| CN101022149A (en) * | 2007-03-02 | 2007-08-22 | 中国科学院上海硅酸盐研究所 | Alloy electrod matched with cobalt antimonide thermoelectric component and one-step process connecting technology |
| CN101101955A (en) * | 2007-07-03 | 2008-01-09 | 中国科学院上海硅酸盐研究所 | Alloy pole for cobalt antimonides-based thermal electrical part and part making method |
| CN101114692A (en) * | 2007-08-10 | 2008-01-30 | 中国科学院上海硅酸盐研究所 | Method for manufacturing cobalt stibium antimonide based thermoelectric device |
| CN101828278A (en) * | 2007-10-15 | 2010-09-08 | 住友化学株式会社 | Thermoelectric conversion module |
| CN101136450A (en) * | 2007-10-16 | 2008-03-05 | 中国科学院上海硅酸盐研究所 | Pi type CoSb3 based thermoelectric converting device and method for producing the same |
| CN101847686A (en) * | 2009-03-26 | 2010-09-29 | 中国科学院上海硅酸盐研究所 | Thermoelectric device, electrode material and manufacturing method thereof |
| CN102412366A (en) * | 2011-09-30 | 2012-04-11 | 中国科学院上海硅酸盐研究所 | Bismuth-telluride-based thermoelectric element and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106299099A (en) * | 2015-05-19 | 2017-01-04 | 中国科学院上海硅酸盐研究所 | A kind of alloy electrode for skutterudite thermoelectric element and preparation method thereof |
| 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 |
| CN113020736A (en) * | 2021-03-25 | 2021-06-25 | 哈尔滨工业大学 | Brazing connection method for skutterudite thermoelectric material and copper electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104347788B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102449790B (en) | Thermoelectric material coated with a protective layer | |
| Zhang et al. | Thermoelectric devices for power generation: recent progress and future challenges | |
| JP5042245B2 (en) | Doped lead telluride for thermoelectric applications | |
| Zhao et al. | Fabrication of a CoSb3-based thermoelectric module | |
| CN100583478C (en) | Pi type CoSb3 based thermoelectric converting device and method for producing the same | |
| Nemoto et al. | Development of an Mg 2 Si unileg thermoelectric module using durable Sb-doped Mg 2 Si legs | |
| CN103219456B (en) | A kind of electrode matched with Mg-Si-Sn base thermoelement and Joining Technology thereof | |
| JP5468554B2 (en) | Semiconductor materials containing doped tin telluride for thermoelectric applications | |
| CN104263986B (en) | A kind of method of supper-fast preparation high-performance SnTe base thermoelectricity material | |
| EP2913857B1 (en) | Mg-Si THERMOELECTRIC CONVERSION MATERIAL, METHOD FOR PRODUCING SAME, SINTERED BODY FOR THERMOELECTRIC CONVERSION, THERMOELECTRIC CONVERSION ELEMENT, AND THERMOELECTRIC CONVERSION MODULE | |
| Pei et al. | Development of integrated two-stage thermoelectric generators for large temperature difference | |
| CN104646671B (en) | A kind of supper-fast preparation Cu2the method of Se base thermoelectric power generating component | |
| Nemoto et al. | Improvement in the durability and heat conduction of uni-leg thermoelectric modules using n-type Mg 2 Si legs | |
| CN103579482B (en) | Bismuth telluride-based thermoelectric generating element and preparation method thereof | |
| CN107794387B (en) | A kind of supper-fast preparation β-Zn4Sb3The method of base block thermoelectric material | |
| CN106159077A (en) | A kind of bismuth telluride-based thermoelectric generating element and preparation method thereof | |
| CN106145062A (en) | A kind of method quickly preparing antimony telluride thermoelectric material | |
| CN103413889B (en) | A kind of bismuth telluride-based thermoelectric device and preparation method thereof | |
| CN104347788A (en) | Skutterudite-based thermoelectric element equipment and preparation method thereof | |
| CN109065697A (en) | A kind of annular Thermoelectric Generator | |
| CN109065700A (en) | A kind of preparation method of annular Thermoelectric Generator | |
| CN105633267B (en) | A kind of Cu2‑xS/CNT composite thermoelectric materials and preparation method thereof | |
| CN107665943A (en) | Thermo-electric device electrode and preparation method thereof and thermo-electric device | |
| CN207529976U (en) | Thermo-electric device and its electrode | |
| CN104362249A (en) | Layered electrode matched with Mg-Si-Sn-based thermoelectric element and connecting technology thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
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 |
|
| CB03 | Change of inventor or designer information |