CN119952173B - A high thermal stability welding method for skutterudite thermoelectric material/electrode based on metal-ceramic composite barrier layer - Google Patents
A high thermal stability welding method for skutterudite thermoelectric material/electrode based on metal-ceramic composite barrier layerInfo
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Abstract
一种基于金属陶瓷复合阻隔层的方钴矿热电材料/电极高热稳定焊接方法，涉及一种用于方钴矿基热电材料与金属电极的连接方法。为了解决方钴矿与金属电极之间存在剧烈的元素扩散，使得其强度和界面电阻增大，进而焊接接头强度低和服役寿命降低的问题。本发明以金属陶瓷复合相作为扩散阻隔层的连接强度高，接头电阻低，长期服役下反应层厚度增长缓慢，因此保持良好的力学性能与使用性能。本发明可以通过选择不同的难熔金属和陶瓷调控整体阻隔层的组成和比例，可以通过控制焊接温度及保温时间可以控制界面反应层的种类、厚度及分布方式，进而控制焊接接头的强度及热/电输运性能。
A high thermal stability welding method for skutterudite thermoelectric materials/electrodes based on a metal-ceramic composite barrier layer relates to a method for connecting skutterudite-based thermoelectric materials and metal electrodes. In order to solve the problem that there is intense element diffusion between skutterudite and metal electrodes, which increases their strength and interface resistance, and thus the weld joint strength is low and the service life is reduced. The present invention uses a metal-ceramic composite phase as a diffusion barrier layer, which has high connection strength and low joint resistance. The reaction layer thickness increases slowly under long-term service, thereby maintaining good mechanical properties and performance. The present invention can regulate the composition and proportion of the overall barrier layer by selecting different refractory metals and ceramics, and can control the type, thickness and distribution of the interface reaction layer by controlling the welding temperature and holding time, thereby controlling the strength and heat/electricity transport performance of the weld joint.
Description
Technical Field
The invention relates to a skutterudite thermoelectric material/electrode welding method.
Background
Thermoelectric materials are an important class of materials with the function of converting heat energy and electric energy. By utilizing the Seebeck effect and the Peltier effect, the material has wide application in thermoelectric generation and thermoelectric refrigeration. Skutterudite thermoelectric material (SKD) is used as a representative of intermediate-temperature thermoelectric material, and the service temperature range is 300-600 ℃ because of good thermoelectric property and mechanical property, and has practical application potential.
The last step in the manufacture of thermoelectric devices is to connect the thermoelectric material with the metal electrode, but there is severe diffusion of elements between skutterudite and the metal electrode, so that the strength and interface resistance of the thermoelectric device are increased, and the service life is greatly reduced. At present, no barrier layer metal material capable of meeting long-term service requirements of skutterudite thermoelectric materials exists. Therefore, it is very important to design a method for achieving a reliable connection between skutterudite thermoelectric material and metal electrode for a long period of time.
Conventional metal barrier layers exhibit brittle phases after bonding to skutterudites, and the proportion of brittle phases can be reduced to some extent by adding refractory metals, but often the bonding strength is low due to the difference in thermal expansion coefficients. If other metals are added, the overall diffusion-preventing effect is deteriorated due to the reaction with skutterudite. In summary, the reaction layer between the added barrier layer and skutterudite has a lower strength than the base material while having a higher interfacial resistivity than the base material, so that the reduction of the thickness of the reaction layer is a core purpose of the barrier layer. Therefore, the invention has great practical significance in the reliable connection method of skutterudite thermoelectric material and metal electrode.
Disclosure of Invention
The invention aims to solve the problems that the strength and interface resistance of skutterudite are increased due to severe element diffusion between skutterudite and a metal electrode, and further the strength of a welded joint is low and the service life is reduced.
The skutterudite thermoelectric material/electrode high-thermal stability welding method based on the metal ceramic composite barrier layer comprises the following steps of:
1. The method comprises the steps of performing hot-pressing sintering on a skutterudite thermoelectric material and a barrier layer to obtain skutterudite with a preset barrier layer, wherein the surface of the barrier layer in the skutterudite with the preset barrier layer is a surface to be welded, and respectively pre-treating the surface to be welded of the skutterudite with the preset barrier layer and the surface to be welded of a metal electrode;
Spreading a layer of skutterudite powder in a graphite die, spreading a layer of metal ceramic composite barrier layer powder on the skutterudite powder, and finally performing hot-pressing sintering;
the hot-pressed sintering process comprises heating to 650-760 deg.C at a rate of 10-20 deg.C/min under vacuum condition at a pressure of 40-70MPa, maintaining for 5-30min, and cooling to room temperature at a rate of 20-50 deg.C/min;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is one or more of Mo, V, zr, nb, ta, re, ti, the ceramic powder is one or more of M xSiy、MxNy、MxOy, wherein M is one or more of Ti, zr, mg, al, K, ca, zn, mn, and the mole percentage of the refractory metal powder in the metal ceramic composite barrier layer powder is 60-90%;
2. Assembling skutterudite of a preset barrier layer and a metal electrode, wherein the face to be welded of the skutterudite of the preset barrier layer faces the face to be welded of the metal electrode, placing brazing filler metal between the face to be welded of the skutterudite of the preset barrier layer and the face to be welded of the electrode to obtain a piece to be welded, and finally welding, wherein the welding process comprises the steps of heating to 600-700 ℃ at a rate of 10-20 ℃ and preserving heat for 5-30min in a vacuum brazing furnace with a vacuum degree of below 5X 10 -3 Pa, and then cooling to room temperature at a rate of 10-50 ℃ per min.
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, and a metal ceramic composite phase is formed after hot pressing and sintering, wherein the metal ceramic composite phase is used as a barrier layer, no serious interface reaction exists between the barrier layer, a skutterudite thermoelectric material and a metal electrode in the welding process, and the element diffusion is slow at the metal ceramic composite phase. Meanwhile, compared with the existing Ti barrier layer, the brittle reaction layer of the metal ceramic composite phase is reduced in overall proportion, and the reaction layer degree is also reduced overall. The high thermal expansion coefficient of the ceramic in the metal ceramic composite phase adjusts the integral thermal expansion coefficient, the connection strength is higher, the problem that other metals can react with skutterudite when adjusting the thermal expansion coefficient is also avoided, and the integral diffusion resistance effect is not damaged. Therefore, the metal ceramic composite phase is used as the diffusion barrier layer, the connection strength is high, the joint resistance is low, the thickness of the reaction layer grows slowly under long-term service, and the thickness of the reaction layer only grows from 9.5 mu m to 14.5 mu m after the annealing for 135 hours through test, so that good mechanical property and service performance are maintained. The invention can regulate the composition and proportion of the integral barrier layer by selecting different refractory metals and ceramics, can control the type, thickness and distribution mode of the interface reaction layer by controlling the welding temperature and the heat preservation time, and further control the strength and the heat/electricity transport performance of the welding joint.
The invention relates to another skutterudite thermoelectric material/electrode high-thermal stability welding method based on a metal ceramic composite barrier layer, which comprises the following steps of:
1. Firstly, performing hot-pressing sintering on skutterudite powder to obtain skutterudite, performing hot-pressing sintering on metal ceramic composite barrier layer powder to obtain a preset barrier layer, then performing pretreatment on the surface to be welded of skutterudite, the surface to be welded of a metal electrode and two surfaces of the preset barrier layer, and finally storing the treated skutterudite, the treated metal electrode and the treated preset barrier layer in an anaerobic or inert atmosphere;
the hot-pressing sintering process of skutterudite powder into skutterudite comprises heating to 650-760 deg.C at a rate of 10-20 deg.C/min under vacuum condition at a pressure of 40-70MPa, maintaining for 5-30min, and cooling to room temperature at a rate of 20-50 deg.C/min;
the hot-pressing sintering process of the metal ceramic composite barrier layer powder into a preset barrier layer comprises heating to 650-760 ℃ at a rate of 10-20 ℃ per minute under the condition of vacuum and under the condition of applying 40-70MPa, preserving heat for 5-30min, and cooling to room temperature at a rate of 20-50 ℃ per minute;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is one or more of Mo, V, zr, nb, ta, re, ti, the ceramic powder is one or more of M xSiy、MxNy、MxOy, wherein M is one or more of Ti, zr, mg, al, K, ca, zn, mn, and the mole percentage of the refractory metal powder in the metal ceramic composite barrier layer powder is 60-90%;
2. And placing a preset barrier layer between the skutterudite surface to be welded and the metal electrode surface to be welded to obtain a piece to be welded, and finally welding, wherein the welding process comprises the steps of applying pressure of 5-20MPa in a vacuum brazing furnace with the vacuum degree of below 5X 10 -3 Pa, heating to 600-700 ℃ at the speed of 10-20 ℃ per minute, preserving heat for 5-30 minutes, and then cooling to room temperature at the speed of 10-50 ℃ per minute.
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, and a metal ceramic composite phase is formed after hot pressing and sintering, wherein the metal ceramic composite phase is used as a barrier layer, no serious interface reaction exists between the barrier layer, a skutterudite thermoelectric material and a metal electrode in the welding process, and the element diffusion is slow at the metal ceramic composite phase. Meanwhile, compared with the existing Ti barrier layer, the brittle reaction layer of the metal ceramic composite phase is reduced in overall proportion, and the reaction layer degree is also reduced overall. The high thermal expansion coefficient of the ceramic in the metal ceramic composite phase adjusts the integral thermal expansion coefficient, the connection strength is higher, the problem that other metals can react with skutterudite when adjusting the thermal expansion coefficient is also avoided, and the integral diffusion resistance effect is not damaged. Therefore, the metal ceramic composite phase is used as the diffusion barrier layer, the connection strength is high, the joint resistance is low, the thickness of the reaction layer grows slowly under long-term service, and the thickness of the reaction layer only grows from 8.5 mu m to 15.5 mu m after the annealing for 135 hours through test, so that good mechanical property and service performance are maintained. The invention can regulate the composition and proportion of the integral barrier layer by selecting different refractory metals and ceramics, can control the type, thickness and distribution mode of the interface reaction layer by controlling the welding temperature and the heat preservation time, and further control the strength and the heat/electricity transport performance of the welding joint.
Drawings
FIG. 1 is an SEM image of the weld interface of a cermet composite phase/skutterudite thermoelectric material obtained in example 1;
FIG. 2 is an SEM image of the cermet composite phase/skutterudite thermoelectric material obtained in example 1 after 135h of weld interface annealing.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also comprises any reasonable combination of the specific embodiments.
In the first embodiment, the skutterudite thermoelectric material/electrode high-heat stability welding method based on the metal ceramic composite barrier layer is carried out according to the following steps:
1. The method comprises the steps of performing hot-pressing sintering on a skutterudite thermoelectric material and a barrier layer to obtain skutterudite with a preset barrier layer, wherein the surface of the barrier layer in the skutterudite with the preset barrier layer is a surface to be welded, and respectively pre-treating the surface to be welded of the skutterudite with the preset barrier layer and the surface to be welded of a metal electrode;
Spreading a layer of skutterudite powder in a graphite die, spreading a layer of metal ceramic composite barrier layer powder on the skutterudite powder, and finally performing hot-pressing sintering;
the hot-pressed sintering process comprises heating to 650-760 deg.C at a rate of 10-20 deg.C/min under vacuum condition at a pressure of 40-70MPa, maintaining for 5-30min, and cooling to room temperature at a rate of 20-50 deg.C/min;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is one or more of Mo, V, zr, nb, ta, re, ti, the ceramic powder is one or more of M xSiy、MxNy、MxOy, wherein M is one or more of Ti, zr, mg, al, K, ca, zn, mn, and the mole percentage of the refractory metal powder in the metal ceramic composite barrier layer powder is 60-90%;
2. Assembling skutterudite of a preset barrier layer and a metal electrode, wherein the face to be welded of the skutterudite of the preset barrier layer faces the face to be welded of the metal electrode, placing brazing filler metal between the face to be welded of the skutterudite of the preset barrier layer and the face to be welded of the electrode to obtain a piece to be welded, and finally welding, wherein the welding process comprises the steps of heating to 600-700 ℃ at a rate of 10-20 ℃ and preserving heat for 5-30min in a vacuum brazing furnace with a vacuum degree of below 5X 10 -3 Pa, and then cooling to room temperature at a rate of 10-50 ℃ per min.
In the embodiment, the metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, a metal ceramic composite phase is formed after hot-pressing sintering, the metal ceramic composite phase is used as a barrier layer, no serious interface reaction is caused between the barrier layer and skutterudite thermoelectric material and the metal electrode in the welding process, and the element diffusion is slow at the metal ceramic composite phase. Meanwhile, compared with the existing Ti barrier layer, the brittle reaction layer of the metal ceramic composite phase in the embodiment has the advantages that the overall proportion is reduced, and the reaction layer degree is also reduced overall. The high thermal expansion coefficient of the ceramic in the metal ceramic composite phase adjusts the integral thermal expansion coefficient, the connection strength is higher, the problem that other metals can react with skutterudite when adjusting the thermal expansion coefficient is also avoided, and the integral diffusion resistance effect is not damaged. Therefore, the metal ceramic composite phase is used as the diffusion barrier layer in the embodiment, the connection strength is high, the joint resistance is low, the thickness of the reaction layer grows slowly under long-term service, and the thickness of the reaction layer only grows from 9.5 mu m to 14.5 mu m after the annealing for 135 hours through test, so that good mechanical property and service performance are maintained. The embodiment can regulate the composition and proportion of the integral barrier layer by selecting different refractory metals and ceramics, and can control the type, thickness and distribution mode of the interface reaction layer by controlling the welding temperature and the heat preservation time, thereby controlling the strength and the heat/electricity transport performance of the welding joint.
The second specific embodiment is different from the first specific embodiment in that the pretreatment process comprises the steps of sequentially carrying out metallographic abrasive paper step by step, polishing, cleaning and drying on the surface to be welded, and cleaning by adopting ethanol or acetone.
In the third embodiment, the thickness of the barrier layer in the first step is 20-200 μm, which is different from that in the first or second embodiments.
In a fourth embodiment, the metal electrode in the first step is Cu, a Cu-based alloy, ni, a Ni-based alloy, fe or a Fe-based alloy, which is different from the metal electrode in the first to third embodiments.
In the fifth embodiment, the difference between the fifth embodiment and the first to fourth embodiments is that the solder in the second step is copper-based solder paste.
In a sixth embodiment, the skutterudite thermoelectric material/electrode high-heat stability welding method based on the metal ceramic composite barrier layer of the present embodiment is performed according to the following steps:
1. Firstly, performing hot-pressing sintering on skutterudite powder to obtain skutterudite, performing hot-pressing sintering on metal ceramic composite barrier layer powder to obtain a preset barrier layer, then performing pretreatment on the surface to be welded of skutterudite, the surface to be welded of a metal electrode and two surfaces of the preset barrier layer, and finally storing the treated skutterudite, the treated metal electrode and the treated preset barrier layer in an anaerobic or inert atmosphere;
the hot-pressing sintering process of skutterudite powder into skutterudite comprises heating to 650-760 deg.C at a rate of 10-20 deg.C/min under vacuum condition at a pressure of 40-70MPa, maintaining for 5-30min, and cooling to room temperature at a rate of 20-50 deg.C/min;
the hot-pressing sintering process of the metal ceramic composite barrier layer powder into a preset barrier layer comprises heating to 650-760 ℃ at a rate of 10-20 ℃ per minute under the condition of vacuum and under the condition of applying 40-70MPa, preserving heat for 5-30min, and cooling to room temperature at a rate of 20-50 ℃ per minute;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is one or more of Mo, V, zr, nb, ta, re, ti, the ceramic powder is one or more of M xSiy、MxNy、MxOy, wherein M is one or more of Ti, zr, mg, al, K, ca, zn, mn, and the mole percentage of the refractory metal powder in the metal ceramic composite barrier layer powder is 60-90%;
2. And placing a preset barrier layer between the skutterudite surface to be welded and the metal electrode surface to be welded to obtain a piece to be welded, and finally welding, wherein the welding process comprises the steps of applying pressure of 5-20MPa in a vacuum brazing furnace with the vacuum degree of below 5X 10 -3 Pa, heating to 600-700 ℃ at the speed of 10-20 ℃ per minute, preserving heat for 5-30 minutes, and then cooling to room temperature at the speed of 10-50 ℃ per minute.
In the embodiment, the metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, a metal ceramic composite phase is formed after hot-pressing sintering, the metal ceramic composite phase is used as a barrier layer, no serious interface reaction is caused between the barrier layer and skutterudite thermoelectric material and the metal electrode in the welding process, and the element diffusion is slow at the metal ceramic composite phase. Meanwhile, compared with the existing Ti barrier layer, the brittle reaction layer of the metal ceramic composite phase in the embodiment has the advantages that the overall proportion is reduced, and the reaction layer degree is also reduced overall. The high thermal expansion coefficient of the ceramic in the metal ceramic composite phase adjusts the integral thermal expansion coefficient, the connection strength is higher, the problem that other metals can react with skutterudite when adjusting the thermal expansion coefficient is also avoided, and the integral diffusion resistance effect is not damaged. Therefore, the metal ceramic composite phase is used as the diffusion barrier layer in the embodiment, the connection strength is high, the joint resistance is low, the thickness of the reaction layer grows slowly under long-term service, and the thickness of the reaction layer only grows from 8.5 mu m to 15.5 mu m after the annealing for 135 hours through test, so that good mechanical property and service performance are maintained. The embodiment can regulate the composition and proportion of the integral barrier layer by selecting different refractory metals and ceramics, and can control the type, thickness and distribution mode of the interface reaction layer by controlling the welding temperature and the heat preservation time, thereby controlling the strength and the heat/electricity transport performance of the welding joint.
The seventh embodiment is different from the sixth embodiment in that the pretreatment process in the first step comprises sequentially polishing, cleaning and drying the surface to be welded with metallographic abrasive paper step by step, and cleaning with ethanol or acetone.
In the eighth embodiment, the thickness of the barrier layer in the first step is 20-200 μm, which is different from that in the sixth or seventh embodiment.
Embodiment nine the present embodiment differs from one of the sixth to eighth embodiments in that the metal electrode of step one is Cu, a Cu-based alloy, ni, a Ni-based alloy, fe or a Fe-based alloy.
In the tenth embodiment, the difference between the present embodiment and one of the sixth to ninth embodiments is that the solder in the second step is copper-based solder paste.
Example 1:
the skutterudite thermoelectric material/electrode high-thermal stability welding method based on the metal ceramic composite barrier layer of the embodiment is carried out according to the following steps:
1. the method comprises the steps of performing hot-pressing sintering on a skutterudite thermoelectric material and a barrier layer to obtain skutterudite with a preset barrier layer, wherein the surface of the barrier layer in the skutterudite with the preset barrier layer is a surface to be welded, and respectively pre-treating the surface to be welded of the skutterudite with the preset barrier layer and the surface to be welded of a metal electrode;
The pretreatment process comprises the steps of sequentially carrying out metallographic sand paper step by step grinding, polishing, cleaning and drying on the surface to be welded, wherein ethanol is adopted for cleaning;
The preparation method of the skutterudite with the preset barrier layer comprises the steps of paving a layer of skutterudite powder in a graphite die, paving a layer of metal ceramic composite barrier layer powder on the skutterudite powder, and finally performing hot-pressing sintering, wherein the hot-pressing sintering process comprises the steps of heating to 750 ℃ at a rate of 10 ℃ per minute under the condition of applying a pressure of 40MPa in a vacuum environment, preserving heat for 15min, and cooling to room temperature at a rate of 20 ℃ per minute;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is Ti and Nb, the mole percentage of Ti in the metal ceramic composite barrier layer powder is 70%, and the mole percentage of Nb is 20%;
the thickness of the barrier layer is 200 μm;
the metal electrode is a copper-tungsten electrode with the thickness of 2 mm;
2. Assembling skutterudite of a preset barrier layer and a metal electrode, wherein the face to be welded of the skutterudite of the preset barrier layer faces the face to be welded of the metal electrode, and a brazing filler metal is placed between the face to be welded of the skutterudite of the preset barrier layer and the face to be welded of the electrode to obtain a piece to be welded, and finally welding is carried out, wherein the welding process comprises the steps of heating to 675 ℃ at a speed of 10 ℃ per minute in a vacuum brazing furnace with a vacuum degree of below 5X 10 -3 Pa, preserving heat for 15min, and then cooling to room temperature at a speed of 10 ℃ per minute, and the brazing filler metal is copper-based brazing filler metal.
In this example, ti-Nb-TiSi 2 was used as a barrier layer between skutterudite-based thermoelectric material and metal electrode to prevent diffusion of elements. The reaction of Sb element in skutterudite and an electrode can be effectively blocked to form a large amount of intermetallic compounds, the joint has good thermal stability, the SEM image of the interface of the Ti-Nb-TiSi 2 blocking layer/skutterudite thermoelectric material obtained in the embodiment 1 is shown in the figure 1, the reaction layer of the joint is thin, and the element blocking effect is good. FIG. 2 is an SEM image of the cermet composite phase/skutterudite thermoelectric material obtained in example 1 after 135h of annealing at 550℃for 135h, showing an increase in the thickness of the reaction layer from 9.5 μm to 14.5. Mu.m.
Example 2:
the skutterudite thermoelectric material/electrode high-thermal stability welding method based on the metal ceramic composite barrier layer comprises the following steps of:
1. Firstly, performing hot-pressing sintering on skutterudite powder to obtain skutterudite, performing hot-pressing sintering on metal ceramic composite barrier layer powder to obtain a preset barrier layer, then performing pretreatment on the surface to be welded of skutterudite, the surface to be welded of a metal electrode and two surfaces of the preset barrier layer, and finally storing the treated skutterudite, the treated metal electrode and the treated preset barrier layer in an inert atmosphere;
The pretreatment process comprises the steps of sequentially carrying out metallographic sand paper step by step grinding, polishing, cleaning and drying on the surface to be welded, wherein ethanol is adopted for cleaning;
The process for sintering skutterudite powder into skutterudite by hot pressing comprises heating to 750deg.C at a rate of 10deg.C/min under vacuum condition, maintaining for 15min, and cooling to room temperature at a rate of 20deg.C/min;
The hot-pressing sintering process of the metal ceramic composite barrier layer powder into a preset barrier layer comprises the steps of heating to 750 ℃ at a rate of 10 ℃ per minute under the condition of vacuum and under the condition of applying 40MPa, preserving heat for 15min, and cooling to room temperature at a rate of 20 ℃ per minute;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is Ti and Nb, the mole percentage of Ti in the metal ceramic composite barrier layer powder is 70%, and the mole percentage of Nb is 20%;
the thickness of the barrier layer is 200 μm;
the metal electrode is a copper-tungsten electrode with the thickness of 2 mm;
2. Placing a preset barrier layer between a skutterudite surface to be welded and a metal electrode surface to be welded to obtain a piece to be welded, and finally welding, wherein the welding process comprises the steps of applying pressure of 5MPa in a vacuum brazing furnace with the vacuum degree of below 5X 10 -3 Pa, heating to 675 ℃ at the speed of 10 ℃ per minute, preserving heat for 15min, and then cooling to room temperature at the speed of 10 ℃ per minute;
In the embodiment, ti-Nb-TiSi 2 is used as a barrier layer between the skutterudite thermoelectric material and the metal electrode for preventing element diffusion, so that Sb element in skutterudite is effectively blocked from reacting with the electrode to form a large amount of intermetallic compounds, the thermal stability of the joint is good, the reaction layer of the joint is thin, and the element blocking effect is good. After annealing at 550 ℃ for 135 hours, the reaction layer thickness only increased from 8.5 μm to 15.5 μm.
Claims (10)
1. The skutterudite thermoelectric material/electrode high-heat stability welding method based on the metal ceramic composite barrier layer is characterized by comprising the following steps of:
1. The method comprises the steps of performing hot-pressing sintering on a skutterudite thermoelectric material and a barrier layer to obtain skutterudite with a preset barrier layer, wherein the surface of the barrier layer in the skutterudite with the preset barrier layer is a surface to be welded, and respectively pre-treating the surface to be welded of the skutterudite with the preset barrier layer and the surface to be welded of a metal electrode;
Spreading a layer of skutterudite powder in a graphite die, spreading a layer of metal ceramic composite barrier layer powder on the skutterudite powder, and finally performing hot-pressing sintering;
the hot-pressed sintering process comprises heating to 650-760 deg.C at a rate of 10-20 deg.C/min under vacuum condition at a pressure of 40-70MPa, maintaining for 5-30min, and cooling to room temperature at a rate of 20-50 deg.C/min;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is one or more of Mo, V, zr, nb, ta, re, ti, the ceramic powder is one or more of M xSiy、MxNy、MxOy, wherein M is one or more of Ti, zr, mg, al, K, ca, zn, mn, and the mole percentage of the refractory metal powder in the metal ceramic composite barrier layer powder is 60-90%;
2. Assembling skutterudite of a preset barrier layer and a metal electrode, wherein the face to be welded of the skutterudite of the preset barrier layer faces the face to be welded of the metal electrode, placing brazing filler metal between the face to be welded of the skutterudite of the preset barrier layer and the face to be welded of the electrode to obtain a piece to be welded, and finally welding, wherein the welding process comprises the steps of heating to 600-700 ℃ at a rate of 10-20 ℃ and preserving heat for 5-30min in a vacuum brazing furnace with a vacuum degree of below 5X 10 -3 Pa, and then cooling to room temperature at a rate of 10-50 ℃ per min.
2. The skutterudite thermoelectric material/electrode high-thermal stability welding method based on the metal ceramic composite barrier layer, as claimed in claim 1, is characterized in that the pretreatment process comprises the steps of sequentially carrying out metallographic sand paper step by step grinding, polishing, cleaning and drying on a surface to be welded, and cleaning by adopting ethanol or acetone.
3. The method for high heat stability welding of skutterudite thermoelectric material/electrode based on metal ceramic composite barrier layer according to claim 1, wherein the thickness of the barrier layer is 20-200 μm in step one.
4. The method for high thermal stability welding of skutterudite thermoelectric material/electrode based on metal-ceramic composite barrier layer according to claim 1, wherein in step one the metal electrode is Cu, cu-based alloy, ni-based alloy, fe or Fe-based alloy.
5. The skutterudite thermoelectric material/electrode high-heat stability welding method based on a metal ceramic composite barrier layer according to claim 1, characterized in that the solder in the second step is copper-based solder paste.
6. The skutterudite thermoelectric material/electrode high-heat stability welding method based on the metal ceramic composite barrier layer is characterized by comprising the following steps of:
1. Firstly, performing hot-pressing sintering on skutterudite powder to obtain skutterudite, performing hot-pressing sintering on metal ceramic composite barrier layer powder to obtain a preset barrier layer, then performing pretreatment on the surface to be welded of skutterudite, the surface to be welded of a metal electrode and two surfaces of the preset barrier layer, and finally storing the treated skutterudite, the treated metal electrode and the treated preset barrier layer in an anaerobic or inert atmosphere;
the hot-pressing sintering process of skutterudite powder into skutterudite comprises heating to 650-760 deg.C at a rate of 10-20 deg.C/min under vacuum condition at a pressure of 40-70MPa, maintaining for 5-30min, and cooling to room temperature at a rate of 20-50 deg.C/min;
the hot-pressing sintering process of the metal ceramic composite barrier layer powder into a preset barrier layer comprises heating to 650-760 ℃ at a rate of 10-20 ℃ per minute under the condition of vacuum and under the condition of applying 40-70MPa, preserving heat for 5-30min, and cooling to room temperature at a rate of 20-50 ℃ per minute;
The metal ceramic composite barrier layer powder is formed by mixing refractory metal powder and ceramic powder, wherein the refractory metal powder is one or more of Mo, V, zr, nb, ta, re, ti, the ceramic powder is one or more of M xSiy、MxNy、MxOy, wherein M is one or more of Ti, zr, mg, al, K, ca, zn, mn, and the mole percentage of the refractory metal powder in the metal ceramic composite barrier layer powder is 60-90%;
2. Placing a preset barrier layer between a skutterudite surface to be welded and a metal electrode surface to be welded to obtain a piece to be welded, and finally welding;
The welding process comprises the steps of applying pressure of 5-20MPa in a vacuum brazing furnace with vacuum degree of below 5X 10 -3 Pa, heating to 600-700 ℃ at the speed of 10-20 ℃ per min, preserving heat for 5-30min, and then cooling to room temperature at the speed of 10-50 ℃ per min.
7. The skutterudite thermoelectric material/electrode high-thermal stability welding method based on the metal ceramic composite barrier layer as claimed in claim 6, wherein the pretreatment process comprises the steps of sequentially carrying out metallographic sand paper progressive grinding, polishing, cleaning and drying on a surface to be welded, and cleaning by adopting ethanol or acetone.
8. The method for high heat stability welding of skutterudite thermoelectric material/electrode based on metal ceramic composite barrier layer according to claim 6, wherein the thickness of the barrier layer is 20-200 μm in step one.
9. The method for high thermal stability welding of skutterudite thermoelectric material/electrode based on metal-ceramic composite barrier layer according to claim 6, wherein in step one the metal electrode is Cu, cu-based alloy, ni-based alloy, fe or Fe-based alloy.
10. The method for high-heat-stability welding of skutterudite thermoelectric material/electrode based on metal ceramic composite barrier layer according to claim 6, wherein the solder in the second step is copper-based solder paste.
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