CN114497335A - Skutterudite thermoelectric material electrode and connection method of skutterudite thermoelectric material and electrode - Google Patents
Skutterudite thermoelectric material electrode and connection method of skutterudite thermoelectric material and electrode Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 27
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- 229910018985 CoSb3 Inorganic materials 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 14
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- 235000019270 ammonium chloride Nutrition 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 12
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
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- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/81—Structural details of the junction
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/82—Connection of interconnections
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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Abstract
The invention discloses a skutterudite thermoelectric material electrode and a method for connecting a skutterudite thermoelectric material with the electrode. The invention embeds the skutterudite thermoelectric material into the mixture powder of the raw materials, and the skutterudite thermoelectric material reacts and diffuses at a certain temperature, thereby realizing the electrode and CoSb3And connecting the thermoelectric materials. The method has the advantages of short production period, small equipment investment, simple operation and the like, greatly improves the efficiency of connecting the thermoelectric material and the electrode, and is suitable for large-scale production.
Description
Technical Field
The invention relates to a skutterudite thermoelectric material electrode, and also relates to a method for connecting a skutterudite thermoelectric material and the electrode, belonging to the technical field of thermoelectric power generation.
Background
The thermoelectric power generation technology is a technology for directly converting thermal energy into electric energy through the seebeck effect. The thermoelectric power generation device has the advantages of small volume, no movable parts, no noise, no pollution, no maintenance, long service life and the like, and is applied to deep space exploration power supplies and special military power supplies. Meanwhile, the thermoelectric power generation device also has wide application prospect and potential social and economic benefits in the fields of industrial waste heat, automobile exhaust waste heat recovery and the like.
Since most thermoelectric power generation devices typically operate under harsh environmental conditions, such as high temperature, large temperature difference, wide frequency vibration, and extremely long operating time, long term reliability of the devices becomes a significant obstacle that limits industrial applications. El-Genk and other researches find that the output power of a skutterudite device taking Cu as an electrode is reduced by 70% after 150 days of 600 ℃ accelerated test, and the large increase of the contact resistivity of a high-temperature end interface is a main reason of the performance reduction of the device. The heterointerface between the pyroelectric material and the electrodes plays a critical role in the reliability of the device. For devices applied to medium-high temperature power generation, due to the high use temperature, the selection of high-temperature electrode materials and the connection technology are particularly difficult. Among them, CoSb is one of the most potential candidates for the middle temperature region3The skutterudite thermoelectric device has extremely high conversion efficiency of up to 12%. Currently available electrodes and CoSb3The connection mode of the skutterudite thermoelectric material mainly comprises spring pressure contact, brazing, sintering and the like. Early NASA-JPL proposed spring pressure contact for CoSb production3Based on thermoelectric power generation devices, but simple mechanical contact causes large interface resistance and interface thermal resistance, which hinders the improvement of device efficiency (J-Genk MS, Saber HH, Caillat. Efficient segmented thermoelectric units for space power applications]. Energy Conversion &Management, 2003, 44(11): 1755-. For the brazing mode, the solder and the substrate are seriously diffused and have poor stability, so that the requirement of long-term use is difficult to meet. Fan and the like Mo electrode and CoSb by using Ti as a transition layer and adopting a two-step SPS method3Materials are connected, but Mo and CoSb3Has large thermal expansion coefficient difference, large residual stress at the interface, easy generation of cracks and influence on the bonding strength and the reliability of the device (Fan J, Chen L, Bai S, et al3 by spark plasma sintering by inserting a Ti interlayer[J]Materials Letters, 2004, 58(30): 3876-. Later, the technology optimizes the alloy composition through Mo-Cu alloying, and the thermal expansion coefficient of Mo-Cu can be adjusted to be CoSb3The basal filling skutterudite is matched, the residual stress of the interface is greatly reduced, and the interface strength and the device reliability are improved (ZHao D, Li X, He L, et al3/Ti/Mo-Cu thermoelectric joints during accelerated thermal aging[J]. Journal of Alloys &Compounds, 2009, 477(1-2): 425-. However, the method has high requirements on equipment and moulds, high economic benefit is not easy to obtain, and the thickness of the transition layer is not easy to control. Therefore, a low-cost, efficient and reliable connection method is still under development.
Disclosure of Invention
The invention provides a skutterudite thermoelectric material electrode and a connection mode of the electrode and the skutterudite thermoelectric material, aiming at the defects of low efficiency, poor stability, complex process, large equipment investment, high cost and the like of the connection mode of the conventional skutterudite thermoelectric material and the electrode.
The specific technical scheme of the invention is as follows:
a skutterudite thermoelectric material electrode is prepared from the following raw materials in percentage by mass: 25-35% of aluminum powder, 3-5% of ammonium chloride powder and the balance of alumina powder.
Further, the raw materials of the electrode are uniformly mixed and then are roasted in vacuum to obtain the electrode. The roasting temperature is generally 500-550 ℃, and the roasting time is 0.5-2 h. The composition of the electrode obtained by roasting is an aluminum-rich intermetallic compound.
The invention also provides a method for connecting the skutterudite thermoelectric material and the electrode, which comprises the following steps:
(1) putting the uniformly mixed aluminum powder, alumina powder and ammonium chloride powder into a crucible, and then embedding the skutterudite thermoelectric material into the mixture powder;
(2) putting the crucible into a quartz tube, and vacuumizing and sealing;
(3) and (3) heating the quartz tube to the roasting temperature for roasting, cooling after roasting, taking out the skutterudite thermoelectric material, and obtaining an electrode layer on the surface of the skutterudite thermoelectric material, namely realizing the connection between the skutterudite thermoelectric material and the electrode.
Further, the component of the skutterudite thermoelectric material of the invention refers to pure CoSb3Or is CoSb3Doped CoSb formed by filling or doping other elements in matrix3The doped elements of the material can be one or more of Yb, Li, Ir, Na, K, Ca, La, Al and Pd. The skutterudite thermoelectric material is generally in the form of a block.
Further, the crucible is a graphite crucible.
Further, in the step (1), the raw materials of the electrode comprise aluminum powder, aluminum oxide powder and ammonium chloride powder, wherein the content of the aluminum powder is 25-35wt%, the content of the ammonium chloride powder is 3-5wt%, the balance of the aluminum oxide powder is supplemented, and the sum of the aluminum powder, the aluminum oxide powder and the ammonium chloride powder is 100 wt%. Wherein, the aluminum powder provides elements required by the electrode layer, the aluminum oxide powder plays roles of diluting, filling and preventing the aluminum powder from bonding, and the ammonium chloride powder can promote the generation of active aluminum atoms and accelerate the growth speed of the electrode layer. The content of the aluminum powder is not too high or too low, a continuous electrode layer is not easily formed when the content of the aluminum powder is too low, the aluminum powder is easily bonded when the content of the aluminum powder is too high, and the utilization rate of the aluminum powder is reduced. The content of the ammonium chloride powder is not too high, the quality of an electrode layer is reduced due to too high content of the ammonium chloride powder, and an aluminum source is excessively consumed, so that waste is caused.
Further, the particle size of the aluminum powder is less than or equal to 10 micrometers, and the purity of the aluminum powder is greater than or equal to 99.85%; the grain size of the alumina powder is less than or equal to 1 micron, and the purity of the alumina powder is greater than or equal to 99.99 percent. The ammonium chloride powder is AR grade.
Further, in the step (1), the aluminum powder, the alumina powder and the ammonium chloride powder can be uniformly mixed in advance by adopting conventional physical mixing modes such as stirring, grinding and the like, and a dry mixing mode and a wet mixing mode can be adopted. Preferably, the three powders are put into a mortar by adopting a wet mixing mode, absolute ethyl alcohol is added, the mixture is manually ground for 10 to 20 minutes, and the mixture is dried. The addition of anhydrous ethanol can prevent the powders from sticking to each other during grinding to cause uneven mixing.
Further, in the step (1), the skutterudite thermoelectric material is embedded in the central position of the mixture powder, which is beneficial to forming a uniform electrode layer.
Further, in the step (2), the crucible is placed into a quartz tube for vacuum pumping and sealing, and the vacuum degree in the quartz tube is more than 0.01MPa so as to isolate the consumption of the aluminum powder brought by oxygen. The invention has to be sealed, otherwise the gas overflow is serious, which leads to the failure of forming the electrode layer.
Further, in the step (3), the roasting temperature is 500-. Too low temperature can not form an electrode layer, too high temperature can cause more internal defects of the electrode layer, influence the quality of the electrode layer, and easily cause the decomposition of the skutterudite thermoelectric material matrix. The heat preservation time is not suitable to be too long, the thickness of the electrode layer is not obviously increased after the heat preservation time is too long, energy waste can be caused, and the performance of the substrate can be influenced after the heat preservation time is too long.
Furthermore, the heating rate is preferably 5-10 ℃/min, and the performance of the obtained electrode is better at the heating rate.
Further, the thickness of the electrode layer is controlled by controlling the contents of aluminum powder, ammonium chloride powder and aluminum oxide powder, the firing temperature and time, and the like. Generally, the higher the aluminum powder content and the higher the firing temperature and the longer the firing time, the thicker the resulting electrode layer, which is a component of an aluminum-rich intermetallic compound, and which is generally 15 to 55 μm thick, within the given range of conditions. The obtained electrode layer is uniformly distributed on the surface of the skutterudite thermoelectric material, is compact and crack-free, and is firmly combined with the surface of the skutterudite thermoelectric material.
The invention has the following beneficial effects:
the invention selects aluminum powder, alumina powder and ammonium chloride powder as the electricityThe electrode raw material is obtained by embedding the skutterudite thermoelectric material into the electrode raw material, reacting and diffusing the skutterudite thermoelectric material at a certain temperature, and directly forming an electrode on the surface of the skutterudite thermoelectric material in situ, so that the skutterudite thermoelectric material is quickly connected with the electrode. The obtained electrode is uniform, compact and crack-free, and is CoSb3The thermoelectric material is metallurgically bonded, and has a good interface bonding state. The method has the advantages of short production period, small equipment investment, simple operation and the like, greatly improves the efficiency of connecting the skutterudite thermoelectric material and the electrode, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic diagram of the process of the present invention.
FIG. 2 shows CoSb and electrodes in the product prepared in example 13The interface element surface distribution diagram at the thermoelectric material connection position.
FIG. 3 shows CoSb and electrodes in the product prepared in example 13Line scan of interface elements at the junction of the thermoelectric materials.
FIG. 4 shows CoSb and electrodes in the product prepared in example 13Scanning electron microscope photograph of the interface of the thermoelectric material junction.
FIG. 5 shows CoSb and electrodes in the product prepared in example 23Scanning electron microscope photograph of the interface of the thermoelectric material junction.
FIG. 6 shows CoSb and electrodes in the product prepared in comparative example 13Scanning electron microscope photograph of the interface of the thermoelectric material junction.
FIG. 7 shows CoSb and electrodes in the product prepared in comparative example 23Scanning electron microscope photograph of the interface of the thermoelectric material junction.
In the figure, 1, quartz tube, 2, graphite crucible, 3, raw material mixed powder, 4, CoSb3A bulk material.
Detailed Description
For a further understanding of the invention, reference will now be made in detail to specific embodiments of the invention.
In the following examples, the aluminum powder used had a particle size of 10 μm and a purity of 99.85%. The alumina powder used had a particle size of 1 micron and a purity of 99.99%. The ammonium chloride powder used was AR grade.
Example 1
(1) Weighing 20g of three raw material powders (aluminum powder (25%), aluminum oxide powder (71%) and ammonium chloride powder (4%) according to the mass percentage. Putting the three powders into a mortar, adding absolute ethyl alcohol, manually grinding for 10 minutes to uniformly mix the powders, and drying at 50 ℃. Then 2g of the mixed powder was taken out and put into a graphite crucible, and one CoSb was put3The block material is placed in the central position of the powder;
(2) slowly placing the graphite crucible into a quartz tube, vacuumizing and sealing, wherein the vacuum degree is more than 0.01 MPa;
(3) putting the quartz tube into a tube furnace, setting the heating rate to be 10 ℃/min, heating to 550 ℃, and carrying out heat preservation roasting for 2h at the temperature;
(4) and (4) taking out the sample after the furnace is cooled to room temperature, putting the sample into an ultrasonic cleaning machine for ultrasonic cleaning for 5 minutes, and then taking out the sample and drying. After calcination in CoSb3And an electrode layer is obtained on the surface of the block material, so that the connection between the skutterudite thermoelectric material and the electrode is realized.
FIGS. 2 and 3 are the resulting electrodes/CoSb3The interface element surface distribution diagram and the interface element line scanning diagram of the thermoelectric material show that the electrode and the thermoelectric material are metallurgically bonded, element diffusion occurs between the electrode and the thermoelectric material, aluminum element is distributed in the electrode layer in a concentration gradient manner, and the thickness of the electrode layer is about 50 microns.
FIG. 4 is the resulting electrode/CoSb3The scanning electron microscope picture of the interface of the thermoelectric material shows that the electrode layer is dense and has no cracks, and the CoSb is not mixed with the electrode layer3The thermoelectric material bonds well.
Example 2
Following the procedure of example 1 in CoSb3Obtaining an electrode layer on the bulk material, except that: in the step (3), the temperature is raised to 500 ℃ according to the heating rate of 10 ℃/min, and the mixture is roasted for 2h at the temperature. The thickness of the resulting electrode layer was about 20 microns.
FIG. 5 shows the resulting electrode/CoSb3The scanning electron microscope picture of the interface of the thermoelectric material shows that the electrode layer is uniform and compact, and the interface isFlat surface without cracks, and CoSb3The thermoelectric material bonds well.
Example 3
Following the procedure of example 1 in CoSb3Obtaining an electrode layer on the bulk material, except that: in the step (3), the temperature is raised to 550 ℃ according to the heating rate of 5 ℃/min, and the mixture is roasted for 2h at the temperature. The thickness of the obtained electrode layer is about 50 microns, the electrode layer is uniform and compact, the interface is smooth and has no cracks, and the electrode layer is CoSb3The thermoelectric material bonds well.
Example 4
Following the procedure of example 1 in CoSb3Obtaining an electrode layer on the bulk material, except that: in the step (3), the temperature is raised to 500 ℃ according to the heating rate of 10 ℃/min, and the mixture is roasted for 30min at the temperature. The thickness of the obtained electrode layer is about 15 microns, the electrode layer is uniform and compact and has no cracks, and the electrode layer is CoSb3The thermoelectric material bonds well.
Example 5
Following the procedure of example 1 in CoSb3The bulk material yielded an aluminum electrode layer, except that: in the step (1), 20g of three raw material powders (aluminum powder (35%), aluminum oxide powder (60%) and ammonium chloride powder (5%)) are weighed according to the mass percentage. The thickness of the obtained electrode layer is about 55 microns, the electrode layer is uniform and compact and has no cracks, and the electrode layer is CoSb3The thermoelectric material bonds well.
Comparative example 1
Following the procedure of example 1 in CoSb3Obtaining an electrode layer on the bulk material, except that: in the step (3), the temperature is raised to 450 ℃ according to the heating rate of 10 ℃/min, and the mixture is roasted for 2h at the temperature.
FIG. 6 shows the resulting electrode/CoSb3Scanning electron microscope photograph of interface of thermoelectric material, it can be seen from the figure that CoSb is too low in heat treatment temperature3No continuous electrode layer was formed on the surface, and the function of the electrode was not exhibited.
Comparative example 2
Following the procedure of example 1 in CoSb3Obtaining an electrode layer on the bulk material, except that: in the step (3), the temperature is raised according to the temperature of 10 ℃/minThe rate was increased to 600 ℃ and the calcination was carried out at this temperature for 2 h.
FIG. 7 shows the resulting electrode/CoSb3The scanning electron microscope photograph of the interface of the thermoelectric material shows that CoSb is too high due to the high heat treatment temperature3The surface-formed electrode layer is poor in quality, loose in structure, and causes CoSb3Cracks appear inside the matrix.
Comparative example 3
Following the procedure of example 1 in CoSb3Obtaining an electrode layer on the bulk material, except that: in the step (1), 20g of three raw material powders (aluminum powder (15%), aluminum oxide powder (77%) and ammonium chloride powder (8%)) are weighed according to the mass percentage. As a result, it was found that the aluminum powder was excessively consumed by ammonium chloride due to the excessively small content and the excessively large content of ammonium chloride, resulting in CoSb3The surface is formed substantially without electrode layers.
Claims (10)
1. A skutterudite thermoelectric material electrode is characterized in that: the feed is prepared from the following raw materials in percentage by mass: 25-35% of aluminum powder, 3-5% of ammonium chloride powder and the balance of alumina powder.
2. The skutterudite thermoelectric material electrode as set forth in claim 1, wherein: the raw materials are evenly mixed and then are roasted in vacuum to obtain the electrode.
3. The skutterudite thermoelectric material electrode as set forth in claim 2, wherein: the roasting temperature is 500-550 ℃, and the roasting time is 0.5-2 h.
4. A method of connecting a skutterudite thermoelectric material to the electrode of claim 1, comprising the steps of:
(1) putting the uniformly mixed aluminum powder, alumina powder and ammonium chloride powder into a crucible, and then embedding the skutterudite thermoelectric material into the mixture powder;
(2) putting the crucible into a quartz tube, and vacuumizing and sealing;
(3) and (3) heating the quartz tube to the roasting temperature for roasting, cooling after roasting, taking out the skutterudite thermoelectric material, and obtaining an electrode layer on the surface of the skutterudite thermoelectric material.
5. The connecting method according to claim 4, wherein: the crucible is a graphite crucible.
6. The connecting method according to claim 4, wherein: the grain diameter of the aluminum powder is less than or equal to 10 microns, and the grain diameter of the aluminum oxide powder is less than or equal to 1 micron.
7. The connecting method according to claim 4, wherein: the aluminum powder, the alumina powder and the ammonium chloride powder are uniformly mixed by adopting a wet mixing method, and the used solvent is ethanol.
8. The connecting method according to claim 4, wherein: the skutterudite thermoelectric material is buried in the center position of the mixture powder.
9. The connecting method according to claim 4, wherein: the roasting temperature is 500-550 ℃, and the roasting time is 0.5-2 h.
10. The connecting method according to claim 4, wherein: the skutterudite thermoelectric material is CoSb3Or doped CoSb3A material.
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Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07235440A (en) * | 1994-02-24 | 1995-09-05 | Toshiba Corp | Manufacture of laminated ceramic element |
| US5582867A (en) * | 1994-06-28 | 1996-12-10 | Sumitomo Electric Industries, Ltd. | Corrosion-resistant metallic porous member and method of manufacturing the same |
| KR19980037268A (en) * | 1996-11-21 | 1998-08-05 | 김종진 | Manufacturing method of zinc anode suppressed passivation |
| JPH11195817A (en) * | 1997-12-27 | 1999-07-21 | Sumitomo Special Metals Co Ltd | Thermoelectric conversion element |
| 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 |
| CN101397612A (en) * | 2008-10-21 | 2009-04-01 | 同济大学 | Method for preparing skutterudite base thermoelectric block body material |
| 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 |
| KR20110071874A (en) * | 2009-12-22 | 2011-06-29 | 한국세라믹기술원 | Electrode for thermoelectric device and manufacturing method of the same |
| US20130043439A1 (en) * | 2009-09-28 | 2013-02-21 | Lidong Chen | Filled-skutterudite composite material and method of preparing the same |
| CN105679928A (en) * | 2016-01-28 | 2016-06-15 | 济南大学 | Alloy electrode suitable for Cu<2>SnSe<3>-based thermoelectric element and preparation technology of thermoelectric element |
| 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 |
| CN106917026A (en) * | 2015-12-28 | 2017-07-04 | 吕澎沸 | A kind of negative thermal expansion material Zn0.5Sn0.5NMn3And preparation method thereof |
| CN108461619A (en) * | 2018-06-01 | 2018-08-28 | 济南大学 | A kind of preparation method of Se doping skutterudite thermoelectric material |
| CN108550688A (en) * | 2018-05-24 | 2018-09-18 | 中国科学院上海硅酸盐研究所 | A kind of thermo-electric device with adaptive connection layer |
| CN109022863A (en) * | 2018-07-16 | 2018-12-18 | 电子科技大学 | A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga |
| JP2019169534A (en) * | 2018-03-22 | 2019-10-03 | 日立金属株式会社 | Thermoelectric device, thermoelectric conversion module and method for manufacturing thermoelectric device |
| WO2019203392A1 (en) * | 2018-04-16 | 2019-10-24 | 한국전력공사 | Electrode material for thermoelectric power generation module and method for manufacturing same |
| CN110429172A (en) * | 2019-07-17 | 2019-11-08 | 中国科学院上海硅酸盐研究所 | A kind of thermo-electric device and preparation method thereof |
| CN111463341A (en) * | 2019-01-21 | 2020-07-28 | 中国科学院上海硅酸盐研究所 | Low-contact-resistivity half-heusler alloy thermoelectric device and preparation method thereof |
| KR102198279B1 (en) * | 2019-09-06 | 2021-01-05 | 한국에너지기술연구원 | Metalizing structure for skutterudite thermoelectric material including ito layer |
-
2022
- 2022-01-20 CN CN202210063653.9A patent/CN114497335A/en active Pending
Patent Citations (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07235440A (en) * | 1994-02-24 | 1995-09-05 | Toshiba Corp | Manufacture of laminated ceramic element |
| US5582867A (en) * | 1994-06-28 | 1996-12-10 | Sumitomo Electric Industries, Ltd. | Corrosion-resistant metallic porous member and method of manufacturing the same |
| KR19980037268A (en) * | 1996-11-21 | 1998-08-05 | 김종진 | Manufacturing method of zinc anode suppressed passivation |
| JPH11195817A (en) * | 1997-12-27 | 1999-07-21 | Sumitomo Special Metals Co Ltd | Thermoelectric conversion element |
| 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 |
| CN101397612A (en) * | 2008-10-21 | 2009-04-01 | 同济大学 | Method for preparing skutterudite base thermoelectric block body material |
| 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 |
| US20130043439A1 (en) * | 2009-09-28 | 2013-02-21 | Lidong Chen | Filled-skutterudite composite material and method of preparing the same |
| KR20110071874A (en) * | 2009-12-22 | 2011-06-29 | 한국세라믹기술원 | Electrode for thermoelectric device and manufacturing method of the same |
| 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 |
| CN106917026A (en) * | 2015-12-28 | 2017-07-04 | 吕澎沸 | A kind of negative thermal expansion material Zn0.5Sn0.5NMn3And preparation method thereof |
| CN105679928A (en) * | 2016-01-28 | 2016-06-15 | 济南大学 | Alloy electrode suitable for Cu<2>SnSe<3>-based thermoelectric element and preparation technology of thermoelectric element |
| JP2019169534A (en) * | 2018-03-22 | 2019-10-03 | 日立金属株式会社 | Thermoelectric device, thermoelectric conversion module and method for manufacturing thermoelectric device |
| WO2019203392A1 (en) * | 2018-04-16 | 2019-10-24 | 한국전력공사 | Electrode material for thermoelectric power generation module and method for manufacturing same |
| CN108550688A (en) * | 2018-05-24 | 2018-09-18 | 中国科学院上海硅酸盐研究所 | A kind of thermo-electric device with adaptive connection layer |
| CN108461619A (en) * | 2018-06-01 | 2018-08-28 | 济南大学 | A kind of preparation method of Se doping skutterudite thermoelectric material |
| CN109022863A (en) * | 2018-07-16 | 2018-12-18 | 电子科技大学 | A kind of based square cobalt mineral thermoelectric material and preparation method thereof for filling Ga |
| CN111463341A (en) * | 2019-01-21 | 2020-07-28 | 中国科学院上海硅酸盐研究所 | Low-contact-resistivity half-heusler alloy thermoelectric device and preparation method thereof |
| CN110429172A (en) * | 2019-07-17 | 2019-11-08 | 中国科学院上海硅酸盐研究所 | A kind of thermo-electric device and preparation method thereof |
| KR102198279B1 (en) * | 2019-09-06 | 2021-01-05 | 한국에너지기술연구원 | Metalizing structure for skutterudite thermoelectric material including ito layer |
Non-Patent Citations (10)
| Title |
|---|
| ARAI, K；NISHIMOTO, S； ROMANJEK, K； KOMASAKI, M； NAGATOMO, Y； KUROMITSU, Y: "《Development of High-Durability Substrates for Thermoelectric Modules》", 《JOURNAL OF ELECTRONIC MATERIALS》, vol. 48, no. 4, 30 April 2019 (2019-04-30), pages 1976 - 1980 * |
| GU, M ]; XIA, XG ; LI, XY ; HUANG, XY; CHEN, LD: "《Microstructural evolution of the interfacial layer in the Ti-Al/Yb0.6Co4Sb12 thermoelectric joints at high temperature》", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 610, 31 October 2014 (2014-10-31), pages 665 - 670 * |
| LI, JQ ; ZHAO, SY ; CHEN, JL ; BAI, GY ; HU, LP; LIU, FS ; AO, WQ ; LI, Y; XIE, HP; ZHANG, CH: "《Enhanced Interfacial Reliability and Mechanical Strength of CoSb3-Based Thermoelectric Joints with Rationally Designed Diffusion Barrier Materials of Ti-Based Alloys》", 《ACS APPLIED MATERIALS & INTERFACES》, vol. 12, no. 40, 7 October 2020 (2020-10-07), pages 44858 - 44865 * |
| ZHANG, X；MA, XY ； LU, QM；ZHANG, FP； LIU, YQ；ZHANG, JX； WANG, L: "《Thermoelectric Properties of Ag-Doped n-Type (Bi2-xAgxTe3)0.96-(Bi2Se3)0.04 Pseudobinary Alloys》", 《JOURNAL OF ELECTRONIC MATERIALS》, vol. 40, no. 5, 31 May 2011 (2011-05-31), pages 773 - 777 * |
| ZHAO, DG ; LI, XY ; HE, L ; JIANG, W; CHEN, LD: "《Interfacial evolution behavior and reliability evaluation of CoSb3/Ti/Mo-Cu thermoelectric joints during accelerated thermal aging》", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 477, no. 1, 27 May 2009 (2009-05-27), pages 425 - 431 * |
| ZHAO, DG; GENG, HR ; CHEN, LD: "《Microstructure Contact Studies for Skutterudite Thermoelectric Devices》", 《INTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY》, vol. 9, no. 4, 31 August 2012 (2012-08-31), pages 733 - 741 * |
| 张世磊， 郭姗姗， 王磊， 齐恩磊， 王介强: "《微波均相合成Ce0.75Zr0.25O2 粉体及其烧结性》", 《中国粉体技术》, vol. 18, no. 3, 30 June 2012 (2012-06-30), pages 36 - 39 * |
| 张家萌;赵晓洁;毕作振;雷鸣;毕科;: "矿化剂对α-氧化铝粉体结构与成分的影响研究", 电子元件与材料, no. 09, 5 September 2020 (2020-09-05) * |
| 张飞鹏;路清梅;张久兴;张冰心;: "柠檬酸溶胶凝胶法制备CaMnO_3热电粉体及其表征", 功能材料, no. 06, 20 June 2009 (2009-06-20) * |
| 张骐昊；柏胜强；陈立东: "《热电发电器件与应用技术: 现状、挑战与展望》", 《无机材料学报》, vol. 34, no. 3, 31 March 2019 (2019-03-31), pages 279 - 293 * |
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