KR20030092692A - The fabrication method of thermoelectric material united thermoelectric element with electrode - Google Patents
The fabrication method of thermoelectric material united thermoelectric element with electrode Download PDFInfo
- Publication number
- KR20030092692A KR20030092692A KR1020020030440A KR20020030440A KR20030092692A KR 20030092692 A KR20030092692 A KR 20030092692A KR 1020020030440 A KR1020020030440 A KR 1020020030440A KR 20020030440 A KR20020030440 A KR 20020030440A KR 20030092692 A KR20030092692 A KR 20030092692A
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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
- H10N10/01—Manufacture or treatment
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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
- H10N10/81—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
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
-
- 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
Abstract
Description
본 발명은 열전모듈을 제작하는데 필요한 열전소자의 제조 방법에 관한 것으로, 열전소자와 전극을 동시에 소결하여 열전소자와 전극이 일체화된 열전재료를 제조하는 방법에 관한 것이다.The present invention relates to a method of manufacturing a thermoelectric element required for manufacturing a thermoelectric module, and more particularly, to a method of manufacturing a thermoelectric material in which a thermoelectric element and an electrode are integrated by sintering the thermoelectric element and an electrode at the same time.
현재 국내에서 사용되고 있는 대부분의 열전모듈는 러시아, 중국, 일본, 미국 등에서 단결정이나 일방향응고법으로 제조된 열전재료를 특정 치수의 소자로 기계 가공한 후, 패턴이 인쇄된 세라믹 기판에 전극을 접합하고, 다시 전극과 열전소자를 접합하여 열전모듈을 제조하고 있다.Most thermoelectric modules currently used in Korea currently machine thermoelectric materials manufactured by single crystal or unidirectional solidification method in Russia, China, Japan, USA, etc. into elements of specific dimensions, and then join electrodes to the printed ceramic substrates. A thermoelectric module is manufactured by bonding electrodes and thermoelectric elements.
그러나 단결정이나 일방향 응고재의 Bi-Te계 열전재료는 결정학적으로 특유의 벽계면을 가지고 있어 소자가공 시, 깨지기 쉽고 이로 인하여 회수율이 떨어지는 단점이 있다. 또한 도 2에서와 같이, 금속 도금(metallizing)된 세라믹 기판에 전극을 접합한 후, 다시 열전소자를 전극과 접합하여 최종적인 열전모듈을 제조하게 되는데, 이때 금속도금된 세라믹 기판에 먼저 전극을 접합하고 난 후, 열전소자를 접합하는 2회의 접합공정으로 이루어지기 때문에, 공정이 복잡하고, 또한 접합 솔더(solder)의 선정이 어려울 뿐만 아니라 정밀한 치수제어가 되지 않으면 열전소자와 전극간의 간극이 형성되어 접합불량이 발생되기 쉬운 문제점이 있다.However, Bi-Te-based thermoelectric materials of monocrystalline or unidirectional coagulating materials have crystallographically distinct wall interfaces, which are fragile in device processing, and thus have a disadvantage in that the recovery rate is low. In addition, as shown in Figure 2, after the electrode is bonded to the metal plated (metallizing) ceramic substrate, the thermoelectric element is bonded to the electrode again to produce a final thermoelectric module, wherein the electrode is first bonded to the metal plated ceramic substrate After the process, it is made of two joining processes for joining the thermoelectric elements, and the process is complicated, and the selection of the bonding solder is difficult and the gap between the thermoelectric element and the electrode is formed if the precise dimensional control is not performed. There is a problem that a poor bonding is likely to occur.
본 발명은 상기와 같은 문제점을 해소하기 위해, 주조한 Bi-Te계 열전재료를 파쇄하고, 환원처리를 행한 후, 카본 또는 통전성 몰드 속에 전극재료분말과 열전재료분말을 동시에 충진한 후, 방전가압소결장치로 소결하여 전극과 열전소자가 일체화된 열전재료를 얻는 방법을 제공하는 데 본 발명의 목적이 있는 것이다.The present invention, in order to solve the above problems, after crushing the cast Bi-Te-based thermoelectric material, performing a reduction treatment, and simultaneously filling the electrode material powder and the thermoelectric material powder in a carbon or conductive mold, discharge pressure It is an object of the present invention to provide a method of obtaining a thermoelectric material in which an electrode and a thermoelectric element are integrated by sintering with a sintering apparatus.
이와 같은 목적을 달성하기 위해 본 발명은, 열전재료와 전극재료용 분말을 카본 및 통전성 몰드 내에 전극재료/열전재료/전극재료 또는 전극재료와 열전재료 간의 반응이 문제가 될 경우에는 전극재료/확산방지층/열전재료/확산방지층/전극재료 순으로 적층한 후, 진공 또는 불활성 분위기 하에서 방전가압소결하여 전극과 열전소자가 일체화된 열전재료를 얻는 것에 특징이 있다.In order to achieve the above object, the present invention provides the electrode material / diffusion in the case where the reaction between the electrode material / thermoelectric material / electrode material or the electrode material and the thermoelectric material becomes a problem for the thermoelectric material and the electrode material powder in the carbon and the conductive mold. The stacking layer is formed in the order of the prevention layer / thermoelectric material / diffusion prevention layer / electrode material, and then pressurized and discharged under vacuum or inert atmosphere to obtain a thermoelectric material in which the electrode and the thermoelectric element are integrated.
도 1은 본 발명으로 제조된 열전소자와 전극이 일체화된 열전재료의 개략도1 is a schematic diagram of a thermoelectric material and an electrode integrated thermoelectric material manufactured by the present invention
도 2는 기존 열전모듈 접합부의 개략도2 is a schematic view of a conventional thermoelectric module junction
<도면의 주요부분에 대한 부호의 설명><Description of the code | symbol about the principal part of drawing>
1 : 열전소자 2 : 전극1: thermoelectric element 2: electrode
3 : 확산장벽(diffusion barrier) 4 : Ni 도금층3: diffusion barrier 4: Ni plating layer
5 : 솔더링 층(soldering layer) 6 : 메탈라이징 층 (metallizing layer)5: soldering layer 6: metallizing layer
7 : 세라믹 기판7: ceramic substrate
이하 본 발명에 대해서 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
도 1은 본 발명으로 제조된 일체화된 열전재료의 모식도를 나타낸 것이다. 기본적으로 열전소자(1)와 전극(2)으로 구성되어 있지만, 열전소자 성분(Bi, Sb, Te, Se)과 솔더(solder) 성분과의 계면반응이 문제가 될 경우에는, 전극과 열전소자 사이에 확산방지층(diffusion barrier)(3)을 삽입한 형태로 구성되어 있다.Figure 1 shows a schematic diagram of the integrated thermoelectric material produced by the present invention. Basically, it is composed of the thermoelectric element 1 and the electrode 2, but when the interfacial reaction between the thermoelectric elements (Bi, Sb, Te, Se) and the solder component becomes a problem, the electrode and the thermoelectric element The diffusion barrier layer 3 is inserted in between.
이러한 일체화된 열전재료를 제조하기 위해서는, 진공 주조한 Bi-Te계 열전재료를 분말 형태로 파쇄하고, 350∼500℃ 온도범위에서 1∼10 시간동안 환원처리를 행해준다. 이렇게 얻어진 분말을 카본 및 통전성 몰드(금속 및 WC 등) 속에 전극재료/(확산방지층)/열전재료/(확산방지층)/전극재료의 순서로 분말을 적층 및 가압한 후, 통전가압소결장치를 이용하여 온도구간 200∼500℃, 압력 1∼50MPa의 조건하에서 소결을 행하여 열전소자와 전극이 일체화된 열전재료를 제조하는 것이다.In order to manufacture such an integrated thermoelectric material, the vacuum cast Bi-Te-based thermoelectric material is crushed in powder form and subjected to a reduction treatment for 1 to 10 hours at a temperature in the 350 to 500 ° C range. The powder thus obtained is laminated and pressurized in the order of electrode material / (diffusion layer) / thermoelectric material / (diffusion layer) / electrode material in carbon and conductive molds (metal and WC, etc.) Then, sintering is carried out under a temperature range of 200 to 500 캜 and a pressure of 1 to 50 MPa to produce a thermoelectric material in which the thermoelectric element and the electrode are integrated.
이상에서 상술한 바와 같이 본 발명은, 열전소자와 전극이 일체화된 열전재료를 제조하는 방법으로써, 열전모듈 제조 시, 접합공정을 줄일 수 있을 뿐만 아니라 전극과 열전소자가 일체화되어 있기 때문에, 전극가공이 불필요하고, 소자 가공 시 손상이 적어 소자가공이 용이하고, 회수율이 높은 장점이 있다.As described above, the present invention is a method of manufacturing a thermoelectric material in which a thermoelectric element and an electrode are integrated, and in the manufacturing of a thermoelectric module, not only can the bonding process be reduced, but also the electrode and the thermoelectric element are integrated, so that electrode processing is performed. There is no need for this, and there is little damage during device processing, so that device processing is easy and recovery rate is high.
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100786633B1 (en) * | 2005-12-20 | 2007-12-21 | 한국생산기술연구원 | METHOD FOR MANUFACTURING Bi-Te BASED THERMOELECTRIC MATERIALS |
KR100841418B1 (en) * | 2006-11-29 | 2008-06-25 | 희성금속 주식회사 | Fabrication of a precious metal target using a spark plasma sintering |
KR20110135057A (en) * | 2010-06-10 | 2011-12-16 | 엘지이노텍 주식회사 | Cooling thermoelectric element and method of manufacturing method of the same |
KR101101704B1 (en) * | 2009-12-22 | 2012-01-05 | 한국세라믹기술원 | Electrode for thermoelectric device and manufacturing method of the same |
KR20120057448A (en) * | 2010-11-26 | 2012-06-05 | 현대자동차주식회사 | Thermoelectric device and method for manufacturing the same |
KR20130036079A (en) * | 2011-09-30 | 2013-04-09 | 엘지이노텍 주식회사 | The thermoelectric device manufacturing method |
KR101395565B1 (en) * | 2012-09-17 | 2014-05-15 | 한국세라믹기술원 | Manufacturing method of bismuth telluride thermoelectric material |
KR20160059657A (en) * | 2014-11-19 | 2016-05-27 | 국방과학연구소 | Fabrication method of PbTe thermoelectric materials for decrease of contact resistivity between thermoelectric part and electrode part |
WO2021205803A1 (en) * | 2020-04-10 | 2021-10-14 | パナソニックIpマネジメント株式会社 | Thermoelectric transducer, thermoelectric module, binder and method for manufacturing thermoelectric transducer |
WO2022259758A1 (en) * | 2021-06-08 | 2022-12-15 | パナソニックIpマネジメント株式会社 | Thermoelectric conversion material, composition for thermoelectric conversion material, thermoelectric conversion element, thermoelectric conversion module, and method for producing thermoelectric conversion material |
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KR100786633B1 (en) * | 2005-12-20 | 2007-12-21 | 한국생산기술연구원 | METHOD FOR MANUFACTURING Bi-Te BASED THERMOELECTRIC MATERIALS |
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