JP2016157843A - Thermoelectric conversion device - Google Patents
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本発明は、熱電変換装置に関する。 The present invention relates to a thermoelectric conversion device.
現在、世界のエネルギーは、その多くを化石燃料の燃焼エネルギーに依存しているが、熱サイクルを使用する発電システムの場合、そのエネルギーの多くを廃熱として未利用のまま廃棄しているのが現状である。一方、地球環境の保全が世界的規模で議論されるようになり、エネルギーの未利用分の有効利用技術開発が精力的に進められている。 Currently, much of the world's energy depends on the combustion energy of fossil fuels, but in the case of power generation systems that use thermal cycles, most of that energy is discarded as waste heat. Currently. On the other hand, global environmental conservation has been debated on a global scale, and development of effective utilization technology for unused energy has been energetically promoted.
この中で、熱電変換を用いた発電は、比較的低品質の熱においても直接電気に変換することが可能であるため、現状の未利用の廃熱を回収できる技術であり、最近のエネルギー問題や環境問題の深刻化に伴い、熱電変換に対する期待度はますます大きくなっている。 Among these, power generation using thermoelectric conversion can directly convert even relatively low-quality heat into electricity. As the environmental problems become more serious, expectations for thermoelectric conversion are increasing.
この熱電変換とは、異なる2種の金属やｐ型半導体とｎ型半導体等の熱電変換材料に温度差を与えると、両端に熱起電力が発生するゼーベック効果を利用して、熱エネルギーを直接電力に変換する技術であり、モーターやタービン等の可動部がまったくなく、また、老廃物もないという優れた特徴を有している。 This thermoelectric conversion is the direct application of thermal energy using the Seebeck effect in which thermoelectromotive force is generated at both ends when a temperature difference is given to two different metals or thermoelectric conversion materials such as p-type and n-type semiconductors. It is a technology that converts power into electric power and has excellent features such as no moving parts such as motors and turbines, and no waste.
図１は、従来の熱電変換装置の一例の概略断面図である。図中、１０１はセラミック製の高温側基板、１０２はセラミック製の低温側基板、１０３は高温側電極、１０４は低温側電極、１０５はｎ型熱電変換材料からなるｎ型熱電変換体、１０６はｐ型熱電変換材料からなるｐ型熱電変換体である。 FIG. 1 is a schematic cross-sectional view of an example of a conventional thermoelectric conversion device. In the figure, 101 is a ceramic high temperature side substrate, 102 is a ceramic low temperature side substrate, 103 is a high temperature side electrode, 104 is a low temperature side electrode, 105 is an n type thermoelectric converter made of an n type thermoelectric conversion material, and 106 is It is a p-type thermoelectric converter made of a p-type thermoelectric conversion material.
熱電変換装置はｎ型熱電変換体１０５とｐ型熱電変換体１０６が半田等のろう材を介して、それぞれ高温側電極１０３と低温側電極１０４に接合されている。 In the thermoelectric converter, an n-type thermoelectric converter 105 and a p-type thermoelectric converter 106 are joined to a high temperature side electrode 103 and a low temperature side electrode 104, respectively, via a brazing material such as solder.
このように、熱電変換材料と電極材料を使用して熱電変換装置を作製する場合、ｐ型、ｎ型の各熱電変換材料と電極材料とを高温部と低温部で接合する必要がある。 Thus, when producing a thermoelectric conversion apparatus using a thermoelectric conversion material and an electrode material, it is necessary to join each p-type and n-type thermoelectric conversion material and an electrode material at a high temperature part and a low temperature part.
これらの接合は、熱電変換装置を比較的低温で使用する場合は特に問題ないが、比較的高温で使用する場合は、熱電変換材料、電極材料およびその接合に用いる材料との間の熱膨張係数の整合性が重要であり、熱膨張係数の差が大きい場合は、大きな熱応力が発生し、それに起因して接合部分の劣化、故障等が生じる等の問題が生じていた。
これらの問題点を解決するため、以下のような提案がなされていた。
These junctions are not particularly problematic when the thermoelectric conversion device is used at a relatively low temperature, but when used at a relatively high temperature, the coefficient of thermal expansion between the thermoelectric conversion material, the electrode material, and the material used for the junction is used. When the difference in thermal expansion coefficient is large, a large thermal stress is generated, which causes problems such as deterioration of the joint portion and failure.
In order to solve these problems, the following proposals have been made.
例えば、特許文献１（特開平１０−２０９５０９号公報）には、ｐ型熱電半導体およびｎ型熱電半導体の接合端部と電極層との間に中間層が形成された熱電変換装置が提案されている。 For example, Patent Document 1 (Japanese Patent Laid-Open No. 10-209509) proposes a thermoelectric conversion device in which an intermediate layer is formed between a junction end of a p-type thermoelectric semiconductor and an n-type thermoelectric semiconductor and an electrode layer. Yes.
また、特許文献２（特許第３９２０４０３号公報には、吸熱側電極と、放熱側電極と、前記吸熱側電極と放熱側電極の間に並列に配置されてその吸熱側電極と放熱側電極により電気的に直列に接続されたＰ型半導体層とＮ型半導体層を有する熱電変換装置において、前記吸熱側電極と放熱側電極のうちの少なくとも一方の電極が、両端部付近に前記Ｐ型半導体層ならびにＮ型半導体層と接合する半導体接合領域をそれぞれ有し、その２つの半導体接合領域の間に、当該電極の一方の側端縁から他方の側端縁に向けて当該電極の中心点０付近を通過するように切り込まれた第１の切欠部と、当該電極の他方の側端縁から一方の側端縁に向けて当該電極の中心点０付近を通過するように切り込まれた第２の切欠部とを設けて、平面上において前記電極の一方の側転縁上における第１の切欠部の中心と前記電極の他方の側端縁上における第２の切欠部の中心とが互いにずれており、その第１の切欠部と第２の切欠部の間に幅狭の通電部が形成されている熱電変換装置が提案されている。 Further, Patent Document 2 (Japanese Patent No. 3920403 discloses an endothermic side electrode, a heat radiating side electrode, and the heat absorbing side electrode and the heat radiating side electrode arranged in parallel between the heat absorbing side electrode and the heat radiating side electrode. In a thermoelectric conversion device having a P-type semiconductor layer and an N-type semiconductor layer connected in series, at least one of the heat absorption side electrode and the heat dissipation side electrode is located near both ends of the P type semiconductor layer and Each has a semiconductor junction region to be bonded to the N-type semiconductor layer, and between the two semiconductor junction regions, the vicinity of the center point 0 of the electrode from one side edge to the other side edge of the electrode A first cutout portion that is cut so as to pass through, and a second cutout portion that passes through the vicinity of the center point 0 of the electrode from the other side edge of the electrode toward the one side edge. A notch portion of the The center of the first notch on one side edge of the pole and the center of the second notch on the other side edge of the electrode are offset from each other, and the first notch and the second notch There has been proposed a thermoelectric conversion device in which a narrow energization portion is formed between the notches.
さらに、特許文献３（特許第５４０５９９３号公報）には、充填スクッテルダイト構造のＳｂ系の熱電変換部材と、電極部材と、を有する熱電変換モジュールであって、前記熱電変換部材と前記電極部材とが接合部材で接合されており、前記接合部材は、Ｆｅ−Ｍ（Ｍは、Ｃｒ、Ｍｏ、Ｗ、Ｖ、Ｎｂ、Ｔａ、からなる群から選択される少なくとも一種の元素）合金、Ｃｏ−Ｍ合金、および、Ｎｉ−Ｍ合金、からなる群より選択される少なくとも一種の合金からなる熱電変換モジュールが提案されている。 Further, Patent Document 3 (Japanese Patent No. 5405993) discloses a thermoelectric conversion module having an Sb-based thermoelectric conversion member having a filled skutterudite structure, and an electrode member, the thermoelectric conversion member and the electrode member. Are bonded by a bonding member, and the bonding member is an Fe-M alloy (M is at least one element selected from the group consisting of Cr, Mo, W, V, Nb, Ta), Co- A thermoelectric conversion module made of at least one alloy selected from the group consisting of M alloy and Ni-M alloy has been proposed.
しかしながら、上記特許文献１に提案された熱電変換装置によると、熱電半導体の接合端部では凹部が観察され、この凹部に、接合層（材）や中間層（材）や電極層（材）が入り込んだ構造となっていることによって、熱膨張（係数）差に起因する応力を緩和することができているが、中間層が、熱電材料と電極材料の構成元素と同じ構成元素を含む構造となっていないために、応力の緩和はまだ不十分であるという不具合が生じている。 However, according to the thermoelectric conversion device proposed in Patent Document 1, a concave portion is observed at the junction end portion of the thermoelectric semiconductor, and the junction layer (material), the intermediate layer (material), and the electrode layer (material) are formed in the concave portion. Although it is possible to relieve the stress caused by the difference in thermal expansion (coefficient) due to the embedded structure, the intermediate layer includes the same constituent elements as the constituent elements of the thermoelectric material and the electrode material. As a result, there is a problem that stress relaxation is still insufficient.
また、上記特許文献２に提案された熱電変換装置によると、半導体層と電極の熱膨張係数の違いを有効に吸収し、接合強度を保持することにより、熱サイクルを繰り返しても性能劣化が少ない、動作信頼性に優れ、耐用寿命の長い熱電変換装置を提供することができるが、電極形状が複雑なため、生産性が悪く、電極製造の歩留まりも非常に小さくなってしまうという不具合が生じている。 In addition, according to the thermoelectric conversion device proposed in Patent Document 2, the difference in the thermal expansion coefficient between the semiconductor layer and the electrode is effectively absorbed, and the bonding strength is maintained, so that the performance deterioration is small even when the thermal cycle is repeated. Although it is possible to provide a thermoelectric conversion device with excellent operational reliability and a long service life, the electrode shape is complicated, resulting in poor productivity and extremely low electrode manufacturing yield. Yes.
また、上記特許文献３に提案された熱電変換モジュールによると、熱電変換モジュールの温度が作動などにより大幅に変化しても、熱電変換部材と電極部材との接合を良好に維持することができる熱電変換モジュールを提供することができるが、中間層が、熱電材料と電極材料の構成元素と同じ構成元素を含む構造となっていないために、接合を良好に維持することはまだ不十分であるという不具合が生じている。 Further, according to the thermoelectric conversion module proposed in Patent Document 3, even if the temperature of the thermoelectric conversion module changes significantly due to operation or the like, it is possible to maintain a good junction between the thermoelectric conversion member and the electrode member. Although a conversion module can be provided, it is still insufficient to maintain good bonding because the intermediate layer is not structured to contain the same constituent elements as the constituent elements of the thermoelectric and electrode materials There is a problem.
そこで、本発明の目的は、熱電変換材料と電極材料との接合が良好に維持され、熱サイクルの繰り返し特性が良好な、耐用寿命の長い熱電変換装置を提供することにある。 Accordingly, an object of the present invention is to provide a thermoelectric conversion device having a long useful life, in which the bonding between the thermoelectric conversion material and the electrode material is maintained well, the thermal cycle repeatability is good.
本発明は、熱電変換材料と電極材料とを有する熱電変換装置において、前記熱電変換材料からなる熱電変換体と前記電極材料からなる電極との間に中間層が具備され、前記中間層が、少なくとも前記熱電変換材料の構成元素と前記電極材料の構成元素の両方を含有する組成からなることを特徴とする熱電変換装置である。 The present invention provides a thermoelectric conversion device having a thermoelectric conversion material and an electrode material, wherein an intermediate layer is provided between the thermoelectric conversion body made of the thermoelectric conversion material and the electrode made of the electrode material, and the intermediate layer has at least A thermoelectric conversion device comprising a composition containing both the constituent elements of the thermoelectric conversion material and the constituent elements of the electrode material.
本発明によれば、熱電変換材料と電極材料との接合が良好に維持され、熱サイクルの繰り返し特性が良好な、耐用寿命の長い熱電変換装置を提供することができた。 According to the present invention, it is possible to provide a thermoelectric conversion device having a long service life, in which the bonding between the thermoelectric conversion material and the electrode material is maintained well, the thermal cycle repeatability is good.
以下、本発明の実施形態について図面を用いて説明する。
図２は、本発明の熱電変換装置の一例の概要を示したものである。熱電変換体をｐ型とｎ型一対として簡略化して示している。
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 2 shows an outline of an example of the thermoelectric conversion device of the present invention. The thermoelectric converter is shown in a simplified form as a pair of p-type and n-type.
図２に示すように本実施の形態の熱電変換装置は、少なくともｐ型の熱電変換材料からなるｐ型熱電変換体２０１、ｎ型の熱電変換材料からなるｎ型熱電変換体２０２、中間層２０３、高温側電極２０４および低温側電極２０５を具備している。 As shown in FIG. 2, the thermoelectric conversion device according to the present embodiment includes at least a p-type thermoelectric converter 201 made of a p-type thermoelectric conversion material, an n-type thermoelectric converter 202 made of an n-type thermoelectric conversion material, and an intermediate layer 203. The high temperature side electrode 204 and the low temperature side electrode 205 are provided.
ｐ型の熱電変換材料からなるｐ型熱電変換体２０１、ｎ型の熱電変換材料からなるｎ型熱電変換体２０２は、中間層２０３を介して高温側電極２０４および低温側電極２０５の電極材料に接合されている。 A p-type thermoelectric converter 201 made of a p-type thermoelectric conversion material and an n-type thermoelectric converter 202 made of an n-type thermoelectric conversion material are used as electrode materials for the high temperature side electrode 204 and the low temperature side electrode 205 via an intermediate layer 203. It is joined.
ここで、ｐ型熱電変換体２０１およびｎ型熱電変換体２０２を構成する熱電変換材料としては、例えばＢｉ−Ｔｅ系材料、Ｐｂ−Ｔｅ系材料、Ａｇ−Ｓｂ−Ｔｅ系材料、Ｓｉ−Ｇｅ系材料、Ｆｅ−Ｓｉ系あるいはＭｎ−Ｓｉ系あるいはＣｒ−Ｓｉ系あるいはＭｇ−Ｓｉ系のシリサイド系材料、スクッテルダイト系材料、酸化物系材料、有機物系材料をはじめとした種々の熱電材料を用いることができ、特に制限されない。 Here, as the thermoelectric conversion material constituting the p-type thermoelectric converter 201 and the n-type thermoelectric converter 202, for example, a Bi-Te-based material, a Pb-Te-based material, an Ag-Sb-Te-based material, or a Si-Ge-based material. Various thermoelectric materials including materials, Fe-Si-based, Mn-Si-based, Cr-Si-based, or Mg-Si-based silicide-based materials, skutterudite-based materials, oxide-based materials, and organic materials are used. There is no particular limitation.
高温側電極２０４および低温側電極２０５を構成する電極材料としては、例えばＦｅおよびその合金、Ｃｏおよびその合金、Ｎｉおよびその合金、Ａｕおよびその合金、Ａｇおよびその合金、Ｃｕおよびその合金、Ｃｒおよびその合金、Ｔｉおよびその合金、Ａｌおよびその合金をはじめとした金属系材料の他、セラミック材料等の非金属材料および導電性高分子等をはじめとした有機材料を用いることができるが、特に制限することはなく、導電性の材料を用いることができる。 Examples of electrode materials constituting the high temperature side electrode 204 and the low temperature side electrode 205 include Fe and its alloys, Co and its alloys, Ni and its alloys, Au and their alloys, Ag and their alloys, Cu and their alloys, Cr and In addition to metallic materials such as alloys thereof, Ti and alloys thereof, Al and alloys thereof, non-metallic materials such as ceramic materials and organic materials such as conductive polymers can be used, but there is a particular limitation. There is no need to use a conductive material.
ここで、熱電変換材料と電極材料とが直接接合していると、熱電変換材料と電極材料の熱膨張係数の差が大きいとそこで大きな熱応力が生じるため、使用を繰り返しているうちに密着性が低下し、接合部分の一部が破断してしまうという不具合が生じる。 Here, if the thermoelectric conversion material and the electrode material are directly bonded, a large difference in the thermal expansion coefficient between the thermoelectric conversion material and the electrode material will cause a large thermal stress there. Decreases, and a problem arises in that a part of the joint portion is broken.
そこで、本発明では、熱電変換体２０１、２０２と電極２０４、２０５の間に中間層２０３を具備しており、熱電変換体（以下、熱電変換材料と称することがある。）２０１、２０２は、中間層２０３を介して電極（以下、電極材料と称することがある。）２０４、２０５に接合されている。 Therefore, in the present invention, the intermediate layer 203 is provided between the thermoelectric converters 201 and 202 and the electrodes 204 and 205, and the thermoelectric converters (hereinafter sometimes referred to as thermoelectric conversion materials) 201 and 202 are: Bonded to electrodes (hereinafter also referred to as electrode materials) 204 and 205 via an intermediate layer 203.
中間層２０３としては、種々の材料を使用することができるが、繰り返し使用した場合にも接合部分が破断しないように、材料を選択することが必要である。そのために、中間層２０３が、直接接している前記熱電変換材料２０１，２０２の構成元素と前記電極材料２０４，２０５の構成元素の両方を含有することが重要となる。中間層の構成元素は、熱電変換材料および電極材料の各構成元素以外の元素を含むものであっても良いが、熱電変換材料および電極材料の両方の構成元素を含むことが必要である。 Various materials can be used for the intermediate layer 203, but it is necessary to select materials so that the joint portion does not break even when used repeatedly. Therefore, it is important that the intermediate layer 203 contains both the constituent elements of the thermoelectric conversion materials 201 and 202 and the constituent elements of the electrode materials 204 and 205 that are in direct contact with each other. The constituent elements of the intermediate layer may include elements other than the constituent elements of the thermoelectric conversion material and the electrode material, but it is necessary to include constituent elements of both the thermoelectric conversion material and the electrode material.
この時、中間層２０３の熱膨張率は、熱電変換材料２０１、２０２と電極材料２０４、２０５の熱膨張率の間の値にすることが好ましい。 At this time, the thermal expansion coefficient of the intermediate layer 203 is preferably set to a value between the thermal expansion coefficients of the thermoelectric conversion materials 201 and 202 and the electrode materials 204 and 205.
ここで、中間層２０３の組成は、前記熱電変換材料の構成元素が前記電極側よりも前記熱電変換体側の方で多く、前記電極材料の構成元素が前記熱電変換体側よりも前記電極側の方で多くなるような組成とすることが好ましい。特に、前記中間層の組成は、前記熱電変換体側から前記電極側になるにつれて、徐々に前記熱電変換材料の構成元素が多い組成から前記電極材料の構成元素が多い組成へと組成変化する構成にすると、熱電変換材料２０１、２０２との界面、および電極材料２０４、２０５との界面が同じ組成とすることが可能となるため、熱膨張係数の差がなく、使用を繰り返しても接合部分の密着性が低下することがないため、繰り返し耐久性の大きい熱電変換装置を提供することができる。 Here, the composition of the intermediate layer 203 is such that the constituent elements of the thermoelectric conversion material are more on the thermoelectric converter side than the electrode side, and the constituent elements of the electrode material are on the electrode side rather than the thermoelectric converter side. It is preferable to make the composition so as to increase. In particular, the composition of the intermediate layer gradually changes from a composition with many constituent elements of the thermoelectric conversion material to a composition with many constituent elements of the electrode material as it goes from the thermoelectric converter side to the electrode side. Then, the interface with the thermoelectric conversion materials 201 and 202 and the interface with the electrode materials 204 and 205 can have the same composition. Therefore, a thermoelectric conversion device having high durability can be provided.
このような中間層の形成方法としては、熱電変換材料の構成元素と電極材料の構成元素との組成割合を変化させた層を順に熱電変換体側あるいは電極側から積層し、次いで加圧成型及び一体焼結することによって、組成が変化した中間層を作製することができる。 As a method for forming such an intermediate layer, layers in which the composition ratios of the constituent elements of the thermoelectric conversion material and the constituent elements of the electrode material are changed are sequentially laminated from the thermoelectric converter side or the electrode side, and then pressed and integrated. By sintering, an intermediate layer having a changed composition can be produced.
なお熱電変換材料２０１、２０２と中間層２０３との間、および中間層２０３と電極材料２０４、２０５との間に、新たに接合層を設けても問題ない。 Note that there is no problem even if a new bonding layer is provided between the thermoelectric conversion materials 201 and 202 and the intermediate layer 203 and between the intermediate layer 203 and the electrode materials 204 and 205.
以下、本発明の実施例について説明するが、本発明は下記実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to the following examples.
実施例１
ｐ型の熱電変換材料としてCa3Co4O9を用い、n型の熱電変換材料としてCaMnO3を用いて切削加工により、各材料を5mm×5mm×7mmの角柱状に加工した。
Example 1
Each material was processed into a prismatic shape of 5 mm × 5 mm × 7 mm by cutting using Ca 3 Co 4 O 9 as a p-type thermoelectric conversion material and CaMnO 3 as an n-type thermoelectric conversion material.
ｐ型の熱電変換材料；Ca3Co4O9の両端面には、中間層としてＡｇペースト中にCa3Co4O9粉末とＮｉ粉末を混合したものを塗布し、n型の熱電変換材料；CaMnO3の両端面には中間層としてＡｇペーストにCaMnO3粉末とNi粉末を混合したものを塗布した。この中間層の概念図を図３に示した。図３中、３０１はＡｇペースト、３０２はn型（又はp型）熱電変換材料、３０３は電極材料のNi粉末である。 p-type thermoelectric conversion material; on both end faces of Ca 3 Co 4 O 9, by applying a mixture of Ca 3 Co 4 O 9 powder and Ni powder in the Ag paste as an intermediate layer, n-type thermoelectric conversion material ; on both end faces of CaMnO 3 was applied a mixture of CaMnO 3 powder and Ni powder Ag paste as an intermediate layer. A conceptual diagram of this intermediate layer is shown in FIG. In FIG. 3, 301 is an Ag paste, 302 is an n-type (or p-type) thermoelectric conversion material, and 303 is an Ni powder as an electrode material.
この両端に中間層を塗布したｐ型熱電変換材料とｎ型熱電変換材料を１８対並べ、上下に電極材料としてＮｉを、ｐ型熱電変換材料とｎ型熱電変換材料が直列に接続されるように貼付けした。さらに、電極材料上にアルミナ基板をセラミックスボンドで貼付けして乾燥し、熱電変換装置を作製した。 18 pairs of p-type thermoelectric conversion material and n-type thermoelectric conversion material coated with an intermediate layer on both ends are arranged, Ni is used as an electrode material above and below, and p-type thermoelectric conversion material and n-type thermoelectric conversion material are connected in series. Pasted on. Furthermore, an alumina substrate was attached to the electrode material with a ceramic bond and dried to produce a thermoelectric conversion device.
高温側にブロックヒーターを使用し、低温側には水冷ブロックを使用し、ヒートサイクル試験を実施した。ヒートサイクル試験は高温側の温度を２００℃から６００℃の間を毎分２０℃の速度で昇降温し、６００℃で１時間保持するように制御して実施した。 A heat cycle test was performed using a block heater on the high temperature side and a water cooling block on the low temperature side. The heat cycle test was carried out by controlling the temperature on the high temperature side so as to rise and fall between 200 ° C. and 600 ° C. at a rate of 20 ° C. per minute and hold at 600 ° C. for 1 hour.
ヒートサイクルを１００サイクルまで実施したが、サイクル毎に測定した熱電変換装置の内部抵抗は増加せず、熱サイクルの繰り返し特性が良好である熱電変換装置が作製できた。 Although the heat cycle was performed up to 100 cycles, the internal resistance of the thermoelectric conversion device measured for each cycle did not increase, and a thermoelectric conversion device having good heat cycle repeatability could be produced.
実施例２
ｐ型の熱電変換材料としてMnSi1.73を用い、n型の熱電変換材料としてMg2Si0.4Sn0.6を用いて切削加工により、各材料を5mm×5mm×7mmの角柱状に加工した。
Example 2
Each material was processed into a prismatic shape of 5 mm × 5 mm × 7 mm by cutting using MnSi 1.73 as a p-type thermoelectric conversion material and using Mg 2 Si 0.4 Sn 0.6 as an n-type thermoelectric conversion material.
ｐ型の熱電変換材料；MnSi1.73の両端面には、中間層としてＡｇペースト中にMnSi1.73粉末とＮｉ粉末を混合したものを塗布し、n型の熱電変換材料；Mg2Si0.4Sn0.6の両端面には中間層としてＡｇペーストにMg2Si0.4Sn0.6粉末とNi粉末を混合したものを塗布した。 On both end faces of MnSi 1.73, it was coated a mixture of MnSi 1.73 powder and Ni powder in the Ag paste as an intermediate layer, n-type thermoelectric conversion material; thermoelectric conversion material of a p-type Mg 2 Si 0.4 Sn 0.6 A mixture of Ag paste and Mg 2 Si 0.4 Sn 0.6 powder and Ni powder was applied to both end faces as an intermediate layer.
この両端に中間層を塗布したｐ型熱電変換材料とｎ型熱電変換材料を１８対並べ、上下に電極材料としてＮｉを、ｐ型熱電変換材料とｎ型熱電変換材料が直列に接続されるように貼付けした。さらに、電極材料上にアルミナ基板をセラミックスボンドで貼付けして乾燥し、熱電変換装置を作製した。 18 pairs of p-type thermoelectric conversion material and n-type thermoelectric conversion material coated with an intermediate layer on both ends are arranged, Ni is used as an electrode material above and below, and p-type thermoelectric conversion material and n-type thermoelectric conversion material are connected in series. Pasted on. Furthermore, an alumina substrate was attached to the electrode material with a ceramic bond and dried to produce a thermoelectric conversion device.
高温側にブロックヒーターを使用し、低温側には水冷ブロックを使用し、ヒートサイクル試験を実施した。ヒートサイクル試験は高温側の温度を２００℃から６００℃の間を毎分２０℃の速度で昇降温し、６００℃で１時間保持するように制御して実施した。 A heat cycle test was performed using a block heater on the high temperature side and a water cooling block on the low temperature side. The heat cycle test was carried out by controlling the temperature on the high temperature side so as to rise and fall between 200 ° C. and 600 ° C. at a rate of 20 ° C. per minute and hold at 600 ° C. for 1 hour.
ヒートサイクルを１００サイクルまで実施したが、サイクル毎に測定した熱電変換装置の内部抵抗は増加せず、熱サイクルの繰り返し特性が良好である熱電変換装置が作製できた。 Although the heat cycle was performed up to 100 cycles, the internal resistance of the thermoelectric conversion device measured for each cycle did not increase, and a thermoelectric conversion device having good heat cycle repeatability could be produced.
実施例３
ｐ型の熱電変換材料としてCa3Co4O9を用い、Ca3Co4O9上にＮｉの含有量を20%、40%、60%、80%（重量基準）と変化させたCa3Co4O9/Ni混合粉末を積層し、加圧成型した。これを一体焼結することにより、Ca3Co4O9からＮｉまで徐々に組成が変化する電極一体型ｐ型熱電変換材料を作製した。この電極一体型ｐ型熱電変換材料の概念図を図４に示した。図４中、４０１はｐ型の熱電変換材料であるCa3Co4O9からなる層、４０２はCa3Co4O9／20%Ｎｉからなる層、４０３はCa3Co4O9／40%Ｎｉからなる層、４０４はCa3Co4O9／60%Ｎｉからなる層、４０５はCa3Co4O9／80%Ｎｉからなる層、４０６はＮｉ電極である。
Example 3
using Ca 3 Co 4 O 9 as the p-type thermoelectric conversion material, Ca 3 Co 4 on O 9 content of Ni 20%, 40%, 60 %, Ca 3 was changed to 80% (by weight) Co 4 O 9 / Ni mixed powder was laminated and pressure molded. By integrally sintering this, an electrode-integrated p-type thermoelectric conversion material whose composition gradually changed from Ca 3 Co 4 O 9 to Ni was produced. A conceptual diagram of this electrode-integrated p-type thermoelectric conversion material is shown in FIG. In Figure 4, a layer made of Ca 3 Co 4 O 9 is a thermoelectric conversion material of a p-type 401, 402 consists of Ca 3 Co 4 O 9/20 % Ni layers 403 Ca 3 Co 4 O 9/40 A layer made of% Ni, 404 is a layer made of Ca 3 Co 4 O 9 /60% Ni, 405 is a layer made of Ca 3 Co 4 O 9 /80% Ni, and 406 is a Ni electrode.
同様にn型の熱電変換材料としてCaMnO3を用い、CaMnO3上にＮｉの含有量を20%、40%、60%、80%（重量基準）と変化させたCaMnO3/Ni混合粉末を積層し、加圧成型した。これを一体焼結することにより、CaMnO3からＮｉまで徐々に組成が変化する電極一体型ｎ型熱電変換材料を作製した。 Similarly the CaMnO 3 used as n-type thermoelectric conversion material, laminating a Ni content on the CaMnO 3 20%, 40%, a 60%, 80% CaMnO 3 / Ni mixed powder was changed (by weight) And then pressure-molded. By integrally sintering this, an electrode-integrated n-type thermoelectric conversion material whose composition gradually changed from CaMnO 3 to Ni was produced.
これらの電極一体型のｐ型熱電変換材料とｎ型熱電変換材料を切削加工により、各々を5mm×5mm×7mmの角柱状に加工した。 These electrode-integrated p-type thermoelectric conversion material and n-type thermoelectric conversion material were each cut into a prismatic shape of 5 mm × 5 mm × 7 mm by cutting.
この電極一体型のｐ型熱電変換材料とｎ型熱電変換材料を１８対並べ、これをさらにＮｉで、ｐ型熱電変換材料とｎ型熱電変換材料が直列になるように接続した。さらに、電極材料上にアルミナ基板をセラミックスボンドで貼付けして乾燥し、熱電変換装置を作製した。 18 pairs of this electrode-integrated p-type thermoelectric conversion material and n-type thermoelectric conversion material were arranged, and this was further connected with Ni so that the p-type thermoelectric conversion material and the n-type thermoelectric conversion material were in series. Furthermore, an alumina substrate was attached to the electrode material with a ceramic bond and dried to produce a thermoelectric conversion device.
高温側にブロックヒーターを使用し、低温側には水冷ブロックを使用し、ヒートサイクル試験を実施した。ヒートサイクル試験は高温側の温度を２００℃から６００℃の間を毎分２０℃の速度で昇降温し、６００℃で１時間保持するように制御して実施した。 A heat cycle test was performed using a block heater on the high temperature side and a water cooling block on the low temperature side. The heat cycle test was carried out by controlling the temperature on the high temperature side so as to rise and fall between 200 ° C. and 600 ° C. at a rate of 20 ° C. per minute and hold at 600 ° C. for 1 hour.
ヒートサイクルを１００サイクルまで実施したが、サイクル毎に測定した熱電変換装置の内部抵抗は増加せず、熱サイクルの繰り返し特性が良好である熱電変換装置が作製できた。 Although the heat cycle was performed up to 100 cycles, the internal resistance of the thermoelectric conversion device measured for each cycle did not increase, and a thermoelectric conversion device having good heat cycle repeatability could be produced.
実施例４
ｐ型の熱電変換材料としてMnSi1.73を用い、MnSi1.73上にＮｉの含有量を20%、40%、60%、80%（重量基準）と変化させたMnSi1.73/Ni混合粉末を積層し、加圧成型した。これを一体焼結することにより、MnSi1.73からＮｉまで徐々に組成が変化する電極一体型ｐ型熱電変換材料を作製した。この電極一体型ｐ型熱電変換材料の電極とｐ型熱電変換材料を除いた部分の平均の熱膨張率は、ＮｉとMnSi1.73の間に設定することができた。
Example 4
used MnSi 1.73 as p-type thermoelectric conversion material, by stacking a Ni content on the MnSi 1.73 20%, 40%, a 60%, 80% MnSi 1.73 / Ni mixed powder was changed (by weight), Press molded. By integrally sintering this, an electrode-integrated p-type thermoelectric conversion material whose composition gradually changed from MnSi 1.73 to Ni was produced. The average coefficient of thermal expansion of the electrode-integrated p-type thermoelectric conversion material excluding the electrode and the p-type thermoelectric conversion material could be set between Ni and MnSi 1.73 .
同様にn型の熱電変換材料としてMg2Si0.4Sn0.6を用い、Mg2Si0.4Sn0.6上にＮｉの含有量を20%、40%、60%、80%（重量基準）と変化させたMg2Si0.4Sn0.6/Ni混合粉末を積層し、加圧成型した。これを一体焼結することにより、Mg2Si0.4Sn0.63からＮｉまで徐々に組成が変化する電極一体型ｎ型熱電変換材料を作製した。この電極一体型ｎ型熱電変換材料の電極とｎ型熱電変換材料を除いた部分の平均の熱膨張率は、ＮｉとMg2Si0.4Sn0.63の間に設定することができた。 Similarly, Mg 2 Si 0.4 Sn 0.6 was used as the n-type thermoelectric conversion material, and the Ni content was changed to 20%, 40%, 60%, and 80% (by weight) on Mg 2 Si 0.4 Sn 0.6 . Mg 2 Si 0.4 Sn 0.6 / Ni mixed powder was laminated and pressure molded. By integrally sintering this, an electrode-integrated n-type thermoelectric conversion material whose composition gradually changed from Mg 2 Si 0.4 Sn 0.63 to Ni was produced. The average coefficient of thermal expansion of the electrode-integrated n-type thermoelectric conversion material excluding the electrode and the n-type thermoelectric conversion material could be set between Ni and Mg 2 Si 0.4 Sn 0.63 .
これらの電極一体型のｐ型熱電材料とｎ型熱電材料を切削加工により、各々を5mm×5mm×7mmの角柱状に加工した。 These electrode-integrated p-type thermoelectric material and n-type thermoelectric material were each cut into a prismatic shape of 5 mm × 5 mm × 7 mm by cutting.
この電極一体型のｐ型熱電材料とｎ型熱電材料を１８対並べ、これをさらにＮｉで、ｐ型熱電材料とｎ型熱電材料が直列になるように接続した。さらに、電極材料上にアルミナ基板をセラミックスボンドで貼付けして乾燥し、熱電変換装置を作製した。 Eighteen pairs of this electrode-integrated p-type thermoelectric material and n-type thermoelectric material were arranged, and these were further connected with Ni so that the p-type thermoelectric material and the n-type thermoelectric material were in series. Furthermore, an alumina substrate was attached to the electrode material with a ceramic bond and dried to produce a thermoelectric conversion device.
高温側にブロックヒーターを使用し、低温側には水冷ブロックを使用し、ヒートサイクル試験を実施した。ヒートサイクル試験は高温側の温度を２００℃から６００℃の間を毎分２０℃の速度で昇降温し、６００℃で１時間保持するように制御して実施した。 A heat cycle test was performed using a block heater on the high temperature side and a water cooling block on the low temperature side. The heat cycle test was carried out by controlling the temperature on the high temperature side so as to rise and fall between 200 ° C. and 600 ° C. at a rate of 20 ° C. per minute and hold at 600 ° C. for 1 hour.
ヒートサイクルを１００サイクルまで実施したが、サイクル毎に測定した熱電変換装置の内部抵抗は増加せず、熱サイクルの繰り返し特性が良好である熱電変換装置が作製できた。 Although the heat cycle was performed up to 100 cycles, the internal resistance of the thermoelectric conversion device measured for each cycle did not increase, and a thermoelectric conversion device having good heat cycle repeatability could be produced.
なお、実施例３，４においては、中間層におけるＮｉの含有量を20%、40%、60%、80%と変化させたが、0%、20%、40%、60%、80%、100%と変化させれば、各熱電変換体との界面、および電極との界面が同じ組成となる。また、Ｎｉの含有量をさらに細かく変化させた層構成とすることにより、焼結後の組成変化をほぼ連続的にすることができる。その結果、熱膨張係数の差がなく、使用を繰り返しても接合部分の密着性が低下することがない熱電変換装置が得られる。 In Examples 3 and 4, the content of Ni in the intermediate layer was changed to 20%, 40%, 60%, and 80%, but 0%, 20%, 40%, 60%, 80%, If it is changed to 100%, the interface with each thermoelectric converter and the interface with the electrode have the same composition. Further, by adopting a layer structure in which the Ni content is further finely changed, the composition change after sintering can be made almost continuous. As a result, it is possible to obtain a thermoelectric conversion device that has no difference in thermal expansion coefficient and does not deteriorate the adhesiveness of the joined portion even after repeated use.
以上、実施例で示したように、本発明により、熱電変換材料と電極材料との間に中間層が具備され、前記中間層が、少なくとも前記熱電変換材料の構成元素と前記電極材料の構成元素を含有することにより、熱電変換材料と電極材料の熱膨張係数の違いから生じる応力を有効に吸収することにより、熱サイクルの繰り返し特性が良好な熱電変換装置を提供することが可能になった。 As described above, as shown in the examples, according to the present invention, an intermediate layer is provided between the thermoelectric conversion material and the electrode material, and the intermediate layer includes at least a constituent element of the thermoelectric conversion material and a constituent element of the electrode material. As a result, it is possible to provide a thermoelectric conversion device with good thermal cycle repeatability by effectively absorbing stress resulting from the difference in thermal expansion coefficient between the thermoelectric conversion material and the electrode material.
１０１ 高温側基板
１０２ 低温側基板
１０３、２０４ 高温側電極
１０４、２０５ 低温側電極
１０５、２０２ ｎ型熱電変換体
１０６、２０１ ｐ型熱電変換体
２０３ 中間層
３０１ Ａｇペースト
３０２ n型（又はp型）熱電変換材料
３０３ Ni粉末
４０１ Ca3Co4O9からなる層
４０２ Ca3Co4O9／20%Ｎｉからなる層
４０３ Ca3Co4O9／40%Ｎｉからなる層
４０４ Ca3Co4O9／60%Ｎｉからなる層
４０５ Ca3Co4O9／80%Ｎｉからなる層
４０６ Ｎｉ電極
101 High-temperature side substrate 102 Low-temperature side substrate 103, 204 High-temperature side electrode 104, 205 Low-temperature side electrode 105, 202 n-type thermoelectric converter 106, 201 p-type thermoelectric converter 203 Intermediate layer 301 Ag paste 302 n-type (or p-type) thermoelectric conversion material 303 Ni powder 401 Ca 3 Co 4 consisting O 9 layers 402 Ca 3 Co 4 O 9 / consisting 20% Ni layer 403 Ca 3 Co 4 O consists 9/40% Ni layer 404 Ca 3 Co 4 O 9 /60% Ni layer 405 Ca 3 Co 4 O 9 /80% Ni layer 406 Ni electrode
Claims (4)
前記熱電変換材料からなる熱電変換体と前記電極材料からなる電極との間に中間層が具備され、
前記中間層が、少なくとも前記熱電変換材料の構成元素と前記電極材料の構成元素の両方を含有する組成であることを特徴とする熱電変換装置。 In a thermoelectric conversion device having a thermoelectric conversion material and an electrode material,
An intermediate layer is provided between the thermoelectric converter made of the thermoelectric conversion material and the electrode made of the electrode material,
The intermediate layer has a composition containing at least both a constituent element of the thermoelectric conversion material and a constituent element of the electrode material.
The thermal expansion coefficient as a whole of the intermediate layer has a value between the thermal expansion coefficient of the thermoelectric converter and the thermal expansion coefficient of the electrode. Thermoelectric converter.
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| KR20210089686A (en) | 2018-11-16 | 2021-07-16 | 가부시기가이샤야스나가 | Stanide-based thermoelectric conversion element and stanide-based thermoelectric conversion module |
| WO2021153550A1 (en) * | 2020-01-31 | 2021-08-05 | 国立研究開発法人産業技術総合研究所 | Thermoelectric conversion module |
| US20230157174A1 (en) * | 2020-01-31 | 2023-05-18 | National Institute Of Advanced Industrial Science And Technology | Thermoelectric conversion module |
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