JP3981738B2 - Thermoelectric conversion element - Google Patents

Thermoelectric conversion element Download PDF

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JP3981738B2
JP3981738B2 JP2004380904A JP2004380904A JP3981738B2 JP 3981738 B2 JP3981738 B2 JP 3981738B2 JP 2004380904 A JP2004380904 A JP 2004380904A JP 2004380904 A JP2004380904 A JP 2004380904A JP 3981738 B2 JP3981738 B2 JP 3981738B2
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thermoelectric conversion
conversion element
thermal conductivity
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thermoelectric
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JP2006186255A (en
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雅敏 武田
直之 佐藤
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Nagaoka University of Technology
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本発明は、温度差を利用して熱を電気に変換する熱電変換素子に関するものである。   The present invention relates to a thermoelectric conversion element that converts heat into electricity using a temperature difference.

従来、温度差を利用して熱を電気に変換する熱電変換素子として、例えばＢi−Ｔe系の半導体を利用したものが知られている。この半導体を利用した熱電変換素子は、例えば図３に示すように、Ｐ型半導体１０とＮ型半導体２０を接合して電気的に接続し、接合側を高温にさらすとともに分岐側を低温にさらすことにより、その温度差を利用して発電することができるものである。また、従来より時計等に用いられている熱電変換素子の構造は、例えば図４に示すように、Ｐ型半導体１０やＮ型半導体２０である溶製材または焼結材をブロック状に切り出し、セラミックス等の基板４０上に電極３０を介して配列したものが知られている。（特許文献１、２、３参照）
しかしながら、前記従来例の熱電変換素子は、機械的強度が低く加工性が悪い。従って、自動化が困難で大量生産が困難である。また、基板に高硬度のものを使用するため、柔軟性が悪く曲面箇所等への設置が困難であり、設置箇所が制限される。（特許文献２、３参照）
また、前記問題点を解決するために、図５に示すように、基板４０に柔軟性を有するポリイミド製のフィルムを使用したものがある。（特許文献１参照）しかしながら、この場合においては、発電効率が悪いという問題がある。
特開２００３−１３３６００号公報 特許第３５７３４４８号公報 特開平１１−２５１６４８号公報 2. Description of the Related Art Conventionally, as a thermoelectric conversion element that converts heat into electricity using a temperature difference, for example, a device that uses a Bi-Te based semiconductor is known. In the thermoelectric conversion element using this semiconductor, for example, as shown in FIG. 3, a P-type semiconductor 10 and an N-type semiconductor 20 are joined and electrically connected, and the junction side is exposed to a high temperature and the branch side is exposed to a low temperature. Therefore, it is possible to generate power using the temperature difference. In addition, the structure of a thermoelectric conversion element conventionally used in a watch or the like is formed by cutting a melted material or a sintered material, which is a P-type semiconductor 10 or an N-type semiconductor 20, into a block shape, for example, as shown in FIG. And the like arranged on the substrate 40 via the electrode 30 is known. (See Patent Documents 1, 2, and 3)
However, the thermoelectric conversion element of the conventional example has low mechanical strength and poor workability. Therefore, automation is difficult and mass production is difficult. In addition, since a substrate having a high hardness is used, the flexibility is poor and it is difficult to install on a curved surface or the like, and the installation location is limited. (See Patent Documents 2 and 3)
Moreover, in order to solve the said problem, as shown in FIG. However, in this case, there is a problem that power generation efficiency is poor.
JP 2003-133600 A Japanese Patent No. 3573448 Japanese Patent Laid-Open No. 11-251648

解決しようとする課題は、機械的強度が高く、加工性に優れ、従って自動化が容易で大量生産が容易、しかも曲面等への設置も可能で設置場所が制限されることのない、発電効率の高い熱電変換素子を提供するという点である。   The problems to be solved are high mechanical strength, excellent workability, easy automation, easy mass production, installation on curved surfaces, etc. This is to provide a high thermoelectric conversion element.

本発明は、前記課題を解決するために、温度差を利用して熱を電気に変換する熱電変換素子であって、Ｐ型材料からなる薄膜のＰ型熱電素子とＮ型材料からなる薄膜のＮ型熱電素子とで構成された熱電変換モジュールの両面に、2種類以上の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板を設け、熱伝導率の高い材料が前記基板の外面の一部分に位置するように構成したことを特徴とするものである。   In order to solve the above-mentioned problems, the present invention is a thermoelectric conversion element that converts heat into electricity using a temperature difference, and includes a thin P-type thermoelectric element made of P-type material and a thin-film made of N-type material. Provided on both sides of a thermoelectric conversion module composed of an N-type thermoelectric element is a flexible film-like substrate composed of two or more materials having different thermal conductivities, and a material having a high thermal conductivity is provided on the substrate. It is configured to be located on a part of the outer surface.

また、請求項１に記載の熱電変換素子において、前記熱伝導率の異なる材料のうち熱伝導率の低い方は少なくとも絶縁体であることを特徴とするものである。   Further, in the thermoelectric conversion element according to claim 1, the one having a lower thermal conductivity among the materials having different thermal conductivities is at least an insulator.

また、請求項１に記載の熱電変換素子において、前記熱伝導率の低い材料が前記熱電変換モジュール側に位置するように構成したことを特徴とするものである。   The thermoelectric conversion element according to claim 1, wherein the material having the low thermal conductivity is positioned on the thermoelectric conversion module side.

また、請求項１〜請求項３に記載の熱電変換素子において、前記熱伝導率の低い材料がポリイミドなどの樹脂であり、前記熱伝導率の高い材料が銅などの金属であることを特徴とする熱電変換素子。   The thermoelectric conversion element according to claim 1, wherein the low thermal conductivity material is a resin such as polyimide, and the high thermal conductivity material is a metal such as copper. Thermoelectric conversion element.

本発明の熱電変換素子は、Ｐ型材料からなる薄膜のＰ型熱電素子とＮ型材料からなる薄膜のＮ型熱電素子とで構成された熱電変換モジュールの両面に、2種類以上の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板を設け、熱伝導率の高い材料が前記基板の外面の一部分に位置するように構成したので、機械的強度が高く、加工性に優れ、従って自動化が容易で大量生産が容易、しかも曲面等への設置も可能で設置場所が制限されることのない、発電効率の高い熱電変換素子を提供することができる。   The thermoelectric conversion element of the present invention has two or more kinds of thermal conductivity on both sides of a thermoelectric conversion module composed of a thin P-type thermoelectric element made of P-type material and a thin-film N-type thermoelectric element made of N-type material. Since a flexible film-like substrate composed of different materials is provided and a material having high thermal conductivity is located on a part of the outer surface of the substrate, the mechanical strength is high, and the workability is excellent. Accordingly, it is possible to provide a thermoelectric conversion element with high power generation efficiency that can be easily automated, mass-produced, can be installed on a curved surface, and does not limit the installation location.

本発明の熱電変換素子は、温度差を利用して熱を電気に変換する熱電変換素子であって、Ｐ型材料からなる薄膜のＰ型熱電素子とＮ型材料からなる薄膜のＮ型熱電素子とで構成された熱電変換モジュールの両面に、2種類以上の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板を設け、熱伝導率の高い材料が前記基板の外面の一部分に位置するように構成したものである。このように構成することにより、機械的強度が高く、加工性に優れ、従って自動化が容易で大量生産が容易、しかも曲面等への設置も可能で設置場所が制限されることのない、発電効率の高い熱電変換素子を提供することができる。   The thermoelectric conversion element of the present invention is a thermoelectric conversion element that converts heat into electricity using a temperature difference, and is a thin P-type thermoelectric element made of P-type material and a thin-film N-type thermoelectric element made of N-type material A flexible film-like substrate composed of two or more types of materials having different thermal conductivities is provided on both sides of the thermoelectric conversion module composed of the above, and a material having a high thermal conductivity is provided on a part of the outer surface of the substrate. It is comprised so that it may be located. With this configuration, the mechanical strength is high, the workability is excellent, the automation is easy, the mass production is easy, the installation on a curved surface is possible, and the installation location is not limited. A high thermoelectric conversion element can be provided.

本発明の一実施例について、図１に基づき説明する。図１に示した熱電変換素子は、温度差を利用して熱を電気に変換する熱電変換素子であり、Ｐ型材料からなる薄膜のＰ型熱電素子１とＮ型材料からなる薄膜のＮ型熱電素子２とを直列接続となるように成膜し、その両側に電極３を成膜して熱電変換モジュール６を構成し、この熱電変換モジュール６の両面に２種類の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板４、５を設けたものである。   An embodiment of the present invention will be described with reference to FIG. The thermoelectric conversion element shown in FIG. 1 is a thermoelectric conversion element that converts heat into electricity using a temperature difference, and is a thin P-type thermoelectric element 1 made of P-type material and a thin-film N-type made of N-type material. The thermoelectric element 2 is formed into a film so as to be connected in series, and electrodes 3 are formed on both sides thereof to form a thermoelectric conversion module 6. Two types of materials having different thermal conductivities are formed on both surfaces of the thermoelectric conversion module 6. Are provided with film-like substrates 4 and 5 having flexibility.

フィルム状基板４、５は、熱電変換モジュール６側に熱伝導率の低い材料４１、５１を設け、この熱伝導率の低い材料４１、５１として絶縁体であるポリイミドなどの樹脂を用いた。   For the film-like substrates 4 and 5, materials 41 and 51 having low thermal conductivity are provided on the thermoelectric conversion module 6 side, and a resin such as polyimide as an insulator is used as the materials 41 and 51 having low thermal conductivity.

また、フィルム状基板４、５は、熱電変換モジュール６の接合面と反対側に、熱伝導率の高い材料４２、５２が基板４、５の外面の一部分に位置するように設け、この熱伝導率の高い材料４２、５２として銅などの金属を用いた。   Further, the film-like substrates 4 and 5 are provided on the opposite side of the joining surface of the thermoelectric conversion module 6 so that the materials 42 and 52 having high thermal conductivity are located on a part of the outer surfaces of the substrates 4 and 5. Metals such as copper were used as the high-rate materials 42 and 52.

フィルム状基板４、５の材料選定においては、材料が安価で入手が容易であること、柔軟性が高いこと、加工が容易であることなどから、熱伝導率の低い材料４１、５１として絶縁体であるポリイミドを選定し、熱伝導率の高い材料４２、５２として銅を選定した。   In selecting materials for the film-like substrates 4 and 5, since the materials are inexpensive and readily available, have high flexibility, and are easy to process, the materials 41 and 51 having low thermal conductivity are insulators. Was selected, and copper was selected as the materials 42 and 52 having high thermal conductivity.

以上のように、熱電変換モジュール６の両面に熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板４、５を設けたが、これは基板４、５の上下面に温度差を加えた時の各層の熱流束の違いから基板４、５内部に温度差を生じさせるためである。   As described above, the flexible film-like substrates 4 and 5 made of materials having different thermal conductivities are provided on both surfaces of the thermoelectric conversion module 6, and this causes a temperature difference between the upper and lower surfaces of the substrates 4 and 5. This is because a temperature difference is caused inside the substrates 4 and 5 due to the difference in heat flux of each layer when added.

そして、フィルム状基板４、５は、熱電変換モジュール６側に熱伝導率の低い材料４１、５１を設け、熱電変換モジュール６の接合面と反対側に、熱伝導率の高い材料４２、５２が基板４、５の外面の一部分に位置するように設けることで、基板４、５の厚さ方向の温度勾配を、基板４、５の面内方向の温度勾配に効率よく変換することができる。この温度勾配を利用して、熱電変換モジュール６で効率良く発電を行うことができる。   The film-like substrates 4 and 5 are provided with materials 41 and 51 having low thermal conductivity on the thermoelectric conversion module 6 side, and materials 42 and 52 having high thermal conductivity are provided on the side opposite to the joint surface of the thermoelectric conversion module 6. By providing so as to be located on a part of the outer surface of the substrates 4 and 5, the temperature gradient in the thickness direction of the substrates 4 and 5 can be efficiently converted into the temperature gradient in the in-plane direction of the substrates 4 and 5. Using this temperature gradient, the thermoelectric conversion module 6 can efficiently generate power.

次に、熱電変換素子の下面に熱を加えた際の、熱電変換素子の上下面温度差と熱電変換モジュール６の内面温度差についてシミュレーション及び実測した結果を図２に示す。実測値（図中＊印）とシミュレーション値（図中実線）はほぼ一致した。上下面温度差５４℃で内面温度差１６．３℃が発生した。この際の熱電変換モジュール６の膜厚は４μｍ、ポリイミド４１、５１の膜厚は２５μｍ、銅４２、５２の膜厚は１２μｍである。なお、銅４２、５２は、基板４、５の外面の面積の約半分に設定した。   Next, FIG. 2 shows the results of simulation and actual measurement on the temperature difference between the upper and lower surfaces of the thermoelectric conversion element and the inner surface temperature of the thermoelectric conversion module 6 when heat is applied to the lower surface of the thermoelectric conversion element. The measured values (marked with * in the figure) and the simulated values (solid line in the figure) almost coincided. An inner surface temperature difference of 16.3 ° C. occurred with an upper / lower surface temperature difference of 54 ° C. At this time, the thermoelectric conversion module 6 has a thickness of 4 μm, the polyimides 41 and 51 have a thickness of 25 μm, and the coppers 42 and 52 have a thickness of 12 μm. The copper 42 and 52 were set to about half the area of the outer surface of the substrates 4 and 5.

本発明の熱電変換素子を、例えば５１４０個集積した場合の発電は、電力７．４６ｍＷと想定される。この場合、熱電材料（熱電素子）に希土類材料ＣｅＰｄ３−ＹｂＰｄを使用した。   For example, power generation when 5140 thermoelectric conversion elements of the present invention are integrated is assumed to have an electric power of 7.46 mW. In this case, the rare earth material CePd3-YbPd was used for the thermoelectric material (thermoelectric element).

以上の説明では、熱電変換モジュール６の両面に2種類の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板４、５について説明したが、基板４、５には、種々の条件によっては、３種類以上の熱伝導率の異なる材料を使用した方が、基板４、５の厚さ方向の温度勾配を、基板４、５の面内方向の温度勾配に、より効率よく変換することができる場合がある。これにより熱電変換モジュール６でより効率良く発電を行うことができる。   In the above description, the flexible film-like substrates 4 and 5 made of two kinds of materials having different thermal conductivities on both surfaces of the thermoelectric conversion module 6 have been described. Depending on the type, materials using three or more kinds of materials having different thermal conductivities can more efficiently convert the temperature gradient in the thickness direction of the substrates 4 and 5 into the temperature gradient in the in-plane direction of the substrates 4 and 5. There are cases where it is possible. As a result, the thermoelectric conversion module 6 can generate power more efficiently.

以上のように本発明の熱電変換素子は、柔軟なフィルム状基板４、５を用いるので、熱電変換モジュール６への熱ショック等を緩和でき、機械的強度を高めることができ、薄膜プロセス、印刷プロセスを利用して製造プロセスの自動化、簡略化が可能となり、大面積化が可能となるなどの利点を有することができる。また、パイプなど曲面への設置が可能となり、従来の熱電変換素子では設置が困難であった箇所への設置も可能である。さらに、フィルム状基板４、５は、熱電変換モジュール６側に熱伝導率の低い材料４１、５１を設け、熱電変換モジュール６の接合面と反対側に、熱伝導率の高い材料４２、５２が基板４、５の外面の一部分に位置するように設けることで、基板４、５の厚さ方向の温度勾配を、基板４、５の面内方向の温度勾配に効率よく変換することができる。この温度勾配を利用して、熱電変換モジュール６で効率良く発電を行うことができる。つまり、本発明の熱電変換素子は、Ｐ型材料からなる薄膜のＰ型熱電素子１とＮ型材料からなる薄膜のＮ型熱電素子２とで構成された熱電変換モジュール６の両面に、2種類以上の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板４、５を設け、熱伝導率の高い材料４２、５２が前記基板４、５の外面の一部分に位置するように構成したので、機械的強度が高く、加工性に優れ、従って自動化が容易で大量生産が容易、しかも曲面等への設置も可能で設置場所が制限されることのない、発電効率の高い熱電変換素子を提供することができる。   As described above, since the thermoelectric conversion element of the present invention uses the flexible film-like substrates 4 and 5, the heat shock to the thermoelectric conversion module 6 can be alleviated, the mechanical strength can be increased, the thin film process, the printing The manufacturing process can be automated and simplified by using the process, and an advantage that the area can be increased can be obtained. In addition, it can be installed on a curved surface such as a pipe, and can be installed in a place where it was difficult to install with a conventional thermoelectric conversion element. Further, the film-like substrates 4 and 5 are provided with materials 41 and 51 having low thermal conductivity on the thermoelectric conversion module 6 side, and materials 42 and 52 having high thermal conductivity are provided on the side opposite to the joining surface of the thermoelectric conversion module 6. By providing so as to be located on a part of the outer surface of the substrates 4 and 5, the temperature gradient in the thickness direction of the substrates 4 and 5 can be efficiently converted into the temperature gradient in the in-plane direction of the substrates 4 and 5. Using this temperature gradient, the thermoelectric conversion module 6 can efficiently generate power. That is, two types of thermoelectric conversion elements of the present invention are provided on both sides of a thermoelectric conversion module 6 composed of a thin P-type thermoelectric element 1 made of P-type material and a thin-film N-type thermoelectric element 2 made of N-type material. The flexible film-like substrates 4 and 5 made of materials having different thermal conductivities are provided, and the materials 42 and 52 having high thermal conductivities are located on a part of the outer surfaces of the substrates 4 and 5. Therefore, it has high mechanical strength, excellent workability, and therefore is easy to automate and mass production, and can be installed on curved surfaces, etc. Can be provided.

本発明の一実施例の主要部概要構成を示す断面図である。It is sectional drawing which shows the principal part outline structure of one Example of this invention. 本発明の一実施例の実験結果を示すグラフである。It is a graph which shows the experimental result of one Example of this invention. 従来例を示す説明図である。It is explanatory drawing which shows a prior art example. 従来例を示す断面図である。It is sectional drawing which shows a prior art example. 他の従来例を示す断面図である。It is sectional drawing which shows another prior art example.

符号の説明Explanation of symbols

１ Ｐ型熱電素子
２ Ｎ型熱電素子
４ 基板
５ 基板
６ 熱電変換モジュール
４２ 熱伝導率の高い材料
５２ 熱伝導率の高い材料

DESCRIPTION OF SYMBOLS 1 P type thermoelectric element 2 N type thermoelectric element 4 Board | substrate 5 Board | substrate 6 Thermoelectric conversion module 42 Material with high heat conductivity 52 Material with high heat conductivity

Claims (4)

温度差を利用して熱を電気に変換する熱電変換素子であって、Ｐ型材料からなる薄膜のＰ型熱電素子とＮ型材料からなる薄膜のＮ型熱電素子とで構成された熱電変換モジュールの両面に、2種類以上の熱伝導率の異なる材料で構成された柔軟性を有するフィルム状基板を設け、熱伝導率の高い材料が前記基板の外面の一部分に位置するように構成したことを特徴とする熱電変換素子。   A thermoelectric conversion element that converts heat into electricity using a temperature difference, and includes a thin P-type thermoelectric element made of P-type material and a thin-film N-type thermoelectric element made of N-type material A flexible film-like substrate composed of two or more types of materials having different thermal conductivities is provided on both sides of the substrate, and the material having a high thermal conductivity is located on a part of the outer surface of the substrate. A characteristic thermoelectric conversion element. 請求項１に記載の熱電変換素子において、前記熱伝導率の異なる材料のうち熱伝導率の低い方は少なくとも絶縁体であることを特徴とする熱電変換素子。   2. The thermoelectric conversion element according to claim 1, wherein the one having a lower thermal conductivity among the materials having different thermal conductivities is at least an insulator. 3. 請求項１に記載の熱電変換素子において、前記熱伝導率の低い材料が前記熱電変換モジュール側に位置するように構成したことを特徴とする熱電変換素子。   2. The thermoelectric conversion element according to claim 1, wherein the material having a low thermal conductivity is positioned on the thermoelectric conversion module side. 3. 請求項１〜請求項３のいずれかに記載の熱電変換素子において、前記熱伝導率の低い材料がポリイミドなどの樹脂であり、前記熱伝導率の高い材料が銅などの金属であることを特徴とする熱電変換素子。

The thermoelectric conversion element according to any one of claims 1 to 3, wherein the material having a low thermal conductivity is a resin such as polyimide, and the material having a high thermal conductivity is a metal such as copper. A thermoelectric conversion element.

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