JP6505585B2 - Thermoelectric conversion element - Google Patents
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Description
本発明は、良好な熱電変換性能を有する熱電変換素子に関する。 The present invention relates to a thermoelectric conversion element having good thermoelectric conversion performance.
熱エネルギーと電気エネルギーを相互に変換することができる熱電変換材料が、熱によって発電する発電素子やペルチェ素子のような熱電変換素子に用いられている。
熱電変換素子は、熱エネルギーを直接電力に変換することができ、可動部を必要としない等の利点を有する。そのため、複数の熱電変換素子を接続してなる熱電変換モジュール（発電装置）は、例えば、焼却炉や工場の各種の設備など、排熱される部位に設けることで、動作コストを掛ける必要なく、簡易に電力を得ることができる。
A thermoelectric conversion material capable of mutually converting thermal energy and electrical energy is used for a thermoelectric conversion element such as a power generation element that generates electricity by heat or a Peltier element.
The thermoelectric conversion element can convert thermal energy directly into electric power, and has the advantage of not requiring a movable part. Therefore, the thermoelectric conversion module (power generation device) formed by connecting a plurality of thermoelectric conversion elements can be simplified, for example, by providing the thermoelectric conversion module at a site where exhaust heat is generated, such as an incinerator or various facilities of a factory. Power can be obtained.
熱電変換素子は、一般的に、板状の基板の上に電極を有し、電極の上に熱電変換層（発電層）を有し、熱電変換層の上に板状の電極を有してなる構成を有する。このような熱電変換素子は、uni leg型の熱電変換素子とも呼ばれている。
すなわち、通常の熱電変換素子は、電極で熱電変換層を厚さ方向に挟持し、熱電変換層の厚さ方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換させている。
The thermoelectric conversion element generally has an electrode on a plate-like substrate, a thermoelectric conversion layer (power generation layer) on the electrode, and a plate-like electrode on the thermoelectric conversion layer. The configuration is as follows. Such a thermoelectric conversion element is also called a unileg type thermoelectric conversion element.
That is, in a general thermoelectric conversion element, a thermoelectric conversion layer is sandwiched between electrodes in the thickness direction, a temperature difference is generated in the thickness direction of the thermoelectric conversion layer, and thermal energy is converted into electrical energy.
これに対し、特許文献１および２には、熱電変換層の厚さ方向ではなく、高熱伝導部と低熱伝導部とを有する基板を用いて、熱電変換層の面方向に温度差を生じさせて熱エネルギーを電気エネルギーに変換する熱電変換素子が記載されている。
具体的には、特許文献１には、Ｐ型材料およびＮ型材料で形成された熱電変換層の両面に、熱伝導率が異なる２種類の材料で構成された柔軟性を有するフィルム基板を設け、熱伝導率が異なる材料を、基板の外面で、かつ、通電方向の逆位置に位置するように構成した熱電変換素子が記載されている。
On the other hand, in Patent Documents 1 and 2, a temperature difference is generated in the surface direction of the thermoelectric conversion layer not using the thickness direction of the thermoelectric conversion layer but using a substrate having a high thermal conductivity portion and a low thermal conductivity portion. A thermoelectric conversion element is described which converts thermal energy into electrical energy.
Specifically, in Patent Document 1, on both sides of a thermoelectric conversion layer formed of a P-type material and an N-type material, a flexible film substrate composed of two kinds of materials having different thermal conductivities is provided. A thermoelectric conversion element is described in which materials different in thermal conductivity are positioned on the outer surface of the substrate and at a position opposite to the direction of current flow.
また、特許文献２には、シート状の第１絶縁性部および第２絶縁性部と、両絶縁性部の間に収容される熱起電力を取り出すための第１端部および第２端部を有する板状の熱電変換層と、熱電変換層と第１絶縁性部との間に配置される、第１端部の第１絶縁性部側を覆う、第１絶縁性部よりも熱伝導率が高い第１高熱伝導性部と、板状部材と第２絶縁性部との間に配置された、板状部材の第２端部の第２絶縁性部側を覆う、第２絶縁性部よりも熱伝導率が高い第２高熱伝導性部とを有する素子が記載されている。 Further, in Patent Document 2, a first end and a second end for extracting a thermoelectromotive force accommodated between the sheet-shaped first insulating portion and the second insulating portion and the both insulating portions. Heat conduction than the first insulating portion covering the first insulating portion side of the first end portion disposed between the thermoelectric conversion layer having the plate and the thermoelectric conversion layer and the first insulating portion A second insulating portion covering the second insulating portion side of the second end portion of the plate-like member disposed between the plate-like member and the second insulating portion, the first high thermal conductivity portion having a high rate of An element is described which has a second high thermal conductivity part having a thermal conductivity higher than that of the part.
このような高熱伝導部と低熱伝導部とを有する基板を用い、熱電変換層の面方向に温度差を生じさせて熱エネルギーを電気エネルギーに変換する熱電変換素子は、『in plane型の熱電変換素子』とも呼ばれている。 A thermoelectric conversion element that converts thermal energy into electrical energy by using a substrate having such a high thermal conductivity portion and a low thermal conductivity portion and causing a temperature difference in the surface direction of the thermoelectric conversion layer is referred to as “in-plane type thermoelectric conversion It is also called "element".
in plane型の熱電変換素子は、基板に設けられる高熱伝導部によって熱電変換層の面方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換する。そのため、薄い熱電変換層でも、温度差が生じる距離を長くして、効率の良い発電ができる。
さらに、熱電変換層を薄いシート状にできるので、フレキシブル性にも優れ、曲面等への設置も容易な熱電変換モジュールが得られる。
The in-plane type thermoelectric conversion element converts thermal energy into electrical energy by causing a temperature difference in the surface direction of the thermoelectric conversion layer by the high thermal conductivity portion provided on the substrate. Therefore, even with a thin thermoelectric conversion layer, efficient distance generation can be performed by increasing the distance at which a temperature difference occurs.
Furthermore, since the thermoelectric conversion layer can be formed into a thin sheet, it is possible to obtain a thermoelectric conversion module that is excellent in flexibility and easy to install on a curved surface or the like.
ところが、本発明者らの検討によれば、in plane型の熱電変換素子でも、使用状況等によっては充分な発電量が得られない場合も有り、特に、自然空冷下においては、水冷や強制空冷下に比べ、発電量が低下し易い傾向にあることが判明した。 However, according to the study of the present inventors, even in-plane type thermoelectric conversion elements may not be able to obtain a sufficient amount of power generation depending on the use conditions, etc., and in particular, water cooling or forced air cooling under natural air cooling. It turned out that the amount of power generation tends to decrease compared to the bottom.
本発明の目的は、このような従来技術の問題点を解決することにあり、基板に設けられた高熱伝導部および低熱伝導部によって、熱電変換層の面方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換する熱電変換素子において、自然空冷下であっても発電量を向上できる熱電変換素子を提供することにある。 The object of the present invention is to solve the problems of the prior art as described above, and a high thermal conductivity portion and a low thermal conductivity portion provided on the substrate cause a temperature difference in the surface direction of the thermoelectric conversion layer A thermoelectric conversion element for converting energy into electric energy, which is to provide a thermoelectric conversion element capable of improving the amount of power generation even under natural air cooling.
本発明者らは、上記課題を解決すべく鋭意検討した結果、シート状の低熱伝導部、ならびに、低熱伝導部に設けられる、低熱伝導部よりも熱伝導率が高い第１高熱伝導部、を有する基板と、基板に設けられる熱電変換層と、熱電変換層を覆う被覆層と、被覆層に設けられる、被覆層よりも熱伝導率が高く、かつ、面方向に第１高熱伝導部と完全に重複しない第２高熱伝導部と、面方向に熱電変換層を挟んで熱電変換層に接続される一対の電極と、第１高熱伝導部の、熱電変換層とは反対側の面に設置される接合部材と、を有することにより、上記課題を解決できることを見出し、本発明を完成させた。
すなわち、本発明は、以下の構成の熱電変換素子を提供する。
As a result of intensive studies to solve the above problems, the present inventors have found a sheet-like low thermal conductivity part, and a first high thermal conductivity part provided in the low thermal conductivity part and having a thermal conductivity higher than that of the low thermal conductivity part. The substrate, the thermoelectric conversion layer provided on the substrate, the covering layer covering the thermoelectric conversion layer, the thermal conductivity of the covering layer provided on the covering layer is higher than that of the covering layer, and complete with the first high thermal conductivity portion in the surface direction A second high thermal conductivity portion that does not overlap the two, a pair of electrodes connected to the thermoelectric conversion layer across the thermoelectric conversion layer in the surface direction, and the first high thermal conductivity portion on the surface opposite to the thermoelectric conversion layer It has been found that the above-mentioned problems can be solved by including the following joint members, and the present invention has been completed.
That is, the present invention provides a thermoelectric conversion element having the following configuration.
（１） シート状の低熱伝導部、ならびに、低熱伝導部に設けられる、低熱伝導部よりも熱伝導率が高い第１高熱伝導部、を有する基板と、
基板に設けられる熱電変換層と、
熱電変換層を覆う被覆層と、
被覆層に設けられる、被覆層よりも熱伝導率が高く、かつ、面方向に第１高熱伝導部と完全に重複しない第２高熱伝導部と、
面方向に熱電変換層を挟んで熱電変換層に接続される一対の電極と、
第１高熱伝導部の、熱電変換層とは反対側の面に設置される接合部材と、を有する熱電変換素子。
（２） 接合部材は、厚み方向における熱伝導率が、面方向における熱伝導率よりも高い（１）に記載の熱電変換素子。
（３） 接合部材の形成材料が、金属、合金、および、フィラーを垂直配向した樹脂のいずれかである（１）または（２）に記載の熱電変換素子。
（４） 接合部材の、第１高熱伝導部とは反対側の面に配置される、面方向の熱伝導率が厚み方向の熱伝導率よりも高い熱伝導シートを有する（１）〜（３）のいずれかに記載の熱電変換素子。
（５） 熱伝導シートが凹部を有し、
接合部材が熱伝導シートの凹部に嵌合している（４）に記載の熱電変換素子。
（６） 第２高熱伝導部の熱抵抗が、第１高熱伝導部の熱抵抗よりも小さい（１）〜（５）のいずれかに記載の熱電変換素子。
（７） 基板は、低熱伝導部よりも熱伝導率が高い第３高熱伝導部を有し、
第３高熱伝導部の厚みは、第１高熱伝導部と接合部材との合計厚みよりも薄く、さらに、面方向に第１高熱伝導部と離間し、かつ、面方向に熱電変換層および第２高熱伝導部と少なくとも一部が重複する（１）〜（６）のいずれかに記載の熱電変換素子。
（８） 被覆層が、樹脂製のシート、あるいはさらに、樹脂製のシートと熱電変換層との間に設けられる粘着層からなるものであり、
第２高熱伝導部が、金属製で、被覆層の熱電変換層と逆側の面に設けられる（１）〜（７）のいずれかに記載の熱電変換素子。
（９） 被覆層が粘着性を有するものであり、さらに、
第２高熱伝導部が、貫通しない溝を有する金属製のシートであり、
金属製のシートは、溝の少なくとも一部が面方向に第１高熱伝導部と重複するように、溝を被覆層に向けて被覆層に設けた構成を有する（１）〜（７）のいずれかに記載の熱電変換素子。
（１０） 基板の低熱伝導部が樹脂製であり、
第１高熱伝導部が、金属製で、低熱伝導部の熱電変換層と逆側の面に設けられる（１）〜（９）のいずれかに記載の熱電変換素子。
(1) A substrate having a sheet-like low thermal conductivity portion, and a first high thermal conductivity portion provided in the low thermal conductivity portion and having a thermal conductivity higher than that of the low thermal conductivity portion;
A thermoelectric conversion layer provided on the substrate,
A covering layer covering the thermoelectric conversion layer,
A second high thermal conductivity portion provided to the coating layer, having a thermal conductivity higher than that of the coating layer, and not completely overlapping with the first high thermal conductivity portion in the plane direction;
A pair of electrodes connected to the thermoelectric conversion layer across the thermoelectric conversion layer in the surface direction;
The thermoelectric conversion element which has a joining member installed in the field on the opposite side to the thermoelectric conversion layer of the 1st high heat conduction part.
(2) The thermoelectric conversion element according to (1), wherein the thermal conductivity in the thickness direction of the joining member is higher than the thermal conductivity in the surface direction.
(3) The thermoelectric conversion element according to (1) or (2), wherein the forming material of the bonding member is either a metal, an alloy, or a resin in which the filler is vertically oriented.
(4) A heat conductive sheet having a thermal conductivity in the surface direction higher than that in the thickness direction, which is disposed on the surface opposite to the first high thermal conductivity portion of the bonding member (1) to (3) The thermoelectric conversion element according to any one of the above.
(5) The heat conductive sheet has a recess,
The thermoelectric conversion element according to (4), wherein the bonding member is fitted in the concave portion of the heat conductive sheet.
(6) The thermoelectric conversion element according to any one of (1) to (5), wherein the thermal resistance of the second high thermal conductivity portion is smaller than the thermal resistance of the first high thermal conductivity portion.
(7) The substrate has a third high thermal conductivity portion whose thermal conductivity is higher than that of the low thermal conductivity portion,
The thickness of the third high thermal conductivity part is thinner than the total thickness of the first high thermal conductivity part and the joining member, and further, the first high thermal conductivity part is separated in the surface direction, and the thermoelectric conversion layer and the second The thermoelectric conversion element in any one of (1)-(6) which at least one part overlaps with a highly heat-conductive part.
(8) The covering layer is a sheet made of resin or an adhesive layer provided between the sheet made of resin and the thermoelectric conversion layer,
The thermoelectric conversion element according to any one of (1) to (7), wherein the second high thermal conductivity portion is made of metal and provided on the surface of the covering layer opposite to the thermoelectric conversion layer.
(9) The coating layer is tacky, and further,
The second high thermal conductivity portion is a metal sheet having a non-penetrating groove,
The metal sheet has a configuration in which the groove is directed to the covering layer in the covering layer so that at least a part of the groove overlaps the first high thermal conductivity portion in the surface direction, any of (1) to (7) Thermoelectric conversion element described in.
(10) The low thermal conductivity part of the substrate is made of resin,
The thermoelectric conversion element according to any one of (1) to (9), wherein the first high thermal conductivity portion is made of metal and provided on the surface of the low thermal conductivity portion opposite to the thermoelectric conversion layer.
このような本発明によれば、基板に設けられた高熱伝導部および低熱伝導部によって、熱電変換層の面方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換する熱電変換素子において、自然空冷下であっても発電量を向上できる熱電変換素子を提供することができる。 According to the present invention, in the thermoelectric conversion element, thermal energy is converted into electrical energy by causing a temperature difference in the surface direction of the thermoelectric conversion layer by the high thermal conductivity portion and the low thermal conductivity portion provided on the substrate. It is possible to provide a thermoelectric conversion element capable of improving the amount of power generation even under natural air cooling.
以下、本発明の熱電変換素子について、添付の図面に示される好適実施態様を基に詳細に説明する。
本発明の熱電変換素子は、シート状の低熱伝導部、ならびに、低熱伝導部に設けられる、低熱伝導部よりも熱伝導率が高い第１高熱伝導部、を有する基板と、
基板に設けられる熱電変換層と、
熱電変換層を覆う被覆層と、
被覆層に設けられる、被覆層よりも熱伝導率が高く、かつ、面方向に第１高熱伝導部と完全に重複しない第２高熱伝導部と、
面方向に熱電変換層を挟んで熱電変換層に接続される一対の電極と、
第１高熱伝導部の、熱電変換層とは反対側の面に設置される接合部材と、を有する熱電変換素子である。
Hereinafter, the thermoelectric conversion element of the present invention will be described in detail based on the preferred embodiments shown in the attached drawings.
The thermoelectric conversion element of the present invention comprises a sheet-like low thermal conductivity part, and a substrate having a first high thermal conductivity part provided in the low thermal conductivity part and having a thermal conductivity higher than that of the low thermal conductivity part.
A thermoelectric conversion layer provided on the substrate,
A covering layer covering the thermoelectric conversion layer,
A second high thermal conductivity portion provided to the coating layer, having a thermal conductivity higher than that of the coating layer, and not completely overlapping with the first high thermal conductivity portion in the plane direction;
A pair of electrodes connected to the thermoelectric conversion layer across the thermoelectric conversion layer in the surface direction;
It is a thermoelectric conversion element which has the joining member installed in the field on the opposite side to the thermoelectric conversion layer of the 1st high heat conduction part.
図１（Ａ）に、本発明の熱電変換素子の一例を斜視図によって概念的に示す。また、図１（Ｂ）に、図１（Ａ）に示す熱電変換素子を正面から見た正面図を示す。 FIG. 1A conceptually shows an example of the thermoelectric conversion element of the present invention in a perspective view. Moreover, the front view which looked at the thermoelectric conversion element shown to FIG. 1 (A) from the front at FIG. 1 (B) is shown.
図１（Ａ）および図１（Ｂ）に示す熱電変換素子１０は、基本的に、第１基板１２と、熱電変換層１６と、粘着層１８と、第２基板２０と、電極２６および電極２８と、接合部材２２とを有して構成される。
具体的には、第１基板１２の表面には、熱電変換層１６が設けられる。また、第１基板１２の表面には、熱電変換層１６を第１基板１２の基板面方向に挟むようにして、熱電変換層１６に接続して電極２６および電極２８（電極対）が設けられる。さらに、第１基板１２、熱電変換層１６、電極２６および電極２８を覆うように、粘着層１８が設けられ、この粘着層１８には、第２基板２０が貼着される。さらに、第１基板１２の熱電変換層１６とは反対側の面にある第１高熱伝導部１２ｂ上に接合部材２２が配置される。
The thermoelectric conversion element 10 shown in FIG. 1A and FIG. 1B basically includes the first substrate 12, the thermoelectric conversion layer 16, the adhesive layer 18, the second substrate 20, the electrode 26, and the electrode 28 and the joint member 22 are configured.
Specifically, the thermoelectric conversion layer 16 is provided on the surface of the first substrate 12. Further, on the surface of the first substrate 12, the thermoelectric conversion layer 16 is connected to the thermoelectric conversion layer 16 so as to sandwich the thermoelectric conversion layer 16 in the substrate surface direction of the first substrate 12, and an electrode 26 and an electrode 28 (electrode pair) are provided. Further, an adhesive layer 18 is provided to cover the first substrate 12, the thermoelectric conversion layer 16, the electrode 26 and the electrode 28, and the second substrate 20 is attached to the adhesive layer 18. Further, the bonding member 22 is disposed on the first high thermal conductivity portion 12 b on the surface of the first substrate 12 opposite to the thermoelectric conversion layer 16.
図１（Ａ）および図１（Ｂ）に示すように、第１基板１２は、シート状（フィルム状、板状）の低熱伝導部１２ａと、低熱伝導部１２ａの一面に設けられる第１高熱伝導部１２ｂとを有する。第１高熱伝導部１２ｂは、低熱伝導部１２ａよりも熱伝導率が高い。
他方、第２基板２０も、シート状の低熱伝導部２０ａと、低熱伝導部に設けられる第２高熱伝導部２０ｂとを有する。第２高熱伝導部２０ｂは、粘着層１８および低熱伝導部２０ａよりも熱伝導率が高い。
さらに、後に詳述するが、第２高熱伝導部２０ｂは、面方向に第１高熱伝導部１２ｂと完全に重複しない。
本発明において、『面方向』とは、第１基板１２の基板面方向すなわちシート状の低熱伝導部１２ａの面方向である。
As shown in FIGS. 1A and 1B, the first substrate 12 is a sheet-like (film-like, plate-like) low thermal conductive part 12a and a first high heat provided on one surface of the low thermal conductive part 12a. And a conductive portion 12b. The first high thermal conductivity portion 12 b has a thermal conductivity higher than that of the low thermal conductivity portion 12 a.
On the other hand, the second substrate 20 also has a sheet-like low thermal conductivity part 20 a and a second high thermal conductivity part 20 b provided in the low thermal conductivity part. The second high thermal conductivity portion 20 b has a thermal conductivity higher than that of the adhesive layer 18 and the low thermal conductivity portion 20 a.
Furthermore, as will be described in detail later, the second high thermal conductivity portion 20b does not completely overlap the first high thermal conductivity portion 12b in the surface direction.
In the present invention, the “plane direction” is the substrate surface direction of the first substrate 12, that is, the surface direction of the sheet-like low thermal conductivity portion 12 a.
熱電変換素子１０においては、第１基板１２が本発明における基板に、粘着層１８および第２基板２０の低熱伝導部２０ａが本発明における被覆層に、それぞれ対応する。 In the thermoelectric conversion element 10, the first substrate 12 corresponds to the substrate in the present invention, and the adhesive layer 18 and the low thermal conductivity portion 20a of the second substrate 20 correspond to the covering layer in the present invention.
熱電変換素子１０において、両基板は、第１高熱伝導部１２ｂと第２高熱伝導部２０ｂとが、電極２６と電極２８との離間方向に異なる位置となるように配置される。
電極２６と電極２８との離間方向とは、すなわち通電方向である。以下、電極２６と電極２８との離間方向、すなわち、通電方向であり、かつ、熱電変換層１６における伝熱方向でもある方向を、『離間方向』とも言う。
In the thermoelectric conversion element 10, both substrates are arranged such that the first high thermal conductivity portion 12b and the second high thermal conductivity portion 20b are at different positions in the direction in which the electrode 26 and the electrode 28 are separated.
The separation direction between the electrode 26 and the electrode 28 is, in other words, the conduction direction. Hereinafter, the direction in which the electrodes 26 and the electrodes 28 are separated, that is, the direction of current flow and also the direction of heat transfer in the thermoelectric conversion layer 16 is also referred to as the “separation direction”.
熱電変換素子１０は、低熱伝導部１２ａおよび第１高熱伝導部１２ｂを有する第１基板１２と、低熱伝導部２０ａおよび第２高熱伝導部２０ｂを有する第２基板２０とを有し、第１高熱伝導部１２ｂと第２高熱伝導部２０ｂとを面方向に異なる位置として、熱電変換層１６および粘着層１８を、第１基板１２と第２基板とで挟持した構成を有する。
すなわち、熱電変換素子１０は、前述のin plane型の熱電変換素子であって熱電変換層１６の面方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換する。
この点に関しては、後に詳述する。
The thermoelectric conversion element 10 includes a first substrate 12 having a low thermal conductivity portion 12a and a first high thermal conductivity portion 12b, and a second substrate 20 having a low thermal conductivity portion 20a and a second high thermal conductivity portion 20b. The thermoelectric conversion layer 16 and the adhesive layer 18 are sandwiched between the first substrate 12 and the second substrate, with the conductive portion 12 b and the second high thermal conductivity portion 20 b different in the surface direction.
That is, the thermoelectric conversion element 10 is the above-described in-plane type thermoelectric conversion element, generates a temperature difference in the surface direction of the thermoelectric conversion layer 16, and converts thermal energy into electrical energy.
This point will be described in detail later.
図示例の熱電変換素子１０において、第１基板１２および第２基板２０は、配置位置、表裏や面方向（基板面方向）の向きが異なるのみで、基本的な構成は同じである。すなわち、第１基板１２および第２基板２０において、低熱伝導部１２ａおよび低熱伝導部２０ａ、ならびに、第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂは、同じものである。
従って、以下の説明では、第１基板１２と第２基板２０とを区別する必要が有る場合を除いて、第１基板１２を代表例として説明を行う。
In the thermoelectric conversion element 10 of the illustrated example, the first substrate 12 and the second substrate 20 have the same basic configuration except that the arrangement position, the front and back, and the direction of the surface direction (substrate surface direction) are different. That is, in the first substrate 12 and the second substrate 20, the low thermal conductivity portion 12a and the low thermal conductivity portion 20a, and the first high thermal conductivity portion 12b and the second high thermal conductivity portion 20b are the same.
Therefore, in the following description, the first substrate 12 will be described as a representative example except in the case where it is necessary to distinguish between the first substrate 12 and the second substrate 20.
図示例の熱電変換素子１０において、第１基板１２（第２基板２０）は、低熱伝導部１２ａ（低熱伝導部２０ａ）の離間方向を端部から所定部分まで覆うように、低熱伝導部１２ａに第１高熱伝導部１２ｂを積層してなる構成を有する。
従って、第１基板１２の一面は、離間方向の端部から所定領域までが低熱伝導部１２ａで、残りの半分の領域は第１高熱伝導部１２ｂとなる。また、第１基板１２の他方の面は、全面が低熱伝導部１２ａとなる。
熱電変換素子１０では、第１基板１２の低熱伝導部１２ａの第１高熱伝導部１２ｂが形成されていない側の面が、熱電変換層１６の形成面となる。また、第２基板２０は、第２高熱伝導部２０ｂが形成されていない側の面が、熱電変換層１６（粘着層１８）側の面となる。
In the thermoelectric conversion element 10 of the illustrated example, the first substrate 12 (second substrate 20) is formed on the low thermal conductivity portion 12a so as to cover the separation direction of the low thermal conductivity portion 12a (low thermal conductivity portion 20a) from the end portion to a predetermined portion. It has the structure formed by laminating | stacking the 1st high heat conduction part 12b.
Therefore, one surface of the first substrate 12 is the low thermal conductivity portion 12a from the end in the separation direction to the predetermined region, and the remaining half region is the first high thermal conductivity portion 12b. The entire surface of the other surface of the first substrate 12 is the low thermal conductive portion 12a.
In the thermoelectric conversion element 10, the surface of the low thermal conductivity portion 12a of the first substrate 12 on the side where the first high thermal conductivity portion 12b is not formed is the surface on which the thermoelectric conversion layer 16 is formed. The surface of the second substrate 20 on which the second high thermal conductivity portion 20b is not formed is the surface on the side of the thermoelectric conversion layer 16 (the adhesive layer 18).
なお、本発明の熱電変換素子において、第１基板１２は、低熱伝導部の表面に高熱伝導部を積層してなる構成以外にも、各種の構成が利用可能である。例えば、第１基板は、低熱伝導部１２ａとなる板状物の、一方の面の所定領域に凹部を形成して、この凹部に、第１高熱伝導部１２ｂを組み込んだ構成でもよい。 In the thermoelectric conversion element of the present invention, various configurations can be used for the first substrate 12 in addition to the configuration in which the high thermal conductivity portion is laminated on the surface of the low thermal conductivity portion. For example, the first substrate may have a configuration in which a recess is formed in a predetermined region of one surface of a plate-like material to be the low thermal conductivity portion 12a, and the first high thermal conductivity portion 12b is incorporated in the recess.
低熱伝導部１２ａは、ガラス板、セラミックス板、プラスチックフィルムなどの樹脂材料（高分子材料）からなるフィルムなど、絶縁性を有し、かつ、熱電変換層１６や電極２６等の形成等に対する十分な耐熱性を有するものであれば、各種の材料からなる物が利用可能である。
好ましくは、低熱伝導部１２ａには、樹脂材料からなるフィルムが利用される。低熱伝導部１２ａに樹脂材料からなるフィルムを用いることにより、軽量化やコストの低下を計ると共に、可撓性を有する熱電変換素子１０（熱電変換モジュール）が作製可能となり、好ましい。
The low thermal conductivity portion 12a is insulating such as a film made of a resin material (polymer material) such as a glass plate, a ceramic plate, or a plastic film, and has sufficient insulation for forming the thermoelectric conversion layer 16, electrodes 26 and the like. As long as it has heat resistance, materials made of various materials can be used.
Preferably, a film made of a resin material is used for the low thermal conductivity portion 12a. By using a film made of a resin material for the low thermal conductive portion 12a, weight reduction and cost reduction can be achieved, and a flexible thermoelectric conversion element 10 (thermoelectric conversion module) can be produced, which is preferable.
低熱伝導部１２ａに利用可能な樹脂材料としては、具体的には、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート、ポリ（１，４−シクロヘキシレンジメチレンテレフタレート）、ポリエチレン−２，６−フタレンジカルボキシレート等のポリエステル樹脂、ポリイミド、ポリカーボネート、ポリプロピレン、ポリエーテルスルホン、シクロオレフィンポリマー、ポリエーテルエーテルケトン（ＰＥＥＫ）、トリアセチルセルロース（ＴＡＣ）等の樹脂、ガラスエポキシ、液晶性ポリエステル等が例示される。
中でも、熱伝導率、耐熱性、耐溶剤性、入手の容易性や経済性等の点で、ポリイミド、ポリエチレンテレフタレート、ポリエチレンナフタレート等からなるフィルムは、好適に利用される。
Specific examples of resin materials that can be used for the low thermal conductive portion 12 a include polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylene dimethylene terephthalate), polyethylene-2, 6-Phthalene dicarboxylate, polyester resin such as polyimide, polycarbonate, polypropylene, polyether sulfone, cycloolefin polymer, polyether ether ketone (PEEK), resin such as triacetyl cellulose (TAC), glass epoxy, liquid crystalline polyester, etc. Is illustrated.
Among them, a film made of polyimide, polyethylene terephthalate, polyethylene naphthalate or the like is suitably used in view of thermal conductivity, heat resistance, solvent resistance, availability and economy.
本発明において、高熱伝導部および低熱伝導部とは、隣接する層（隣接する高熱伝導部もしくは低熱伝導部）に対して熱伝導率が高い、もしくは低いことを示す。隣接する高熱伝導部と低熱伝導部との熱伝導率の比は、１００：１以上が好ましく、５００：１以上がより好ましく、１０００：１以上がさらに好ましい。
従って、第１高熱伝導部１２ｂは、低熱伝導部１２ａ（あるはさらに粘着層１８）よりも熱伝導率が高いものであれば、各種の材料からなるものが例示される。
第１高熱伝導部１２ｂの形成材料としては、具体的には、熱伝導率等の点で、金、銀、銅、アルミニウム等の各種の金属が例示される。中でも、熱伝導率、経済性等の点で、銅やアルミニウムは好適に利用される。また、可撓性を有する熱電変換素子（熱電変換モジュール）を得られる等の点で、第１高熱伝導部１２ｂには、金属製のシート（金属箔を含む）も、好適に利用される。
In the present invention, the high thermal conductivity portion and the low thermal conductivity portion indicate that the thermal conductivity is high or low with respect to the adjacent layer (adjacent high thermal conductivity portion or low thermal conductivity portion). The ratio of the thermal conductivity of the adjacent high thermal conductivity portion to the low thermal conductivity portion is preferably 100: 1 or more, more preferably 500: 1 or more, and still more preferably 1000: 1 or more.
Therefore, as long as the thermal conductivity of the first high thermal conductivity portion 12b is higher than that of the low thermal conductivity portion 12a (or the adhesive layer 18), those made of various materials are exemplified.
Specific examples of the material for forming the first high thermal conductivity portion 12b include various metals such as gold, silver, copper, and aluminum in terms of thermal conductivity and the like. Among them, copper and aluminum are suitably used in terms of thermal conductivity, economy and the like. In addition, a metal sheet (including a metal foil) is also suitably used for the first high thermal conductivity portion 12b in that a flexible thermoelectric conversion element (thermoelectric conversion module) can be obtained.
なお、本発明において、第１基板１２の厚さ、低熱伝導部１２ａの厚さ、第１高熱伝導部１２ｂの厚さ等は、第１高熱伝導部１２ｂおよび低熱伝導部１２ａの形成材料、熱電変換素子１０の大きさ等に応じて、適宜、設定すればよい。
なお、本発明において、厚さとは、言い換えれば、第１基板１２、熱電変換層１６、粘着層１８および第２基板２０（被覆層）の積層方向のサイズである。また、第１基板１２の厚さとは、第１高熱伝導部１２ｂが無い領域の低熱伝導部１２ａの厚さである。
本発明者らの検討によれば、第１基板１２の厚さは、２〜１００μｍが好ましく、２〜５０μｍがより好ましい。
In the present invention, the thickness of the first substrate 12, the thickness of the low thermal conductivity portion 12a, the thickness of the first high thermal conductivity portion 12b, etc. are the materials of the first high thermal conductivity portion 12b and the low thermal conductivity portion 12a, It may be set appropriately according to the size of the conversion element 10 or the like.
In the present invention, the thickness is, in other words, the size in the stacking direction of the first substrate 12, the thermoelectric conversion layer 16, the adhesive layer 18, and the second substrate 20 (covering layer). Further, the thickness of the first substrate 12 is the thickness of the low thermal conductivity portion 12 a in the region where the first high thermal conductivity portion 12 b is not present.
According to studies of the present inventors, the thickness of the first substrate 12 is preferably 2 to 100 μm, and more preferably 2 to 50 μm.
また、第１基板１２の面方向の大きさ、第１基板１２における第１高熱伝導部１２ｂの面方向の面積率等も、低熱伝導部１２ａおよび第１高熱伝導部１２ｂの形成材料、熱電変換素子１０の大きさ等に応じて、適宜、設定すればよい。なお、面方向の大きさや面積率とは、すなわち、面方向と直交する方向から見た際の大きさや面積率である。 Further, the size of the first substrate 12 in the surface direction, the area ratio of the first high thermal conductivity portion 12 b in the first substrate 12, etc., the material for forming the low thermal conductivity portion 12 a and the first high thermal conductivity portion 12 b, thermoelectric conversion It may be set appropriately according to the size of the element 10 or the like. Note that the size in the surface direction and the area ratio are, in other words, the size and the area ratio when viewed from the direction orthogonal to the surface direction.
さらに、第１基板１２における第１高熱伝導部１２ｂの面方向の位置も、図示例に限定されず、各種の位置が利用可能である。
例えば、第１基板１２において、第１高熱伝導部１２ｂは、面方向において低熱伝導部１２ａに内包されてもよい。また、第１高熱伝導部１２ｂは、面方向において、一部を第１基板１２の端部に位置し、それ以外の領域が低熱伝導部１２ａに内包されてもよい。
さらに、第１基板１２は、面方向に複数の第１高熱伝導部１２ｂを有してもよい。
Furthermore, the position in the surface direction of the first high thermal conductivity portion 12b in the first substrate 12 is not limited to the illustrated example, and various positions can be used.
For example, in the first substrate 12, the first high thermal conductivity portion 12b may be enclosed in the low thermal conductivity portion 12a in the plane direction. In addition, a part of the first high thermal conductivity portion 12b may be located at the end of the first substrate 12 in the surface direction, and the other region may be included in the low thermal conductivity portion 12a.
Furthermore, the first substrate 12 may have a plurality of first high thermal conductivity portions 12 b in the surface direction.
なお、図１（Ａ）および図１（Ｂ）に示す熱電変換素子１０は、第１基板１２と第２基板２０との間での温度差を生じ易い好ましい態様として、第１基板１２および第２基板２０は、共に、第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂを積層方向の外側に位置している。
しかしながら、本発明は、これ以外にも、第１基板１２が第１高熱伝導部１２ｂを積層方向の外側に位置し、第２基板２０が第２高熱伝導部２０ｂを積層方向の内側に位置するような構成でもよい。
なお、高熱伝導部が金属等の導電性を有する材料で形成され、かつ、高熱伝導部が積層方向の内側に配置される構成において、高熱伝導部と、電極２６、電極２８および熱電変換層１６の少なくとも１つとが電気的に接続されてしまう場合には、高熱伝導部と、電極２６、電極２８および熱電変換層１６の少なくとも１つとの絶縁性を確保するために、間に絶縁層を設けてもよい。
The thermoelectric conversion element 10 shown in FIG. 1 (A) and FIG. 1 (B) has the first substrate 12 and the first substrate 12 and the second substrate 20 as a preferred embodiment that is likely to cause a temperature difference. The two substrates 20 are both located outside the first high thermal conductivity portion 12 b and the second high thermal conductivity portion 20 b in the stacking direction.
However, according to the present invention, the first substrate 12 is located outside the first high thermal conductivity portion 12b in the stacking direction, and the second substrate 20 is located inside the second high thermal conductivity portion 20b in the stacking direction. Such a configuration may be used.
In the configuration in which the high thermal conductivity portion is formed of a conductive material such as metal and the high thermal conductivity portion is disposed inside in the stacking direction, the high thermal conductivity portion, the electrode 26, the electrode 28, and the thermoelectric conversion layer 16 In order to ensure insulation between the high thermal conductivity portion and at least one of the electrode 26, the electrode 28, and the thermoelectric conversion layer 16, an insulating layer is provided between the at least one of the May be
また、第１基板１２の第１高熱伝導部１２ｂおよび第２基板２０の第２高熱伝導部２０ｂは、両者が面方向で完全に重複しなければ、各種のサイズ、形状および位置のものが利用可能である。 In addition, the first high thermal conductivity portion 12b of the first substrate 12 and the second high thermal conductivity portion 20b of the second substrate 20 have various sizes, shapes and positions if they do not completely overlap in the plane direction. It is possible.
前述のように、図１（Ａ）および図１（Ｂ）に示す熱電変換素子では、第１基板１２の第１高熱伝導部１２ｂと、第２基板２０の第２高熱伝導部２０ｂとが、対向する端面が離間するように配置されている。
本発明は、これ以外にも、例えば、第１基板１２の第１高熱伝導部１２ｂを図中左側に移動し、第２基板２０の第２高熱伝導部２０ｂを図中右側に移動して、第１高熱伝導部１２ｂと第２高熱伝導部２０ｂとの対向する端部が、離間方向に同じ位置とする構成でもよい。あるいは、さらに第１基板１２の第１高熱伝導部１２ｂを図中左側に移動し、第２基板２０の第２高熱伝導部２０ｂを図中右側に移動することによって、第１高熱伝導部１２ｂと第２高熱伝導部２０ｂとの一部を、面方向で重複させてもよい。
As described above, in the thermoelectric conversion elements shown in FIGS. 1A and 1B, the first high thermal conductivity portion 12 b of the first substrate 12 and the second high thermal conductivity portion 20 b of the second substrate 20 are, The opposing end faces are arranged to be separated.
In the present invention, for example, the first high thermal conductivity portion 12b of the first substrate 12 is moved to the left in the figure, and the second high thermal conductivity portion 20b of the second substrate 20 is moved to the right in the figure, for example. The opposing ends of the first high thermal conductivity portion 12 b and the second high thermal conductivity portion 20 b may be configured to be at the same position in the separation direction. Alternatively, by further moving the first high thermal conductivity portion 12b of the first substrate 12 to the left in the drawing and moving the second high thermal conductivity portion 20b of the second substrate 20 to the right in the drawing, the first high thermal conductivity portion 12b and A part of the second high thermal conductivity portion 20b may overlap in the surface direction.
あるいは、第１基板に円形の第１高熱伝導部を形成し、第２基板に同サイズの正方形の第３高熱伝導部を形成して、両高熱伝導部の中心を面方向で一致させるように、両基板を配置してもよい。この構成でも、距離は短いが、両高熱伝導部は、端部（周辺）位置が面方向で異なるので、熱電変換層には面方向の温度差が生じ、厚さ方向に温度差を生じさせる熱電変換素子に比して、効率の良い発電が可能である。なお、同サイズの円形および正方形とは、直径と一辺の長さとが一致している円形および正方形である。
すなわち、本発明においては、第１基板と第２基板とで、高熱伝導部が面方向に完全に重複しなければ、第１基板および第２基板は、各種の構成が利用可能である。言い換えれば、第１基板および第２基板は、基板面と垂直方向から見た際に、第１基板と第２基板との高熱伝導部が完全に重なっていなければ、各種の構成が利用可能である。
Alternatively, a circular first high thermal conductivity part is formed on the first substrate, and a square third high thermal conductivity part of the same size is formed on the second substrate so that the centers of the two high thermal conductivity parts coincide in the surface direction. Both substrates may be arranged. Even in this configuration, although the distance is short, the end (periphery) positions of both high thermal conductivity parts are different in the surface direction, so a temperature difference occurs in the surface direction in the thermoelectric conversion layer, causing a temperature difference in the thickness direction Efficient power generation is possible compared to thermoelectric conversion elements. In addition, the circle and the square of the same size are the circle and the square where the diameter and the length of one side correspond.
That is, in the present invention, various configurations can be used for the first substrate and the second substrate as long as the high thermal conductivity portions do not completely overlap in the surface direction between the first substrate and the second substrate. In other words, various configurations can be used for the first substrate and the second substrate if the high thermal conductivity portions of the first substrate and the second substrate do not completely overlap when viewed in the direction perpendicular to the substrate surface. is there.
熱電変換素子１０において、第１基板１２の全面が低熱伝導部１２ａである面には、熱電変換層１６が形成される。
また、熱電変換層１６の上には、粘着層１８を介して第２基板２０が設けられる。第２基板２０は、低熱伝導部２０ａの第２高熱伝導部２０ｂが形成されていない側の面を熱電変換層１６に向けて設けられる。
In the thermoelectric conversion element 10, the thermoelectric conversion layer 16 is formed on the surface of the first substrate 12 which is the low thermal conductive portion 12a.
Further, the second substrate 20 is provided on the thermoelectric conversion layer 16 via the adhesive layer 18. The second substrate 20 is provided with the surface of the low thermal conductivity portion 20 a on the side where the second high thermal conductivity portion 20 b is not formed facing the thermoelectric conversion layer 16.
両基板において、第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂは、熱電変換層１６の面方向に効率的に温度差を生じさせるように配置される。
即ち、両基板の第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂは、熱電変換層１６に対して、面方向に異なる位置に配置されるのが好ましく、第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂの対面する側の端部を熱電変換層１６の離間方向の中心に一致して設けるのがより好ましく、図示例のように、第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂの対面する側の端部が離間方向に離間するように配置されるのがさらに好ましい。
特に、第１高熱伝導部１２ｂと第２高熱伝導部２０ｂとは、離間方向における熱電変換層１６の大きさに対して、離間方向に１０〜９０％離間させるのが好ましく、１０〜５０％離間させるのがより好ましい。
In both substrates, the first high thermal conductivity portion 12 b and the second high thermal conductivity portion 20 b are arranged so as to efficiently cause a temperature difference in the surface direction of the thermoelectric conversion layer 16.
That is, it is preferable that the first high thermal conductivity portion 12b and the second high thermal conductivity portion 20b of both substrates be disposed at different positions in the surface direction with respect to the thermoelectric conversion layer 16, and the first high thermal conductivity portion 12b and the second high thermal conductivity portion It is more preferable that the end on the opposite side of the high thermal conductivity portion 20b be provided coincident with the center of the thermoelectric conversion layer 16 in the separation direction, as in the illustrated example, the first high thermal conductivity portion 12b and the second high thermal conductivity portion 20b. It is further preferred that the ends on the opposite side of the are arranged to be spaced apart in the separating direction.
In particular, the first high thermal conductivity portion 12b and the second high thermal conductivity portion 20b are preferably separated by 10 to 90% in the separation direction with respect to the size of the thermoelectric conversion layer 16 in the separation direction, and 10 to 50% It is more preferable to
また、熱電変換層１６には、面方向に挟むように、電極２６および電極２８からなる電極対が接続される。 Further, an electrode pair consisting of the electrode 26 and the electrode 28 is connected to the thermoelectric conversion layer 16 so as to be sandwiched in the surface direction.
なお、熱電変換素子１０において、第１基板１２の第１高熱伝導部１２ｂを形成されていない側の表面には、必要に応じて、密着層を有してもよい。密着層を有することにより、第１基板１２と、熱電変換層１６や電極２６および電極２８との密着性を良好にして、耐屈曲性など、機械的強度が良好な熱電変換素子（熱電変換モジュール）が得られる。 In the thermoelectric conversion element 10, an adhesion layer may be provided on the surface of the first substrate 12 on which the first high thermal conductivity portion 12b is not formed, if necessary. By having the adhesion layer, the adhesion between the first substrate 12 and the thermoelectric conversion layer 16, the electrode 26, and the electrode 28 is improved, and a thermoelectric conversion element (thermoelectric conversion module with good mechanical strength such as bending resistance) ) Is obtained.
密着層は、第１基板１２（低熱伝導部１２ａ）、熱電変換層１６、電極２６および電極２８の形成材料に応じて、熱電変換層１６や両電極と第１基板１２との密着性を確保できるものであれば、各種のものが利用可能である。
例えば、熱電変換層１６の形成材料として、ニッケルやニッケル合金を用いる場合や、電極２６および電極２８の形成材料として、ニッケル、ニッケル合金、アルミニウム、アルミニウム合金、白金等を用いる場合には、密着層としては、酸化珪素（ＳｉＯ2）、酸化アルミニウム（Ａｌ2Ｏ3）、酸化チタン（ＴｉＯ2）、クロム、チタン等からなる層が例示される。
また、密着層を酸化珪素等の金属酸化物で形成することにより、第１基板１２を通過した水分から熱電変換層１６を保護する、ガスバリア層としての作用も得られる。
The adhesion layer secures the adhesion between the thermoelectric conversion layer 16 or both electrodes and the first substrate 12 in accordance with the formation material of the first substrate 12 (low thermal conductivity portion 12a), the thermoelectric conversion layer 16, the electrode 26, and the electrode 28. If possible, various ones can be used.
For example, when nickel or a nickel alloy is used as a material for forming the thermoelectric conversion layer 16, or when nickel, a nickel alloy, aluminum, an aluminum alloy, platinum or the like is used as a material for forming the electrodes 26 and 28, the adhesion layer As the layer, a layer made of silicon oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), titanium oxide (TiO 2 ), chromium, titanium or the like is exemplified.
In addition, by forming the adhesion layer with a metal oxide such as silicon oxide, the function as a gas barrier layer that protects the thermoelectric conversion layer 16 from moisture that has passed through the first substrate 12 can also be obtained.
熱電変換素子１０は、熱源との接触などによる加熱によって熱電変換層１６の内部に温度差が生じることにより、この温度差に応じて、熱電変換層１６の内部において、この温度差の方向のキャリア密度に差が生じ、電力が発生する。 The thermoelectric conversion element 10 generates a temperature difference inside the thermoelectric conversion layer 16 due to heating by contact with a heat source or the like, and according to this temperature difference, carriers in the direction of this temperature difference inside the thermoelectric conversion layer 16 There is a difference in density and power is generated.
本発明の熱電変換素子１０において、熱電変換層１６は、公知の熱電変換材料を用いる各種の構成が、全て、利用可能である。従って、有機系の熱電変換材料を用いる物であっても、無機系の熱電変換材料を用いるものであってもよい。
熱電変換層１６に用いられる熱電変換材料としては、無機系の熱電変換材料として、（１）ＢｉＳｂＴｅ、ＢｉＳｅＴｅ、ＢｉＴｅなどのＢｉＴｅ系、（２）ＣｏＳｂ3、Ｚｎ4Ｓｂ3などのアンチモン（Ｓｂ）含有化合物、（３）Ｍｇ2Ｓｉ、β―ＦｅＳｉ２、ＳｉＧｅなどのシリサイド化合物、（４）ＳｒＴｉＯ３、ＺｎＯ，ＴｉＯ２などの酸化物半導体、（５）Ｆｅ−Ａｌなどの金属間化合物、（６）ニッケル、ニクロム、クロメル、コンスタンタンなどのニッケル、ならびニッケル合金どの公知の材料が好適に使用できる。
なお、ニッケル合金は、温度差を生じることで発電するニッケル合金が、各種、利用可能である。具体的には、バナジウム、クロム、シリコン、アルミニウム、チタン、モリブデン、マンガン、亜鉛、錫、銅、コバルト、鉄、マグネシウム、ジルコニウムなどの１成分、もしくは、２成分以上と混合したニッケル合金等が例示される。
あるいは、熱電変換層１６に用いられる熱電変換材料としては、例えば、導電性高分子や導電性ナノ炭素材料等の有機材料が好適に例示される。
In the thermoelectric conversion element 10 of the present invention, as the thermoelectric conversion layer 16, all of various configurations using a known thermoelectric conversion material can be used. Therefore, either an organic thermoelectric conversion material or an inorganic thermoelectric conversion material may be used.
As a thermoelectric conversion material used for the thermoelectric conversion layer 16, (1) BiTe-based materials such as BiSbTe, BiSeTe, BiTe, etc., (2) Antimony (Sb) such as CoSb 3 , Zn 4 Sb 3 etc. Containing compounds, (3) Silicide compounds such as Mg 2 Si, β-FeSi 2 , SiGe, (4) oxide semiconductors such as SrTiO 3 , ZnO, TiO 2 , (5) intermetallic compounds such as Fe—Al, 6) Nickel, nickel such as nichrome, chromel, constantan, nickel alloy and any known material can be suitably used.
In addition, the nickel alloy which can generate electric power by producing a temperature difference can utilize various things. Specifically, nickel alloy etc. mixed with one component or two or more components such as vanadium, chromium, silicon, aluminum, titanium, molybdenum, manganese, zinc, tin, copper, cobalt, iron, magnesium, zirconium etc. are exemplified. Be done.
Alternatively, as a thermoelectric conversion material used for the thermoelectric conversion layer 16, for example, an organic material such as a conductive polymer or a conductive nanocarbon material is suitably exemplified.
導電性高分子としては、共役系の分子構造を有する高分子化合物（共役系高分子）が例示される。具体的には、ポリアニリン、ポリフェニレンビニレン、ポリピロール、ポリチオフェン、ポリフルオレン、アセチレン、ポリフェニレンなどの公知のπ共役高分子等が例示される。特に、ポリジオキシチオフェンは、好適に使用できる。 As the conductive polymer, a polymer compound (conjugated polymer) having a conjugated molecular structure is exemplified. Specific examples thereof include known π-conjugated polymers such as polyaniline, polyphenylene vinylene, polypyrrole, polythiophene, polyfluorene, acetylene and polyphenylene. In particular, polydioxythiophene can be suitably used.
導電性ナノ炭素材料としては、具体的には、カーボンナノチューブ、カーボンナノファイバー、グラファイト、グラフェン、カーボンナノ粒子等が例示される。これらは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。以下の説明では、『カーボンナノチューブ』を『ＣＮＴ』とも言う。
中でも、熱電特性がより良好となる理由から、ＣＮＴが好ましく利用される。
Specific examples of the conductive nanocarbon material include carbon nanotubes, carbon nanofibers, graphite, graphene, carbon nanoparticles and the like. These may be used alone or in combination of two or more. In the following description, "carbon nanotube" is also referred to as "CNT".
Among them, CNTs are preferably used because they have better thermoelectric properties.
ＣＮＴには、１枚の炭素膜（グラフェン・シート）が円筒状に巻かれた単層ＣＮＴ、２枚のグラフェン・シートが同心円状に巻かれた２層ＣＮＴ、及び複数のグラフェン・シートが同心円状に巻かれた多層ＣＮＴがある。本発明においては、単層ＣＮＴ、２層ＣＮＴ、多層ＣＮＴを各々単独で用いてもよく、２種以上を併せて用いてもよい。特に、導電性及び半導体特性において優れた性質を持つ単層ＣＮＴおよび２層ＣＮＴを用いることが好ましく、単層ＣＮＴを用いることがより好ましい。
単層ＣＮＴは、半導体性のものであっても、金属性のものであってもよく、両者を併せて用いてもよい。半導体性ＣＮＴと金属性ＣＮＴとを両方を用いる場合、組成物中の両者の含有比率は、組成物の用途に応じて適宜調整することができる。また、ＣＮＴには金属などが内包されていてもよく、フラーレン等の分子が内包されたものを用いてもよい。
ＣＮＴは、修飾あるいは処理されたものであってもよい。さらに、熱電変換層１６にＣＮＴを利用する場合には、ドーパント（アクセプタ）を含んでいてもよい。
In the CNT, a single layer CNT in which one carbon film (graphene sheet) is cylindrically wound, a two-layer CNT in which two graphene sheets are concentrically wound, and a plurality of graphene sheets are concentric There are multi-layered CNTs wound in a shape. In the present invention, single-walled CNTs, double-walled CNTs, and multi-walled CNTs may be used alone or in combination of two or more. In particular, it is preferable to use single-walled CNT and double-walled CNT having excellent properties in conductivity and semiconductor characteristics, and it is more preferable to use single-walled CNT.
The single-walled CNT may be semiconductive or metallic, or both may be used in combination. When using both semiconducting CNT and metallic CNT, the content ratio of both in a composition can be suitably adjusted according to the use of a composition. Further, CNTs may contain metals or the like, or molecules containing molecules such as fullerenes may be used.
The CNTs may be modified or treated. Furthermore, when using CNT for the thermoelectric conversion layer 16, you may contain the dopant (acceptor).
熱電変換層１６を構成する熱電変換材料としては、ニッケルあるいはニッケル合金も好適に例示される。 As a thermoelectric conversion material which comprises the thermoelectric conversion layer 16, nickel or a nickel alloy is also illustrated suitably.
本発明の熱電変換素子１０において、熱電変換層１６の厚さ、面方向の大きさ、基板に対する面方向の面積率等は、熱電変換層１６の形成材料、熱電変換素子１０の大きさ等に応じて、適宜、設定すればよい。 In the thermoelectric conversion element 10 of the present invention, the thickness of the thermoelectric conversion layer 16, the size in the plane direction, the area ratio of the plane direction to the substrate, etc. depend on the forming material of the thermoelectric conversion layer 16, the size of the thermoelectric conversion element 10, etc. Depending on the situation, it may be set appropriately.
このような熱電変換層１６には、面方向に挟持するように、電極２６および電極２８が接続される。熱電変換素子１０において、電極２６および電極２８は、端部を熱電変換層１６に覆われて、熱電変換層１６に接続される。 The electrode 26 and the electrode 28 are connected to such a thermoelectric conversion layer 16 so as to be sandwiched in the surface direction. In the thermoelectric conversion element 10, the electrode 26 and the electrode 28 are connected to the thermoelectric conversion layer 16 with the end portions covered with the thermoelectric conversion layer 16.
電極２６および電極２８は、必要な導電率を有するものであれば、各種の材料で形成可能である。
電極２６および電極２８の形成材料としては、具体的には、銅、銀、金、白金、ニッケル、アルミニウム、コンスタンタン、クロム、インジウム、鉄、銅合金などの金属材料、酸化インジウムスズ（ＩＴＯ）や酸化亜鉛（ＺｎＯ）等の各種のデバイスで透明電極として利用されている材料等が例示される。中でも、銅、金、銀、白金、ニッケル、銅合金、アルミニウム、コンスタンタン等は好ましく例示され、銅、金、銀、白金、ニッケルは、より好ましく例示される。
電極２６および電極２８は、例えば、クロム層の上に銅層を形成してなる構成等、積層電極であってもよい。
The electrode 26 and the electrode 28 can be formed of various materials as long as they have necessary conductivity.
Specifically, the materials for forming the electrodes 26 and 28 include copper, silver, gold, platinum, nickel, aluminum, constantan, metal materials such as chromium, indium, iron, and copper alloys, indium tin oxide (ITO), and the like Examples thereof include materials used as transparent electrodes in various devices such as zinc oxide (ZnO). Among them, copper, gold, silver, platinum, nickel, copper alloy, aluminum, constantan and the like are preferably exemplified, and copper, gold, silver, platinum, nickel are more preferably exemplified.
The electrode 26 and the electrode 28 may be, for example, a laminated electrode, such as a structure in which a copper layer is formed on a chromium layer.
電極２６および電極２８の厚さや大きさ、形状等も、熱電変換層１６の厚さや大きさ、形状、熱電変換素子１０の大きさ等に応じて、適宜、設定すればよい。 The thickness, size, shape, and the like of the electrodes 26 and 28 may be appropriately set according to the thickness, size, and shape of the thermoelectric conversion layer 16, the size of the thermoelectric conversion element 10, and the like.
図示例の熱電変換素子において、電極２６および電極２８は、離間方向の端部を熱電変換層１６に覆われて、熱電変換層１６に接続されている。
本発明は、これ以外にも、電極２６および電極２８は、各種の構成が利用可能である。一例として、図２（Ａ）に概念的に示すように、熱電変換層１６の端部から端面に沿って立ち上がり、熱電変換層１６の上面の端部近傍に到る電極２６および電極２８が例示される。また、図２（Ｂ）に概念的に示すように、熱電変換層１６の端部に当接する電極２６および電極２８も利用可能である。さらに、電極２６と電極２８とは、構成が異なってもよい。
In the thermoelectric conversion element of the illustrated example, the electrode 26 and the electrode 28 are connected to the thermoelectric conversion layer 16 with the end portions in the separation direction covered by the thermoelectric conversion layer 16.
In the present invention, various configurations can be used for the electrode 26 and the electrode 28 besides this. As an example, as conceptually shown in FIG. 2A, the electrode 26 and the electrode 28 rise from the end of the thermoelectric conversion layer 16 along the end face and reach near the end of the upper surface of the thermoelectric conversion layer 16 Be done. Further, as conceptually shown in FIG. 2B, an electrode 26 and an electrode 28 in contact with the end of the thermoelectric conversion layer 16 can also be used. Furthermore, the configurations of the electrode 26 and the electrode 28 may be different.
熱電変換素子１０において、熱電変換層１６、電極２６および電極２８を覆って、粘着層１８が積層される。粘着層１８は、十分な密着力で第２基板２０を貼着するためのものである。また、粘着層１８は、絶縁層としての作用を有してもよい。
粘着層１８の形成材料は、熱電変換層１６、電極２６および電極２８の形成材料と、第２基板２０（低熱伝導部２０ａ）の形成材料とに応じて、絶縁性を有し、かつ、両者を貼着可能なものが、各種、利用可能である。
具体的には、アクリル樹脂、ウレタン樹脂、シリコーン樹脂、エポキシ樹脂、ゴム、ＥＶＡ、α-オレフィンポリビニルアルコール、ポリビニルブチラール、ポリビニルピロリドン、ゼラチン、デンプン等が例示される。また、粘着層１８は、市販の接着剤、粘着剤、両面テープや粘着フィルム等を利用して形成してもよい。
In the thermoelectric conversion element 10, an adhesive layer 18 is stacked so as to cover the thermoelectric conversion layer 16, the electrode 26, and the electrode 28. The adhesive layer 18 is for adhering the second substrate 20 with a sufficient adhesion. In addition, the adhesive layer 18 may have an action as an insulating layer.
The forming material of the adhesive layer 18 has insulating properties according to the forming materials of the thermoelectric conversion layer 16, the electrode 26 and the electrode 28 and the forming material of the second substrate 20 (the low thermal conductive portion 20 a), and both There are a variety of things that can be used.
Specifically, acrylic resin, urethane resin, silicone resin, epoxy resin, rubber, EVA, α-olefin polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, gelatin, starch and the like are exemplified. The adhesive layer 18 may be formed using a commercially available adhesive, adhesive, double-sided tape, adhesive film, or the like.
粘着層１８の厚さは、粘着層１８の形成材料、熱電変換層１６に起因する段差の大きさ等に応じて、熱電変換層１６等と第２基板２０とを十分な密着力で貼着でき、かつ、絶縁できる厚さを、適宜、設定すればよい。なお、粘着層１８は、基本的に、薄い方が、熱電変換性能を高くできる。
具体的には、５〜１００μｍが好ましく、５〜５０μｍがより好ましい。
粘着層１８の厚さを５μｍ以上とすることにより、熱電変換層１６に起因する段差を十分に埋められる、良好な密着性および十分な絶縁性が得られる等の点で好ましい。
粘着層１８の厚さを１００μｍ以下、特に５０μｍ以下とすることにより、熱電変換素子１０（熱電変換モジュール）の薄膜化を計れる、可撓性の良好な熱電変換素子１０を得ることができる、粘着層１８の熱抵抗を小さくでき、より良好な熱電変換性能が得られる等の点で好ましい。
The thickness of the adhesive layer 18 adheres the thermoelectric conversion layer 16 or the like to the second substrate 20 with sufficient adhesion depending on the material of the adhesive layer 18, the size of the step caused by the thermoelectric conversion layer 16, etc. The thickness which can and can be insulated may be set appropriately. In addition, basically, the thinner the adhesive layer 18, the higher the thermoelectric conversion performance can be.
Specifically, 5 to 100 μm is preferable, and 5 to 50 μm is more preferable.
By setting the thickness of the adhesive layer 18 to 5 μm or more, it is preferable in that the step due to the thermoelectric conversion layer 16 can be sufficiently filled, and good adhesion and sufficient insulation can be obtained.
By setting the thickness of the adhesive layer 18 to 100 μm or less, in particular 50 μm or less, it is possible to obtain a flexible flexible thermoelectric conversion element 10 capable of measuring thinning of the thermoelectric conversion element 10 (thermoelectric conversion module) It is preferable in that the thermal resistance of the layer 18 can be reduced and better thermoelectric conversion performance can be obtained.
なお、必要に応じて、密着性を向上するために、熱電変換層１６、電極２６および電極２８と粘着層１８との界面、粘着層１８と第２基板２０との界面の１以上において、界面を形成する表面の少なくとも１面に、プラズマ処理、ＵＶオゾン処理、電子線照射処理等の公知の表面処理を施して、表面の改質や清浄化を行ってもよい。 If necessary, in order to improve adhesion, at one or more of the interfaces between the thermoelectric conversion layer 16, the electrode 26 and the electrode 28 and the adhesive layer 18, and the interface between the adhesive layer 18 and the second substrate 20, an interface The surface may be reformed or cleaned by performing known surface treatment such as plasma treatment, UV ozone treatment, or electron beam irradiation treatment on at least one surface of the surface to form.
前述のように、粘着層１８の上には、低熱伝導部２０ａを粘着層１８側に向けて、第２基板２０が積層、貼着されて、熱電変換素子１０が構成される。また、第１基板１２の第１高熱伝導部１２ｂと第２基板２０の第２高熱伝導部２０ｂとは、離間方向に異なる位置に配置される。
本発明の熱電変換素子１０（熱電変換モジュール）は、基本的に、第１基板１２（第１高熱伝導部）側が熱源３０側となるように設置され、第２基板２０側に放熱フィン等の放熱手段３２が設けられて、使用される。
従って、熱源３０の熱は、第１高熱伝導部１２ｂから低熱伝導部１２ａ等を通過して熱電変換層１６の図中右側に至り、熱電変換層１６を図中左側から図中右側に面方向に伝って、低熱伝導部２０ａ等を通過して、放熱手段３２が設けられる第２高熱伝導部２０ｂから、放熱される。
これにより、前述のように、離間方向において、第１高熱伝導部１２ｂ側すなわち加熱側と、第２高熱伝導部２０ｂ側すなわち冷却側との間で、熱電変換層１６内に温度差が生じ、熱電変換層１６の内部において、この温度差の方向のキャリア密度に差が生じ、発電する。また、電極２６および電極２８に配線を接続することにより、加熱によって発生した電力（電気エネルギー）が取り出される。
As described above, the thermoelectric conversion element 10 is configured by laminating and sticking the second substrate 20 on the adhesive layer 18 with the low thermal conductivity portion 20 a facing the adhesive layer 18 side. Further, the first high thermal conductivity portion 12 b of the first substrate 12 and the second high thermal conductivity portion 20 b of the second substrate 20 are disposed at different positions in the separation direction.
The thermoelectric conversion element 10 (thermoelectric conversion module) of the present invention is basically installed such that the first substrate 12 (first high thermal conductivity portion) side is the heat source 30 side, and the second substrate 20 side is a radiation fin or the like A heat dissipation means 32 is provided and used.
Therefore, the heat of the heat source 30 passes from the first high thermal conductivity portion 12b to the low thermal conductivity portion 12a etc. and reaches the right side of the thermoelectric conversion layer 16 in the figure, and the thermoelectric conversion layer 16 Then, it passes through the low thermal conductivity portion 20a and the like, and is dissipated from the second high thermal conductivity portion 20b in which the thermal radiation means 32 is provided.
As a result, as described above, a temperature difference occurs in the thermoelectric conversion layer 16 between the first high thermal conductivity portion 12 b side, ie, the heating side, and the second high thermal conductivity portion 20 b side, ie, the cooling side, in the separation direction. Within the thermoelectric conversion layer 16, a difference occurs in the carrier density in the direction of this temperature difference, and power is generated. Further, by connecting a wire to the electrode 26 and the electrode 28, electric power (electrical energy) generated by heating is extracted.
このように、前述のin plane型である本発明の熱電変換素子１０は、熱電変換層１６の面方向に温度差を生じさせて、熱エネルギーを電気エネルギーに変換する。そのため、薄い熱電変換層１６でも、熱電変換層１６内において温度差が生じる距離を長くして、効率の良い発電ができる。
さらに、熱電変換層を薄いシート状にできるので、フレキシブル性にも優れ、曲面等への設置も容易な熱電変換モジュールが得られる。
As described above, the thermoelectric conversion element 10 according to the present invention, which is the above-described in-plane type, generates a temperature difference in the surface direction of the thermoelectric conversion layer 16 to convert thermal energy into electrical energy. Therefore, even with the thin thermoelectric conversion layer 16, the distance at which the temperature difference occurs in the thermoelectric conversion layer 16 can be increased to perform efficient power generation.
Furthermore, since the thermoelectric conversion layer can be formed into a thin sheet, it is possible to obtain a thermoelectric conversion module that is excellent in flexibility and easy to install on a curved surface or the like.
ところが、本発明者らの検討によれば、in plane型の熱電変換素子は、このような利点を有する反面、水冷や強制空冷下に比べ、自然空冷下において、発電量が低下し易い傾向にあることが判明した。 However, according to the study of the present inventors, the in-plane type thermoelectric conversion element has such an advantage, but on the other hand, the amount of power generation tends to be reduced under natural air cooling compared to under water cooling or forced air cooling. It turned out to be.
本発明者らは、この原因について検討を重ねた結果、以下の知見を得た。
すなわち、in plane型の熱電変換素子は、高熱伝導部と低熱伝導部とを有する基板を用いて、熱電変換層の面方向に温度差を生じさせる構成を有する。この構成によれば、面方向に温度差を生じさせる距離を長くできる反面、構成上、熱源と、熱電変換層における冷却される側との距離が非常に近くなる。具体的には、熱源３０と、熱電変換層１６における冷却側である離間方向の図中左側の領域との距離は、第１高熱伝導部１２ｂと低熱伝導部１２ａの厚さ分しか無い。
そのため、熱源と基板との間の空気層を介した熱伝導により、熱電変換層の冷却側が加熱され易く、熱電変換層における加熱側と冷却側との間の温度差が小さくなって、発電量が低下してしまう。すなわち、熱電変換層１６の加熱側である離間方向の第１高熱伝導部１２ｂ側の温度と、熱電変換層１６における冷却側である離間方向の第２高熱伝導部２０ｂ側との温度差が小さくなって、発電量が低下してしまう。
特に、自然空冷下では、熱電変換層１６における第２高熱伝導部２０ｂ側すなわち冷却側における冷却が追い付かずに、熱電変換層１６における加熱側と冷却側との温度差が小さくなり易く、発電量が低下し易い。
The present inventors obtained the following knowledge as a result of repeating examination about this cause.
That is, the in-plane type thermoelectric conversion element has a configuration that causes a temperature difference in the surface direction of the thermoelectric conversion layer using a substrate having a high thermal conductivity portion and a low thermal conductivity portion. According to this configuration, the distance for causing a temperature difference in the surface direction can be increased, but the distance between the heat source and the side of the thermoelectric conversion layer to be cooled is very short in terms of the configuration. Specifically, the distance between the heat source 30 and the region on the left side in the drawing in the separation direction which is the cooling side in the thermoelectric conversion layer 16 is only the thickness of the first high thermal conductivity portion 12 b and the low thermal conductivity portion 12 a.
Therefore, the cooling side of the thermoelectric conversion layer is likely to be heated by heat conduction through the air layer between the heat source and the substrate, and the temperature difference between the heating side and the cooling side in the thermoelectric conversion layer becomes small. Will decrease. That is, the temperature difference between the temperature on the side of the first high heat conduction portion 12b in the separation direction which is the heating side of the thermoelectric conversion layer 16 and the temperature on the side of the second high heat conduction portion 20b in the separation direction which is the cooling side of the thermoelectric conversion layer 16 is small. Power generation will be reduced.
In particular, under natural air cooling, the cooling on the second high thermal conductivity portion 20b side of the thermoelectric conversion layer 16, that is, the cooling side does not catch up, and the temperature difference between the heating side and the cooling side in the thermoelectric conversion layer 16 tends to be small. Is easy to lower.
これに対し、本発明の熱電変換素子１０は、第１基板１２の第１高熱伝導部１２ｂの、熱電変換層１６側（低熱伝導部１２ａ側）とは反対側の面に設置される接合部材２２を有する。
本発明の熱電変換素子１０は、第１高熱伝導部１２ｂと熱源３０との間に接合部材２２を配置して、熱源３０と第１基板１２との距離を取ることで、空気層を介した熱伝導を抑制する。その結果、自然放冷下であっても、不要な吸熱による熱電変換層１６の冷却側の加熱を防止して、冷却側を十分に冷却できる。これにより、熱電変換層１６における加熱側と冷却側との温度差が小さくなるのを抑制して、熱電変換層１６の加熱側と冷却側との温度差を確保して、発電量の向上を図ることができる。
On the other hand, the thermoelectric conversion element 10 of the present invention is a bonding member provided on the surface of the first high thermal conductivity portion 12 b of the first substrate 12 opposite to the thermoelectric conversion layer 16 side (low thermal conductivity portion 12 a side). Having 22.
In the thermoelectric conversion element 10 of the present invention, the junction member 22 is disposed between the first high thermal conductivity portion 12 b and the heat source 30 to take a distance between the heat source 30 and the first substrate 12, thereby interposing an air layer. Suppress heat conduction. As a result, even under natural cooling, heating on the cooling side of the thermoelectric conversion layer 16 due to unnecessary heat absorption can be prevented, and the cooling side can be sufficiently cooled. Thereby, the temperature difference between the heating side and the cooling side in the thermoelectric conversion layer 16 is suppressed from being reduced, the temperature difference between the heating side and the cooling side of the thermoelectric conversion layer 16 is secured, and the power generation amount is improved. Can be
接合部材２２は、第１高熱伝導部１２ｂと熱源３０との間に配置されるものであるため、熱源３０の熱を第１高熱伝導部１２ｂに好適に熱伝導できる材料からなるのが好ましく、接合部材２２は、第１高熱伝導部１２ｂの熱伝導率の７０％以上の熱伝導率を有する材料からなるのが好ましい。また、接合部材２２の熱伝導率は、２０Ｗ／（ｍ・Ｋ）以上であるのが好ましく、５０Ｗ／（ｍ・Ｋ）以上であるのがより好ましい。 Since the bonding member 22 is disposed between the first high thermal conductivity portion 12b and the heat source 30, it is preferable that the bonding member 22 be made of a material that can suitably conduct heat of the heat source 30 to the first high thermal conductivity portion 12b, The bonding member 22 is preferably made of a material having a thermal conductivity of 70% or more of the thermal conductivity of the first high thermal conductivity portion 12b. The thermal conductivity of the bonding member 22 is preferably 20 W / (m · K) or more, and more preferably 50 W / (m · K) or more.
具体的には、接合部材２２の形成材料としては、金、銀、銅、ニッケル、アルミニウム等の各種の金属、ニッケル合金、銅合金、銀合金はんだ等の合金、あるいは、炭素繊維や金属粒子等のフィラーを、シリコーンやゴム等の樹脂材料中に分散し、垂直配向した材料などが好適に利用される。
また、接合部材２２の形成材料として、フィラーを垂直配向した材料を用いる場合には、フィラーの配向方向を厚さ方向と一致させることが好ましい。すなわち、接合部材２２の厚さ方向における熱伝導率が、面方向における熱伝導率よりも高いことが好ましい。
接合部材２２として、厚さ方向の熱伝導率が面方向の熱伝導率よりも高いものを用いることで、熱源３０から第１高熱伝導部１２ｂへの伝熱を好適に行いつつ、接合部材２２から外部（空気層）への放熱を抑制することができる。
なお、接合部材２２として、熱伝導率に異方性を有する材料を用いる場合には、厚さ方向における接合部材２２の熱伝導率が第１高熱伝導部１２ｂの熱伝導率の７０％以上であるのが好ましく、また、３０Ｗ／（ｍ・Ｋ）以上であるのが好ましい。
Specifically, as a material for forming the bonding member 22, various metals such as gold, silver, copper, nickel, aluminum, etc., alloys such as nickel alloy, copper alloy, silver alloy solder, carbon fibers, metal particles, etc. The filler of the above is dispersed in a resin material such as silicone or rubber, and a vertically oriented material is suitably used.
Moreover, when using the material which carried out the vertical orientation of the filler as a formation material of the joining member 22, it is preferable to make the orientation direction of a filler correspond with the thickness direction. That is, the thermal conductivity in the thickness direction of the bonding member 22 is preferably higher than the thermal conductivity in the surface direction.
By using a material whose thermal conductivity in the thickness direction is higher than the thermal conductivity in the surface direction as the bonding member 22, the heat transfer from the heat source 30 to the first high heat conduction portion 12 b is suitably performed while the bonding member 22 is performed. It is possible to suppress heat dissipation from the outside to the outside (air layer).
When a material having anisotropy in thermal conductivity is used as the joining member 22, the thermal conductivity of the joining member 22 in the thickness direction is 70% or more of the thermal conductivity of the first high thermal conductivity portion 12b. It is preferably present, and preferably 30 W / (m · K) or more.
また、図１（Ａ）に示すように、接合部材２２は基本的に、面方向において、第１高熱伝導部１２ｂが配置された領域に設置され、第１高熱伝導部１２ｂが配置されない領域（第２高熱伝導部２０ｂが配置された領域）には設置されない。
これにより、冷却側における空気層の厚さを厚くして、熱源３０の熱が、接合部材２２を介して熱電変換層１６の冷却側に伝熱するのを抑制する。
Further, as shown in FIG. 1A, the joining member 22 is basically disposed in the area where the first high thermal conductivity portion 12b is disposed in the plane direction, and the region where the first high thermal conductivity portion 12b is not disposed ( It is not installed in the area | region where the 2nd high heat conduction part 20b is arrange | positioned.
Thus, the thickness of the air layer on the cooling side is increased, and heat transfer from the heat source 30 to the cooling side of the thermoelectric conversion layer 16 via the bonding member 22 is suppressed.
また、接合部材２２の厚さには限定はなく、接合部材の形成材料、熱電変換素子１０のサイズ、第１高熱伝導部１２ｂのサイズ等に応じて適宜設定すればよい。熱源３０と第１基板１２との距離を取り、空気層を介した熱伝導を抑制する観点から、接合部材２２の厚さは、第１高熱伝導部１２ｂの厚さ以上であることが好ましく、第１高熱伝導部１２ｂの厚さの１．５倍以上２．０倍以下であるのがより好ましい。また、接合部材２２の厚さは、０．１ｍｍ以上が好ましく、０．５ｍｍ以上がより好ましく、１．０ｍｍ以上が特に好ましい。 Further, the thickness of the bonding member 22 is not limited, and may be appropriately set according to the forming material of the bonding member, the size of the thermoelectric conversion element 10, the size of the first high heat conduction portion 12b, and the like. From the viewpoint of taking a distance between the heat source 30 and the first substrate 12 and suppressing heat conduction through the air layer, the thickness of the bonding member 22 is preferably equal to or greater than the thickness of the first high thermal conductivity portion 12 b It is more preferable that it is 1.5 times or more and 2.0 times or less of the thickness of the 1st high heat conduction part 12b. Moreover, 0.1 mm or more is preferable, as for the thickness of the joining member 22, 0.5 mm or more is more preferable, and 1.0 mm or more is especially preferable.
ここで、本発明の熱電変換素子においては、さらに、接合部材２２上に配置される、面方向の熱伝導率が厚み方向の熱伝導率よりも高い熱伝導シートを有するのが好ましい。
図３（Ａ）は、熱伝導シートを有する熱電変換素子の一例を概念的に表す斜視図であり、図３（Ｂ）は、図３（Ａ）の接合部材と熱伝導シートとの接続部分を拡大して示す断面図である。
なお、図３（Ａ）に示す熱電変換素子５０は、前述の図１（Ａ）および図１（Ｂ）に示す熱電変換素子１０と、多くの部材を共用するので、同じ部材には同じ符号を付し、以下の説明は、異なる部位を主に行う。
Here, in the thermoelectric conversion element of the present invention, it is preferable to further include a heat conductive sheet disposed on the bonding member 22 and having a thermal conductivity in the surface direction higher than the thermal conductivity in the thickness direction.
FIG. 3A is a perspective view conceptually showing an example of a thermoelectric conversion element having a heat conductive sheet, and FIG. 3B is a connection portion between the bonding member of FIG. 3A and the heat conductive sheet. Is an enlarged cross-sectional view of FIG.
The thermoelectric conversion element 50 shown in FIG. 3 (A) shares many members with the thermoelectric conversion element 10 shown in FIG. 1 (A) and FIG. 1 (B) described above. The following description mainly focuses on different parts.
図３（Ａ）に示す熱電変換素子５０は、接合部材２２の、第１高熱伝導部１２ｂとは反対側の面に配置される熱伝導シート２４を有する。すなわち、熱伝導シート２４は、熱電変換素子５０の第１高熱伝導部１２ｂと熱源３０との間に配置される。
この熱伝導シート２４は、面方向の熱伝導率が、厚み方向の熱伝導率よりも高いものである。また、熱伝導シート２４は、面方向において、第１高熱伝導部１２ｂが配置された領域のみならず、第１高熱伝導部１２ｂが配置されない領域（第２高熱伝導部２０ｂが配置された領域）も包含する大きさを有する。したがって、熱伝導シート２４と、第１基板１２の第１高熱伝導部１２ｂが形成されない領域との間には空気層が形成され、また、熱伝導シート２４の、第１高熱伝導部１２ｂとは反対側の面は全面的に熱源３０と接触する。
The thermoelectric conversion element 50 shown to FIG. 3A has the heat conductive sheet 24 arrange | positioned at the surface on the opposite side to the 1st high heat conduction part 12b of the joining member 22. As shown in FIG. That is, the heat conduction sheet 24 is disposed between the first high heat conduction portion 12 b of the thermoelectric conversion element 50 and the heat source 30.
The heat conduction sheet 24 has a thermal conductivity in the surface direction higher than that in the thickness direction. In addition, the heat conduction sheet 24 is not only the area where the first high heat conduction portion 12b is disposed but also the area where the first high heat conduction portion 12b is not disposed (the area where the second high heat conduction portion 20b is disposed) Also includes the size. Therefore, an air layer is formed between the heat conductive sheet 24 and the area where the first high heat conductive portion 12 b of the first substrate 12 is not formed, and the first high heat conductive portion 12 b of the heat conductive sheet 24 is The opposite surface is in full contact with the heat source 30.
さらに、図３（Ａ）、および、図３（Ｂ）に示す熱電変換素子５０は、好適な態様として、熱伝導シート２４が凹部２４ａを有し、接合部材２２がこの凹部２４ａに嵌合する構成を有する。
なお、本明細書において、接合部材２２が熱伝導シート２４の凹部２４ａに嵌合する構成の場合には、接合部材２２の厚さとは、熱伝導シート２４の表面からの高さとする。すなわち、熱伝導シート２４と第１高熱伝導部１２ｂとの間の距離を、接合部材２２の厚さとする。
Furthermore, as a preferred embodiment of the thermoelectric conversion element 50 shown in FIGS. 3A and 3B, the heat conduction sheet 24 has a recess 24a, and the joining member 22 is fitted in the recess 24a. It has composition.
In the present specification, in the case where the bonding member 22 is fitted in the recess 24 a of the heat conduction sheet 24, the thickness of the bonding member 22 is the height from the surface of the heat conduction sheet 24. That is, the distance between the heat conduction sheet 24 and the first high heat conduction portion 12 b is taken as the thickness of the bonding member 22.
面方向の熱伝導率が厚み方向の熱伝導率よりも高い熱伝導シート２４を、接合部材２２上に配置することにより、熱源３０からの熱が空気層に伝わることを抑制できるので、熱電変換層１６の冷却側の加熱を防止して、冷却側を十分に冷却できる。これにより、熱電変換層１６における加熱側と冷却側との温度差が小さくなるのを抑制して、熱電変換層１６の加熱側と冷却側との温度差を確保して、発電量の向上を図ることができる。 By arranging the heat conduction sheet 24 whose thermal conductivity in the surface direction is higher than the thermal conductivity in the thickness direction on the bonding member 22, the heat from the heat source 30 can be suppressed from being transmitted to the air layer, so Heating on the cooling side of the layer 16 can be prevented, and the cooling side can be sufficiently cooled. Thereby, the temperature difference between the heating side and the cooling side in the thermoelectric conversion layer 16 is suppressed from being reduced, the temperature difference between the heating side and the cooling side of the thermoelectric conversion layer 16 is secured, and the power generation amount is improved. Can be
さらに、熱伝導シート２４に凹部２４ａを形成し、凹部２４ａに接合部材２２を嵌合する構成とすることで、熱伝導シート２４と接合部材２２との面方向の熱伝導により熱源３０からの熱を接合部材２２に伝えることができるため、熱源３０からの熱が空気層に伝わることを抑制しつつ、接合部材２２（第１高熱伝導部１２ｂ）へ熱を好適に伝えることができる。これにより、熱電変換層１６における加熱側はより高い温度に、冷却側は、より低い温度にすることができ、加熱側と冷却側との温度差をより高くできる。 Furthermore, by forming the recess 24 a in the heat conduction sheet 24 and fitting the bonding member 22 to the recess 24 a, the heat conduction from the heat source 30 is caused by the thermal conduction of the heat conduction sheet 24 and the bonding member 22 in the plane direction. Can be transmitted to the bonding member 22. Therefore, the heat can be suitably transferred to the bonding member 22 (the first high heat conducting portion 12b) while suppressing the heat from the heat source 30 from being transferred to the air layer. Thereby, the heating side in the thermoelectric conversion layer 16 can be set to a higher temperature, and the cooling side can be set to a lower temperature, and the temperature difference between the heating side and the cooling side can be further increased.
熱伝導シート２４としては、面方向の熱伝導率が、厚み方向の熱伝導率よりも高いものであれば限定はないが、例えば、グラファイトシート、炭素繊維やグラファイトを分散し、水平配向したシート等を用いることができる。 The heat conductive sheet 24 is not particularly limited as long as the thermal conductivity in the surface direction is higher than the thermal conductivity in the thickness direction, but for example, a sheet in which a graphite sheet, carbon fibers and graphite are dispersed and horizontally oriented Etc. can be used.
また、熱伝導シート２４の厚みは、接合部材２２への熱伝導、空気層への熱伝導の抑制等の観点から、１０μｍ以上が好ましく、１００μｍ以上がより好ましい。 The thickness of the heat conduction sheet 24 is preferably 10 μm or more, and more preferably 100 μm or more, from the viewpoints of heat conduction to the bonding member 22 and suppression of heat conduction to the air layer.
また、本発明の熱電変換素子は、上述した構成に限定はされず、第１基板１２が、低熱伝導部１２ａよりも熱伝導率の高い第３高熱伝導部１２ｃを有していてもよい。
図４は、第３高熱伝導部１２ｃを有する熱電変換素子の一例を示す概略斜視図である。
図４に示す熱電変換素子５２は、第１基板１２が第３高熱伝導部１２ｃを有する以外は、前述の図１（Ａ）および図１（Ｂ）に示す熱電変換素子１０と、同様の構成を有するので同じ部材には同じ符号を付し、以下の説明は、異なる部位を主に行う。
Moreover, the thermoelectric conversion element of the present invention is not limited to the above-described configuration, and the first substrate 12 may have the third high thermal conductive portion 12 c having a thermal conductivity higher than that of the low thermal conductive portion 12 a.
FIG. 4: is a schematic perspective view which shows an example of the thermoelectric conversion element which has the 3rd high heat conduction part 12c.
The thermoelectric conversion element 52 shown in FIG. 4 has the same configuration as the thermoelectric conversion element 10 shown in FIG. 1 (A) and FIG. 1 (B) described above, except that the first substrate 12 has the third high thermal conductivity portion 12c. Therefore, the same members are denoted by the same reference numerals, and the following description will mainly refer to different portions.
図４に示す熱電変換素子５２は、第１基板１２が、面方向に第１高熱伝導部１２ｂと離間し、かつ、面方向に少なくとも一部が熱電変換層１６および第２高熱伝導部２０ｂと重複する第３高熱伝導部１２ｃを有する。
この第３高熱伝導部１２ｃの厚みは、第１高熱伝導部１２ｂと接合部材２２との合計厚みよりも薄い。
In the thermoelectric conversion element 52 shown in FIG. 4, the first substrate 12 is separated from the first high thermal conductivity portion 12 b in the surface direction, and at least a part of the thermoelectric conversion layer 16 and the second high thermal conductivity portion 20 b in the surface direction It has the 3rd high heat conduction part 12c which overlaps.
The thickness of the third high thermal conductivity portion 12 c is thinner than the total thickness of the first high thermal conductivity portion 12 b and the bonding member 22.
このような第３高熱伝導部１２ｃを有することで、熱源と基板との間の空気層を介して伝熱された熱等、熱電変換層１６の冷却側を加熱する不要な熱を、第３高熱伝導部１２ｃから放熱できる。その結果、自然放冷下であっても、不要な吸熱による熱電変換層１６の冷却側の加熱を防止して、冷却側を充分に冷却でき、熱電変換層１６の加熱側と冷却側との温度差を確保して、発電量の向上を図ることができる。 By having such a third high thermal conductivity portion 12 c, unnecessary heat for heating the cooling side of the thermoelectric conversion layer 16, such as heat transferred via the air layer between the heat source and the substrate, can be Heat can be dissipated from the high thermal conductivity portion 12c. As a result, even under natural cooling, heating on the cooling side of the thermoelectric conversion layer 16 due to unnecessary heat absorption can be prevented, and the cooling side can be sufficiently cooled, and the heating side and the cooling side of the thermoelectric conversion layer 16 The temperature difference can be secured to improve the amount of power generation.
第３高熱伝導部１２ｃの厚さは、第１高熱伝導部１２ｂと接合部材２２との合計厚みよりも薄ければ、限定は無い。
ここで、良好な放熱効果が得られる第３高熱伝導部１２ｃの好適な厚さは、例えば低熱伝導部１２ａや電極２６などの周辺部材の熱抵抗、熱電変換素子（熱電変換モジュール）の大きさ等によって、大きく異なる。従って、第３高熱伝導部１２ｃの厚さは、周辺部材の熱抵抗や熱電変換素子の大きさ等に応じて、適宜、決定すればよい。
本発明者らの検討によれば、第３高熱伝導部１２ｃの厚さは、第１高熱伝導部１２ｂの厚さ以下が好ましく、第１高熱伝導部１２ｂの１／２以下がより好ましい。第３高熱伝導部１２ｃの厚さを、第１高熱伝導部１２ｂの厚さ以下とすることにより、自然放冷下であっても、熱電変換層１６の冷却側の加熱を好適に防止し、熱電変換層１６の加熱側と冷却側との温度差を確保して、発電量の向上を図ることができる。
また、第３高熱伝導部１２ｃの厚さは、１０μｍ以上が好ましく、３０μｍ以上がより好ましい。第３高熱伝導部１２ｃが薄すぎると、充分な放熱効果が得られない場合が有るが、５μｍ以上とすることにより、自然放冷下であっても、熱電変換層１６の冷却側の加熱を好適に防止し、熱電変換層１６の加熱側と冷却側との温度差を確保して、発電量の向上を図ることができる。
The thickness of the third highly heat conductive portion 12 c is not limited as long as it is thinner than the total thickness of the first highly heat conductive portion 12 b and the bonding member 22.
Here, the preferable thickness of the third high thermal conductivity portion 12c that can obtain a good heat dissipation effect is, for example, the thermal resistance of peripheral members such as the low thermal conductivity portion 12a and the electrode 26, the size of the thermoelectric conversion element (thermoelectric conversion module) It differs greatly depending on etc. Therefore, the thickness of the third high thermal conductivity portion 12c may be determined as appropriate according to the thermal resistance of the peripheral member, the size of the thermoelectric conversion element, and the like.
According to the study of the present inventors, the thickness of the third high thermal conductivity portion 12c is preferably equal to or less than the thickness of the first high thermal conductivity portion 12b, and more preferably 1/2 or less of the first high thermal conductivity portion 12b. By setting the thickness of the third high thermal conductivity portion 12c to be equal to or less than the thickness of the first high thermal conductivity portion 12b, heating on the cooling side of the thermoelectric conversion layer 16 is suitably prevented even under natural cooling. The temperature difference between the heating side and the cooling side of the thermoelectric conversion layer 16 can be secured to improve the amount of power generation.
Moreover, 10 micrometers or more are preferable and, as for the thickness of the 3rd highly heat-conductive part 12c, 30 micrometers or more are more preferable. If the third high thermal conductivity portion 12c is too thin, sufficient heat dissipation effect may not be obtained, but by setting the thickness to 5 μm or more, heating on the cooling side of the thermoelectric conversion layer 16 is possible even under natural cooling. This can be suitably prevented, and the temperature difference between the heating side and the cooling side of the thermoelectric conversion layer 16 can be secured to improve the amount of power generation.
なお、本発明において、第３高熱伝導部１２ｃが第１高熱伝導部１２ｂおよび接合部材２２の合計厚みよりも薄いとは、接合部材２２の第１高熱伝導部１２ｂと逆側の表面よりも、第３高熱伝導部１２ｃの熱電変換層１６と逆側の表面が、熱電変換層１６側に位置する、という意味でもある。
本発明の熱電変換素子は、基本的に、接合部材２２側を熱源３０側にして使用される。従って、第３高熱伝導部１２ｃが第１高熱伝導部１２ｂおよび接合部材２２の合計厚みよりも薄いとは、使用状態において、接合部材２２の熱源３０側の表面よりも、第３高熱伝導部１２ｃの熱源３０側の表面が、熱源３０から離間していることを意味する。
In the present invention, the fact that the third high thermal conductivity portion 12c is thinner than the total thickness of the first high thermal conductivity portion 12b and the joining member 22 means that the surface of the joining member 22 opposite to the first high thermal conductivity portion 12b is It also means that the surface opposite to the thermoelectric conversion layer 16 of the third high thermal conductivity portion 12 c is located on the side of the thermoelectric conversion layer 16.
The thermoelectric conversion element of the present invention is basically used with the bonding member 22 side being the heat source 30 side. Therefore, the third high thermal conductivity part 12c being thinner than the total thickness of the first high thermal conductivity part 12b and the joining member 22 means that the third high thermal conduction part 12c is more in use than the surface of the joining member 22 on the heat source 30 side. It means that the surface of the heat source 30 side of is separated from the heat source 30.
第３高熱伝導部１２ｃは、低熱伝導部１２ａよりも熱伝導率が高いものであれば、各種の材料からなるものが利用可能である。
第３高熱伝導部１２ｃの形成材料としては、具体的には、熱伝導率等の点で、金属が好ましく、金、銀、銅、アルミニウム等の各種の金属は好適に例示される。中でも、熱伝導率、経済性等の点で、銅やアルミニウムは好適に利用される。また、可撓性を有する熱電変換素子（熱電変換モジュール）を得られる等の点で、第３高熱伝導部１２ｃには、金属製のシート（金属箔も含む）も、好適に利用される。
As the third high thermal conductivity portion 12c, various materials can be used as long as the thermal conductivity is higher than that of the low thermal conductivity portion 12a.
Specifically, the material for forming the third high thermal conductivity portion 12c is preferably a metal in terms of thermal conductivity and the like, and various metals such as gold, silver, copper and aluminum are suitably exemplified. Among them, copper and aluminum are suitably used in terms of thermal conductivity, economy and the like. In addition, a metal sheet (including a metal foil) is also suitably used for the third high thermal conductivity portion 12c in that a flexible thermoelectric conversion element (thermoelectric conversion module) can be obtained.
図４に示す熱電変換素子５２において、第３高熱伝導部１２ｃは、第２高熱伝導部２０ｂと同じ矩形状の平面形状を有し、面方向において第２高熱伝導部２０ｂと完全に重複して設けられる。なお、本発明において、平面形状とは、面方向と直交する方向から見た際の形状である。
しかしながら、本発明は、これに限定はされず、第３高熱伝導部１２ｃは、面方向に第１高熱伝導部１２ｂと離間し、しかも、面方向で熱電変換層１６および第２高熱伝導部２０ｂと少なくとも一部が重複していれば、各種の形状および大きさのものが利用可能であり、また、面方向の配置位置も、各種の位置が利用可能である。
すなわち、第３高熱伝導部１２ｃは、面方向に第１高熱伝導部１２ｂと離間し、しかも、面方向で熱電変換層１６および第２高熱伝導部２０ｂと少なくとも一部が重複していれば、好適に、熱電変換層１６の冷却側の加熱を好適に防止できる。
In the thermoelectric conversion element 52 shown in FIG. 4, the third high thermal conductivity part 12 c has the same rectangular planar shape as the second high thermal conductivity part 20 b, and completely overlaps the second high thermal conductivity part 20 b in the surface direction Provided. In the present invention, the planar shape is a shape when viewed from the direction orthogonal to the surface direction.
However, the present invention is not limited to this, and the third high thermal conductivity portion 12c is separated from the first high thermal conductivity portion 12b in the surface direction, and further, the thermoelectric conversion layer 16 and the second high thermal conductivity portion 20b in the surface direction. And at least a part of them, various shapes and sizes can be used, and various positions in the surface direction can also be used.
That is, if the third high thermal conductivity portion 12c is separated from the first high thermal conductivity portion 12b in the surface direction and at least a part thereof overlaps with the thermoelectric conversion layer 16 and the second high thermal conductivity portion 20b in the surface direction, Preferably, heating on the cooling side of the thermoelectric conversion layer 16 can be suitably prevented.
ここで、前述の第３高熱伝導部１２ｃの厚さと同様、良好な放熱効果が得られる第３高熱伝導部１２ｃの好適な位置、サイズおよび形状等は、例えば低熱伝導部１２ａや電極２６などの周辺部材の熱抵抗、熱電変換素子（熱電変換モジュール）の大きさ等によって、大きく異なる。
従って、第３高熱伝導部１２ｃの位置、サイズおよび形状等は、周辺部材の熱抵抗や熱電変換素子のサイズ等に応じて、熱電変換層１６の冷却側の加熱を好適に防止できる構成を、適宜、決定すればよい。
Here, as with the thickness of the third high thermal conductivity portion 12c described above, the preferable position, size, shape and the like of the third high thermal conductivity portion 12c from which a good heat dissipation effect can be obtained are, for example, the low thermal conductivity portion 12a and the electrode 26. It largely differs depending on the thermal resistance of the peripheral members, the size of the thermoelectric conversion element (thermoelectric conversion module), etc.
Therefore, according to the position, size and shape of the third high thermal conductivity part 12c, the heating side on the cooling side of the thermoelectric conversion layer 16 can be suitably prevented depending on the thermal resistance of the peripheral members, the size of the thermoelectric conversion element, etc. It may be determined as appropriate.
また、本発明の熱電変換素子においては、第３高熱伝導部の冷却を行うのが好ましい。第３高熱伝導部を冷却することにより、第３高熱伝導部からの放熱を、より効率よく行い、自然空冷下であっても、熱電変換層１６における加熱側と冷却側との温度差を保ち、大きな発電量を得ることができる。
第３高熱伝導部の冷却は、公知の各種の方法が利用可能である。好ましい方法として、第３高熱伝導部と第２高熱伝導部とを、低熱伝導部および被覆層よりも熱伝導率が高い接続部材で接続する方法が例示される。
Moreover, in the thermoelectric conversion element of the present invention, it is preferable to cool the third high thermal conductivity portion. By cooling the third high thermal conductivity portion, heat dissipation from the third high thermal conductivity portion is performed more efficiently, and even under natural air cooling, the temperature difference between the heating side and the cooling side in the thermoelectric conversion layer 16 is maintained , A large amount of power can be obtained.
Various known methods can be used to cool the third high thermal conductivity portion. As a preferable method, a method of connecting the third high thermal conductivity portion and the second high thermal conductivity portion by a connection member having a thermal conductivity higher than that of the low thermal conductivity portion and the covering layer is exemplified.
本発明の熱電変換素子において、被覆層は、粘着層１８および第２基板２０を構成する低熱伝導部２０ａによって形成される構成に限定はされない。
例えば、被覆層を粘着層１８のみで構成して、粘着層１８の上に、第２高熱伝導部２０ｂを面方向の同位置に貼着した構成も利用可能である。この構成においては、必要に応じて、粘着層１８の第２高熱伝導部２０ｂで覆われない部分には、樹脂フィルム等を貼着してもよい。
In the thermoelectric conversion element of the present invention, the coating layer is not limited to the configuration formed by the low thermal conductivity portion 20 a constituting the adhesive layer 18 and the second substrate 20.
For example, a configuration in which the covering layer is configured only with the adhesive layer 18 and the second high thermal conductivity portion 20b is attached to the same position in the surface direction on the adhesive layer 18 can also be used. In this configuration, if necessary, a resin film or the like may be attached to a portion of the adhesive layer 18 which is not covered by the second high thermal conductivity portion 20b.
別の例として、図５に概念的に示す熱電変換素子４０のように、第２基板２０に変えて、貫通しない溝部４２ａを有する金属シート４２を用いる構成が例示される。
なお、図５に示す熱電変換素子は、前述の図４に示す熱電変換素子１０と、多くの部材を共用するので、同じ部材には同じ符号を付し、以下の説明は、異なる部位を主に行う。
As another example, a configuration using a metal sheet 42 having a groove portion 42 a which does not penetrate is shown instead of the second substrate 20 as in the thermoelectric conversion element 40 conceptually shown in FIG. 5.
In addition, since the thermoelectric conversion element shown in FIG. 5 shares many members with the thermoelectric conversion element 10 shown in FIG. 4 described above, the same reference numerals are given to the same members, and in the following description, different portions are mainly To do.
この金属シート４２を用いる熱電変換素子４０では、溝部４２ａの少なくとも一部が面方向で第１基板１２の第１高熱伝導部１２ｂと重複するように、溝部を粘着層１８に向けて、金属シート４２を粘着層１８に貼着する。従って、図５に示す例のように、面方向において、溝部４２ａが第１高熱伝導部１２ｂを完全に包含してもよい。
この熱電変換素子４０では、粘着層１８が、本発明における被覆層である。また、粘着層１８は、金属シート４２と熱電変換層１６、電極２６および電極２８とを絶縁する絶縁層としても作用する。
この構成においても、必要に応じて、粘着層１８の金属シート４２で覆われない部分には、樹脂フィルム等を貼着してもよい。
In the thermoelectric conversion element 40 using the metal sheet 42, the groove is directed to the adhesive layer 18 so that at least a part of the groove 42a overlaps with the first high thermal conductivity portion 12b of the first substrate 12 in the surface direction. 42 is attached to the adhesive layer 18. Therefore, as in the example shown in FIG. 5, the groove 42 a may completely include the first high heat conduction portion 12 b in the plane direction.
In the thermoelectric conversion element 40, the adhesive layer 18 is a covering layer in the present invention. The adhesive layer 18 also functions as an insulating layer which insulates the metal sheet 42 from the thermoelectric conversion layer 16, the electrode 26 and the electrode 28.
Also in this configuration, if necessary, a resin film or the like may be attached to the portion of the adhesive layer 18 which is not covered by the metal sheet 42.
このような構成を有する熱電変換素子４０では、金属シート４２と粘着層１８との間には、溝部４２ａに起因する空間が形成される。
金属と空間とでは、熱伝導率は、空間の方が遥かに小さい。また、溝部４２ａは、少なくとも一部が面方向で第１高熱伝導部１２ｂと重複する。
従って、熱電変換素子４０では、金属シート４２の粘着層１８に貼着されている領域が、第２基板２０の第２高熱伝導部２０ｂと同様の第２高熱伝導部として作用し、溝部４２ａによる空間が、低熱伝導部すなわち第２基板２０の第２高熱伝導部２０ｂを有さない領域と同様に作用する。
そのため、同様に、第１基板１２側に熱源３０を設けると、第１高熱伝導部１２ｂから熱電変換層１６に至り、熱電変換層１６を図中右から左へ面方向に移動して、粘着層１８との接触面から金属シート４２に到る熱の流れが生じる。これにより、熱電変換素子４０においても、熱電変換層１６の面方向の長い距離の温度差によって、効率の良い発電が可能である。
In the thermoelectric conversion element 40 having such a configuration, a space resulting from the groove 42 a is formed between the metal sheet 42 and the adhesive layer 18.
With metals and space, the thermal conductivity is much smaller in space. Further, at least a portion of the groove portion 42a overlaps the first high heat conduction portion 12b in the surface direction.
Therefore, in the thermoelectric conversion element 40, the area of the metal sheet 42 attached to the adhesive layer 18 acts as a second high thermal conductivity portion similar to the second high thermal conductivity portion 20b of the second substrate 20, and is formed by the groove 42a. The space acts in the same manner as the low thermal conductivity portion, that is, the region not having the second high thermal conductivity portion 20 b of the second substrate 20.
Therefore, similarly, when the heat source 30 is provided on the first substrate 12 side, it reaches the thermoelectric conversion layer 16 from the first high thermal conductivity portion 12b, and moves the thermoelectric conversion layer 16 in the surface direction from the right to the left in the figure, A heat flow is generated from the contact surface with the layer 18 to the metal sheet 42. Thereby, also in the thermoelectric conversion element 40, efficient electric power generation is possible by the temperature difference of the long distance of the surface direction of the thermoelectric conversion layer 16.
なお、金属シート４２の形成材料は、各種の金属材料が全て利用可能である。
具体的には、銅、アルミニウム、シリコン、ニッケル等の金属や、銅合金、ステンレス、ニッケル合金等の合金が好適に例示される。
In addition, as a forming material of the metal sheet 42, all of various metal materials can be used.
Specifically, metals such as copper, aluminum, silicon and nickel, and alloys such as copper alloy, stainless steel and nickel alloy are preferably exemplified.
本発明の熱電変換素子において、大きな発電量を得るためには、第２高熱伝導部からの放熱が大きい方が好ましい。これに応じて、本発明の熱電変換素子においては、第２高熱伝導部の熱抵抗を、第１高熱伝導部の熱抵抗よりも小さくするのが好ましい。
この一例を、図６に示す。
In the thermoelectric conversion element of the present invention, in order to obtain a large amount of power generation, it is preferable that the heat radiation from the second high thermal conductivity part be large. Accordingly, in the thermoelectric conversion element of the present invention, it is preferable to make the thermal resistance of the second high thermal conductivity portion smaller than the thermal resistance of the first high thermal conductivity portion.
An example of this is shown in FIG.
図１（Ａ）および図１（Ｂ）に示す熱電変換素子１０においては、第１基板１２の第１高熱伝導部１２ｂと第２基板２０の第２高熱伝導部２０ｂとは、全く同じものである。従って、第２高熱伝導部２０ｂと第１高熱伝導部１２ｂとの熱抵抗は同じである。
これに対し、図６に示す熱電変換素子４６は、第１基板１２において、第１高熱伝導部１２ｂの離間方向の長さを短くして、第２高熱伝導部２０ｂの断面積を第１高熱伝導部１２ｂの断面積よりも大きくしている。そのため、第１高熱伝導部１２ｂよりも第２高熱伝導部２０ｂの方が熱が流れ易くなり、第２高熱伝導部２０ｂの熱抵抗が、第１高熱伝導部１２ｂの熱抵抗よりも小さくなる。この際における断面積とは、面方向の断面の断面積である。
これにより、熱源３０から第１高熱伝導部１２ｂを経て熱電変換層１６に到る熱量よりも、第２高熱伝導部２０ｂからの放熱量を大きくして、自然空冷下であっても、熱電変換層１６における加熱側と冷却側との温度差を保ち、大きな発電量を得ることができる。
In the thermoelectric conversion element 10 shown in FIGS. 1 (A) and 1 (B), the first high thermal conductivity portion 12 b of the first substrate 12 and the second high thermal conductivity portion 20 b of the second substrate 20 are completely the same. is there. Accordingly, the thermal resistances of the second high thermal conductivity portion 20b and the first high thermal conductivity portion 12b are the same.
On the other hand, in the thermoelectric conversion element 46 shown in FIG. 6, the length of the first high thermal conductivity portion 12b in the separation direction is shortened in the first substrate 12, and the cross-sectional area of the second high thermal conductivity portion 20b is It is made larger than the cross-sectional area of the conduction part 12b. Therefore, heat flows more easily in the second high thermal conductivity portion 20b than in the first high thermal conductivity portion 12b, and the thermal resistance of the second high thermal conductivity portion 20b becomes smaller than the thermal resistance of the first high thermal conductivity portion 12b. The cross-sectional area in this case is the cross-sectional area of the cross section in the surface direction.
As a result, the amount of heat release from the second high thermal conductivity portion 20b is larger than the amount of heat reaching the thermoelectric conversion layer 16 from the heat source 30 through the first high thermal conductivity portion 12b, and even under natural air cooling A large amount of power generation can be obtained by maintaining the temperature difference between the heating side and the cooling side in the layer 16.
第２高熱伝導部２０ｂの熱抵抗を、第１高熱伝導部１２ｂの熱抵抗よりも小さくする方法は、断面積を調節する方法以外にも、各種の方法が、利用可能である。
すなわち、部材の熱抵抗は、熱の伝導方向と直交する方向の断面積、熱の伝導方向の長さ、および、熱伝導率によって変化する。
これに応じて、第２高熱伝導部２０ｂの熱抵抗を、第１高熱伝導部の熱抵抗よりも小さくする方法は、第２高熱伝導部２０ｂの厚さを第１高熱伝導部１２ｂよりも薄くする方法、第２高熱伝導部２０ｂを第１高熱伝導部１２ｂよりも熱伝導度が高い材料で形成する方法等も利用可能である。また、断面積を調節する方法、厚さを調節する方法、および、形成部材の熱伝導度を選択する方法の、２以上を併用することにより、第２高熱伝導部２０ｂの熱抵抗を、第１高熱伝導部の熱抵抗よりも小さくしてもよい。
As a method of making the thermal resistance of the second high thermal conductivity part 20b smaller than the thermal resistance of the first high thermal conductivity part 12b, various methods can be used other than the method of adjusting the cross-sectional area.
That is, the thermal resistance of the member changes depending on the cross-sectional area in the direction orthogonal to the heat conduction direction, the length of the heat conduction direction, and the thermal conductivity.
According to this, the method of making the thermal resistance of the second high thermal conductive part 20b smaller than the thermal resistance of the first high thermal conductive part makes the thickness of the second high thermal conductive part 20b thinner than the first high thermal conductive part 12b Alternatively, a method of forming the second high thermal conductivity portion 20b with a material having a thermal conductivity higher than that of the first high thermal conductivity portion 12b may be used. Further, the thermal resistance of the second high thermal conductivity portion 20b can be obtained by combining two or more of the method of adjusting the cross-sectional area, the method of adjusting the thickness, and the method of selecting the thermal conductivity of the forming member. It may be smaller than the thermal resistance of the high thermal conductivity part.
また、図７に示す熱電変換素子５４のように、第２基板２０に変えて、貫通しない溝部４２ａを有する金属シート４２を用い、かつ、第２高熱伝導部２０ｂの断面積を第１高熱伝導部１２ｂの断面積よりも大きくして、第２高熱伝導部２０ｂの熱抵抗を第１高熱伝導部１２ｂの熱抵抗よりも小さくした構成としてもよい。 Also, as in the thermoelectric conversion element 54 shown in FIG. 7, instead of the second substrate 20, a metal sheet 42 having grooves 42a that do not penetrate is used, and the cross-sectional area of the second high thermal conductivity portion 20b is a first high thermal conductivity The thermal resistance of the second high thermal conductivity portion 20b may be smaller than the thermal resistance of the first high thermal conductivity portion 12b by making the cross sectional area of the portion 12b larger.
次に、本発明の熱電変換素子を複数用いる熱電変換モジュールについて説明する。
図８（Ａ）〜図８（Ｅ）は、本発明の熱電変換素子１０を、複数、直列に接続してなる、熱電変換モジュールの一例を概念的に示す図である。なお、図８（Ａ）および図８（Ｅ）は正面図、図８（Ｂ）〜図８（Ｄ）は平面図である。
本例において、第１基板１２Ａおよび第２基板２０Ａはそれぞれ、矩形板状の低熱伝導材料の表面に、一方向に長尺な四角柱状の第１高熱伝導部１２ｂおよび第２高熱伝導部２０ｂそれぞれを、四角柱の低熱伝導部に接触する一辺の長さと等間隔で、四角柱の長手方向と直交する方向に配列してなる構成を有する。
すなわち、第１基板１２Ａおよび第２基板２０Ａは、一面の表面の全面が低熱伝導部で、他面の表面が、一方向に延在する低熱伝導部と高熱伝導部とが、延在方向と直交する方向に等間隔で交互に形成された構成を有する（図８（Ａ）、図８（Ｃ）および図８（Ｄ）参照）。
Next, a thermoelectric conversion module using a plurality of thermoelectric conversion elements of the present invention will be described.
FIGS. 8 (A) to 8 (E) are diagrams schematically showing an example of a thermoelectric conversion module in which a plurality of thermoelectric conversion elements 10 of the present invention are connected in series. 8 (A) and 8 (E) are front views, and FIGS. 8 (B) to 8 (D) are plan views.
In this example, the first substrate 12A and the second substrate 20A are respectively formed on the surface of a rectangular plate-shaped low thermal conductive material, and each of the first high thermal conductivity portion 12b and the second high thermal conductivity portion 20b has a square pole shape elongated in one direction. Are arranged in the direction orthogonal to the longitudinal direction of the quadrangular prism at equal intervals to the length of one side contacting the low thermal conductivity portion of the quadrangular prism.
That is, in the first substrate 12A and the second substrate 20A, the entire surface of one surface is a low thermal conductivity portion, and the surface of the other surface is a low thermal conductivity portion and a high thermal conductivity portion extending in one direction. It has a configuration formed alternately at equal intervals in the orthogonal direction (see FIGS. 8A, 8C, and 8D).
また、図８（Ｅ）に示すように、第１高熱伝導部１２ｂの低熱伝導部とは反対側の面には、長尺な四角柱状の接合部材２２が配置されている。図に示すように、面方向において、接合部材２２は第１高熱伝導部１２ｂと同様の大きさ、形状を有し、第１高熱伝導部１２ｂ上に配置される。 Further, as shown in FIG. 8E, on the surface of the first high thermal conductivity portion 12b opposite to the low thermal conductivity portion, a long square columnar joining member 22 is disposed. As shown in the figure, in the plane direction, the bonding member 22 has the same size and shape as the first high heat conduction portion 12b, and is disposed on the first high heat conduction portion 12b.
図８（Ｄ）および図８（Ｅ）に示すように、第１基板１２Ａには、第１高熱伝導部１２ｂの間に、第１高熱伝導部１２ｂと同方向に長尺な第３高熱伝導部１２ｃが形成される。また、前述のように、第３高熱伝導部１２ｃは、第１高熱伝導部１２ｂおよび接合部材２２の合計厚みよりも薄い。
また、図示は省略するが、第３高熱伝導部１２ｃと第２基板２０Ａの第２高熱伝導部２０ｂとは、低熱伝導部および被覆層よりも熱伝導率が高い接続部材で接続されている。
As shown in FIGS. 8 (D) and 8 (E), in the first substrate 12A, between the first high thermal conductivity portions 12b, a third high thermal conductivity long in the same direction as the first high thermal conductivity portions 12b. The portion 12c is formed. Further, as described above, the third high thermal conductivity portion 12 c is thinner than the total thickness of the first high thermal conductivity portion 12 b and the bonding member 22.
Although not shown, the third high thermal conductivity portion 12c and the second high thermal conductivity portion 20b of the second substrate 20A are connected by a connecting member having a thermal conductivity higher than that of the low thermal conductivity portion and the covering layer.
図８（Ｃ）に示すように、熱電変換層１６は矩形の面形状を有し、第１基板１２Ａの全面が低熱伝導部１２ａである側の表面に、低熱伝導部１２ａと第１高熱伝導部１２ｂとの境界と中心とを面方向で一致させて形成される。
熱電変換層１６の図８（Ｃ）の横方向の大きさは、第１高熱伝導部１２ｂの幅に対して０．５倍から２．０倍未満の間に設定される。以下、図８（Ｃ）の横方向を単に『横方向』とも言う。すなわち、横方向とは、低熱伝導部１２ａと第１高熱伝導部１２ｂとの交互の配列方向である。また、第１高熱伝導部１２ｂと熱電変換層１６は、面方向に少なくとも一部が重複するように形成される。
熱電変換層１６は、横方向に、低熱伝導部１２ａと第１高熱伝導部１２ｂとの境界に対して、１境界置きに等間隔で形成される。すなわち、熱電変換層１６は、横方向の中心が、第１高熱伝導部１２ｂの幅の２倍の距離と同じ間隔で等間隔に形成される。
また、熱電変換層１６は、横方向に等間隔に配列された熱電変換層１６の列が、図８（Ｃ）の上下方向に等間隔で配列されるように、二次元的に形成される。以下、図８（Ｃ）の上下方向を単に『上下方向』とも言う。すなわち、上下方向とは、低熱伝導部１２ａと第１高熱伝導部１２ｂの延在方向である。
さらに、図８（Ｃ）に示すように、熱電変換層１６の横方向の配列は、上下方向に隣接する列では、第１高熱伝導部１２ｂの幅の分だけ、横方向にズレて形成される。すなわち、上下方向に隣接する列では、熱電変換層１６は、横方向の中心が、第１高熱伝導部１２ｂの幅の分だけ、互い違いに形成される。
As shown in FIG. 8C, the thermoelectric conversion layer 16 has a rectangular surface shape, and the low thermal conductivity portion 12a and the first high thermal conductivity are provided on the surface on the side where the entire surface of the first substrate 12A is the low thermal conductivity portion 12a. The boundary with the portion 12b and the center are formed to coincide in the plane direction.
The lateral size of the thermoelectric conversion layer 16 in FIG. 8C is set to 0.5 times to less than 2.0 times the width of the first high thermal conductivity portion 12b. Hereinafter, the horizontal direction in FIG. 8C is also referred to simply as the “horizontal direction”. That is, the lateral direction is an alternate arrangement direction of the low thermal conductivity portions 12a and the first high thermal conductivity portions 12b. In addition, the first high thermal conductivity portion 12 b and the thermoelectric conversion layer 16 are formed so that at least a part thereof overlaps in the surface direction.
The thermoelectric conversion layer 16 is formed in the lateral direction at equal intervals, with respect to the boundary between the low thermal conductivity portion 12a and the first high thermal conductivity portion 12b. That is, the thermoelectric conversion layers 16 are formed at equal intervals at the same intervals as the distance twice the width of the first high thermal conductivity portion 12 b in the lateral direction.
Further, the thermoelectric conversion layers 16 are two-dimensionally formed so that the rows of the thermoelectric conversion layers 16 arranged at equal intervals in the lateral direction are arranged at equal intervals in the vertical direction of FIG. 8C. . Hereinafter, the vertical direction in FIG. 8C is also referred to simply as “vertical direction”. That is, the vertical direction is the extending direction of the low heat conducting portion 12a and the first high heat conducting portion 12b.
Furthermore, as shown in FIG. 8C, the horizontal arrangement of the thermoelectric conversion layers 16 is formed laterally shifted by the width of the first high thermal conductivity portion 12b in the row adjacent in the vertical direction. Ru. That is, in the rows adjacent in the vertical direction, the thermoelectric conversion layers 16 are alternately formed such that the centers in the lateral direction are equal to the width of the first high thermal conductivity portion 12b.
ここで、本発明においては、第３高熱伝導部１２ｃと熱電変換層１６は、面方向に少なくとも一部が重複するように形成される。 Here, in the present invention, the third high thermal conductivity portion 12 c and the thermoelectric conversion layer 16 are formed so that at least a part thereof overlaps in the surface direction.
各熱電変換層１６は、電極２６（第２電極２８）によって直列に接続される。具体的には、図８（Ｃ）に示すように、図中横方向の熱電変換層１６の配列において、電極２６が、各熱電変換層１６を横方向に挟むように設けられる。これにより、横方向に配列された熱電変換層１６が、電極２６によって直列に接続される。なお、図８（Ｃ）では、構成を明確にするために、電極２６に網掛けをしている。
熱電変換層１６の横方向の列の端部では、上下方向に隣接する列の熱電変換層１６が、電極２６によって接続される。この横方向の列の端部での電極２６による上下方向の熱電変換層１６の接続は、一方の端部の熱電変換層１６は上側の列の同側端部の熱電変換層１６と接続され、他方の端部の熱電変換層１６は下側の列の同側端部の熱電変換層１６と接続される。
これにより、全ての熱電変換層１６が、横方向に、複数回、折り返した１本の線のように直列で接続される。
Each thermoelectric conversion layer 16 is connected in series by the electrode 26 (second electrode 28). Specifically, as shown in FIG. 8C, in the arrangement of the thermoelectric conversion layers 16 in the lateral direction in the drawing, the electrodes 26 are provided so as to sandwich the respective thermoelectric conversion layers 16 in the lateral direction. Thereby, the thermoelectric conversion layers 16 arranged in the lateral direction are connected in series by the electrodes 26. In FIG. 8C, the electrodes 26 are hatched to clarify the configuration.
At the end of the lateral row of the thermoelectric conversion layers 16, the thermoelectric conversion layers 16 of the vertically adjacent rows are connected by the electrodes 26. The connection of the thermoelectric conversion layer 16 in the vertical direction by the electrode 26 at the end of the lateral row is such that the thermoelectric conversion layer 16 at one end is connected to the thermoelectric conversion layer 16 at the same side of the upper row. The thermoelectric conversion layer 16 at the other end is connected to the thermoelectric conversion layer 16 at the same side end of the lower row.
As a result, all the thermoelectric conversion layers 16 are connected in series in the lateral direction, like a single folded wire.
図８（Ｂ）に概念的に示すように、熱電変換層１６および電極２６の上に、第２基板２０Ａの全面が低熱伝導部２０ａである側を下方にして、かつ、第１基板１２Ａの低熱伝導部１２ａと第１高熱伝導部１２ｂとの境界と、第２基板２０Ａの低熱伝導部２０ａと第２高熱伝導部２０ｂとの境界を一致させて、第２基板２０Ａが積層される。
この積層は、第１基板１２Ａの第１高熱伝導部１２ｂと第２基板２０Ａの第２高熱伝導部２０ｂとが、互い違いになるように行われる。
なお、図示はされないが、第２基板２０Ａの積層に先立ち、第１基板１２Ａを全面的に覆うように、熱電変換層１６および電極２６の上に粘着層１８が形成される。
As conceptually shown in FIG. 8B, on the thermoelectric conversion layer 16 and the electrode 26, the entire surface of the second substrate 20A is the low thermal conductive portion 20a with the side of the first substrate 12A facing downward. The second substrate 20A is stacked such that the boundary between the low thermal conductivity portion 12a and the first high thermal conductivity portion 12b coincides with the boundary between the low thermal conductivity portion 20a of the second substrate 20A and the second high thermal conductivity portion 20b.
This lamination is performed so that the first high thermal conductivity portion 12b of the first substrate 12A and the second high thermal conductivity portion 20b of the second substrate 20A are alternately arranged.
Although not shown, an adhesive layer 18 is formed on the thermoelectric conversion layer 16 and the electrode 26 so as to entirely cover the first substrate 12A prior to the lamination of the second substrate 20A.
従って、第１基板１２Ａの第１高熱伝導部１２ｂと、第２基板２０Ａの低熱伝導部のみの領域とが面方向に一致して対面し、かつ、第１基板１２Ａの低熱伝導部１２ａおよび第３高熱伝導部１２ｃが形成された領域と、第２基板２０Ａの第２高熱伝導部２０ｂが形成された領域とが面方向に一致して対面する。また、第１基板１２Ａにおいて第１高熱伝導部１２ｂの間に形成される第３高熱伝導部１２ｃは、面方向に第２高熱伝導部２０ｂと重複する。
これにより、本発明の熱電変換素子１０を、複数、直列に接続してなる、本発明の熱電変換モジュールが構成される。
Therefore, the first high thermal conductivity portion 12b of the first substrate 12A and the region of only the low thermal conductivity portion of the second substrate 20A face each other in the plane direction, and the low thermal conductivity portion 12a of the first substrate 12A and the The region where the third high thermal conductivity portion 12c is formed and the region where the second high thermal conductivity portion 20b of the second substrate 20A is formed face in the same plane direction. In addition, the third high thermal conductivity portion 12c formed between the first high thermal conductivity portions 12b in the first substrate 12A overlaps the second high thermal conductivity portion 20b in the surface direction.
Thereby, a plurality of thermoelectric conversion elements 10 of the present invention are connected in series to constitute a thermoelectric conversion module of the present invention.
ここで、前述のように、熱電変換層１６の横方向の配列は、上下方向に隣接する列では、熱電変換層１６の横方向の中心線が、第１高熱伝導部１２ｂ（すなわち第２高熱伝導部２０ｂ）の幅の分だけ、横方向にズレて形成される。すなわち、上下方向に隣接する列では、熱電変換層１６は、熱電変換層１６の横方向の中心線が、第１高熱伝導部１２ｂの幅の分だけ、互い違いに形成される。
そのため、折り返した１本の線のように直列に接続された熱電変換層１６は、接続方向の一方向の流れにおいて、全ての熱電変換層１６が、一方の半分が第１基板１２Ａの第１高熱伝導部１２ｂと第２基板２０Ａの低熱伝導部２０ａのみの領域とに対面し、他方の半分が第１基板１２Ａの低熱伝導部１２ａのみの領域と第２基板２０Ａの第２高熱伝導部２０ｂとに対面する。
例えば、図８（Ｃ）の上から下への直列の接続方向で見た場合には、図８（Ａ）〜図８（Ｃ）に示すように、全ての熱電変換層１６が、上流側半分が第１基板１２Ａの第１高熱伝導部１２ｂおよび第２基板２０Ａの低熱伝導部２０ａのみの領域に対面し、下流側の半分が第１基板１２Ａの低熱伝導部１２ａのみの領域および第２基板２０Ａの第２高熱伝導部２０ｂに対面する。
従って、第１基板１２Ａ側に熱源を配置した際に、直列に接続された全ての熱電変換層１６で、接続方向に対する熱の流れ方向すなわち発電した電気の流れ方向が一致し、熱電変換モジュールが適正に発電を行うことができる。
Here, as described above, in the arrangement of the thermoelectric conversion layers 16 in the lateral direction, in the vertically adjacent row, the horizontal center line of the thermoelectric conversion layers 16 is the first high heat conduction portion 12 b (that is, the second high heat conduction portion It is formed to be laterally shifted by the width of the conductive portion 20b). That is, in the row adjacent in the vertical direction, in the thermoelectric conversion layer 16, the horizontal center lines of the thermoelectric conversion layer 16 are alternately formed by the width of the first high heat conduction portion 12 b.
Therefore, the thermoelectric conversion layers 16 connected in series as in one folded line have all the thermoelectric conversion layers 16 with one half being the first substrate 12A in one flow in the connection direction. The high thermal conductivity portion 12b and the region of only the low thermal conductivity portion 20a of the second substrate 20A, the other half being the region of the low thermal conductivity portion 12a of the first substrate 12A only and the second high thermal conductivity portion 20b of the second substrate 20A Face with.
For example, when viewed in the series connection direction from top to bottom in FIG. 8C, as shown in FIGS. 8A to 8C, all the thermoelectric conversion layers 16 are on the upstream side. The half faces the region of only the first high thermal conductivity portion 12b of the first substrate 12A and the low thermal conductivity portion 20a of the second substrate 20A, and the downstream half region of the region of only the low thermal conductivity portion 12a of the first substrate 12A and the second It faces the second high thermal conductivity portion 20b of the substrate 20A.
Therefore, when the heat source is disposed on the first substrate 12A side, the flow direction of heat with respect to the connection direction, that is, the flow direction of the generated electricity is the same in all the thermoelectric conversion layers 16 connected in series. It can generate electricity properly.
以下に、図８（Ａ）〜図８（Ｅ）に示す熱電変換モジュールの製造方法の一例を説明する。なお、熱電変換素子は、この熱電変換モジュールの製造方法に準じて製造できる。 Below, an example of the manufacturing method of the thermoelectric conversion module shown to FIG. 8 (A)-FIG.8 (E) is demonstrated. In addition, a thermoelectric conversion element can be manufactured according to the manufacturing method of this thermoelectric conversion module.
まず、低熱伝導部１２ａ、第１高熱伝導部１２ｂ、および、第３高熱伝導部１２ｃを有する第１基板１２Ａ（第１基板１２）、および、低熱伝導部２０ａ、および、第２高熱伝導部２０ｂを有する第２基板２０Ａ（第２基板２０）を用意する。 First, the first substrate 12A (first substrate 12) having the low thermal conductivity portion 12a, the first high thermal conductivity portion 12b, and the third high thermal conductivity portion 12c, and the low thermal conductivity portion 20a, and the second high thermal conductivity portion 20b A second substrate 20A (second substrate 20) is prepared.
第１基板１２Ａおよび第２基板２０Ａは、フォトリソグラフィー、エッチング、真空蒸着、スパッタリング、印刷技術等を利用して、公知の方法で作製すればよい。
例えば、ポリイミドの両面に銅が積層された銅張ポリイミドフィルムを用意する。この銅張ポリイミドフィルムは、市販品も利用可能である。
この銅張ポリイミドフィルム一面を全てエッチングし、もう一方の面を目的とする高熱伝導部等のパターンとなるようにエッチング（ハーフエッチング）して不要な銅を除去することにより作製することができる。また、低熱伝導部となるシート状物を用意し、このシート状物に、帯状の高熱伝導部を長手方向と直交する方向に貼着し、さらに、高熱伝導部の形成領域外に所定形状の接続部材を貼着して、第１基板１２Ａおよび第２基板２０Ａを作製する方法も利用可能である。
The first substrate 12A and the second substrate 20A may be manufactured by a known method using photolithography, etching, vacuum evaporation, sputtering, a printing technique or the like.
For example, a copper-clad polyimide film in which copper is laminated on both sides of polyimide is prepared. Commercial products of this copper-clad polyimide film are also available.
The entire surface of the copper-clad polyimide film is etched, and the other surface is etched (half-etched) so as to form a pattern of a high thermal conductivity portion or the like to remove unnecessary copper. In addition, a sheet-like material to be a low thermal conductivity part is prepared, and a band-like high thermal conductivity part is attached to the sheet material in a direction orthogonal to the longitudinal direction, and a predetermined shape is formed outside the formation region of the high thermal conductivity part. A method of producing the first substrate 12A and the second substrate 20A by pasting the connecting member is also available.
次いで、第１基板１２Ａの全面が低熱伝導部１２ａである面の熱電変換層１６に対応する位置に、熱電変換層１６を面方向で挟むように、電極２６および電極２８を形成する。
電極２６および電極２８の形成は、メタルマスクを用いる真空蒸着法など、電極２６および電極２８の形成材料等に応じて、公知の方法で行えばよい。
また、電極２６および電極２８の形成に先立ち、電極の形成面にクロム層などの密着層を形成してもよい。
Next, the electrode 26 and the electrode 28 are formed at positions corresponding to the thermoelectric conversion layer 16 on the surface of the first substrate 12A that is the low thermal conductivity portion 12a so as to sandwich the thermoelectric conversion layer 16 in the surface direction.
The formation of the electrode 26 and the electrode 28 may be performed by a known method depending on the formation material of the electrode 26 and the electrode 28 or the like, such as a vacuum evaporation method using a metal mask.
Further, prior to the formation of the electrode 26 and the electrode 28, an adhesion layer such as a chromium layer may be formed on the formation surface of the electrode.
次いで、第１基板１２Ａの全面が低熱伝導部１２ａである面の目的とする位置に、熱電変換層１６を形成する。なお、図示例の熱電変換素子１０においては、熱電変換層１６が、電極２６および電極２８の端部を覆うように形成する。
熱電変換層１６は、用いる熱電変換材料に応じて、公知の方法で形成すればよい。
例えば、熱電変換材料とバインダとを有する塗布組成物を調製して、この塗布組成物をスクリーン印刷やインクジェット等の公知の方法でパターンニングして塗布して、乾燥し、バインダを硬化することにより、バインダに熱電変換材料を分散してなる熱電変換材料を形成する方法が例示される。
また、熱電変換材料としてＣＮＴを用いる場合には、分散剤（界面活性剤）を用いてＣＮＴを水に分散してなる塗布組成物を調製して、この塗布組成物を同様に公知の方法でパターンニングして塗布して、乾燥することにより、主にＣＮＴと界面活性剤とから熱電変換層を形成する方法が例示される。この際においては、塗布組成物を乾燥した後、アルコール等の分散剤を溶解する洗浄剤で熱電変換層を洗浄することで分散剤を除去し、その後、洗浄剤を乾燥することにより、実質的にＣＮＴのみからなる熱電変換層とするのが好ましい。洗浄は、熱電変換層を洗浄剤に浸漬する方法や、熱電変換層を洗浄剤で濯ぐ方法等で行えばよい。
また、熱電変換材料として無機材料を用いる場合には、真空蒸着やスパッタリング等の気相成膜法によって、メタルマスク等を用いる公知の方法で、熱電変換層をパターン形成する方法が例示される。
あるいは、第１基板１２の全面に熱電変換層を形成して、エッチング等によって、熱電変換層１６をパターン形成してもよい。
Next, the thermoelectric conversion layer 16 is formed at a target position of the surface of the first substrate 12A which is the low thermal conductivity portion 12a. In the illustrated example of the thermoelectric conversion element 10, the thermoelectric conversion layer 16 is formed to cover the end portions of the electrode 26 and the electrode 28.
The thermoelectric conversion layer 16 may be formed by a known method according to the thermoelectric conversion material to be used.
For example, a coating composition having a thermoelectric conversion material and a binder is prepared, and the coating composition is patterned and applied by a known method such as screen printing or inkjet, and then dried and cured. The method of forming the thermoelectric conversion material which disperse | distributes a thermoelectric conversion material to a binder is illustrated.
Moreover, when using CNT as a thermoelectric conversion material, a coating composition comprising CNTs dispersed in water is prepared using a dispersing agent (surfactant), and this coating composition is similarly prepared by a known method. The method of forming the thermoelectric conversion layer mainly from CNT and surfactant by patterning, apply | coating, and drying is illustrated. In this case, after drying the coating composition, the dispersant is removed by washing the thermoelectric conversion layer with a detergent that dissolves a dispersant such as alcohol, and then the detergent is substantially dried. It is preferable to use a thermoelectric conversion layer consisting of only CNTs. Cleaning may be performed by a method of immersing the thermoelectric conversion layer in a detergent, a method of rinsing the thermoelectric conversion layer with a detergent, or the like.
Moreover, when using an inorganic material as a thermoelectric conversion material, the method of pattern-forming the thermoelectric conversion layer is illustrated by the well-known method using a metal mask etc. by vapor phase film-forming methods, such as vacuum evaporation and sputtering.
Alternatively, a thermoelectric conversion layer may be formed on the entire surface of the first substrate 12, and the thermoelectric conversion layer 16 may be patterned by etching or the like.
次いで、第１基板１２Ａの全面に対応して、熱電変換層１６、電極２６および第２電極２８を覆って、粘着層１８を形成する。
粘着層１８は、粘着層１８の形成材料に応じて、塗布法等の公知の方法で形成すればよい。また、両面テープや粘着フィルムを利用して粘着層１８を形成してもよい。
あるいは、第１基板１２Ａに粘着層１８を形成するのではなく、第２基板２０Ａの第２高熱伝導部２０ｂが形成されていない面に粘着層１８を形成して、第１基板１２Ａに貼着してもよい。
Next, the adhesive layer 18 is formed to cover the thermoelectric conversion layer 16, the electrode 26 and the second electrode 28 corresponding to the entire surface of the first substrate 12A.
The adhesive layer 18 may be formed by a known method such as a coating method depending on the material for forming the adhesive layer 18. Alternatively, the adhesive layer 18 may be formed using a double-sided tape or an adhesive film.
Alternatively, instead of forming the adhesive layer 18 on the first substrate 12A, the adhesive layer 18 is formed on the surface of the second substrate 20A on which the second high thermal conductivity portion 20b is not formed, and is attached to the first substrate 12A. You may
さらに、粘着層１８の上に、第２基板２０Ａの全面が低熱伝導部２０ａである面を粘着層１８側に向けて、第１基板１２の第１高熱伝導部１２ｂと第２基板２０の第２高熱伝導部２０ｂとが、離間方向に異なる位置となるように、第２基板２０Ａを積層して、熱電変換モジュール（熱電変換素子１０）を作製する。 Furthermore, on the adhesive layer 18, the surface of the second substrate 20A whose entire surface is the low thermal conductivity portion 20a is directed to the adhesive layer 18 side, and the first high thermal conductivity portion 12b of the first substrate 12 and the first high thermal conductivity portion The 2nd board | substrate 20A is laminated | stacked so that the 2 high heat conduction part 20b may become a different position in a separation direction, and the thermoelectric conversion module (thermoelectric conversion element 10) is produced.
本発明の熱電変換モジュール（熱電変換素子）を熱源に接着し、発電する際には、熱伝導接着シートや熱伝導性接着剤を用いてもよい。
熱電変換モジュールの加熱側、もしくは冷却側に貼付して用いられる熱伝導接着シートおよび熱伝導性接着剤には特に限定はない。従って、市販されている熱伝導接着シートや熱伝導性接着剤を用いることができる。熱伝導接着シートとしては、例えば、信越シリコーン社製のＴＣ−５０ＴＸＳ２、住友スリーエム社製のハイパーソフト放熱材 ５５８０Ｈ、電気化学工業社製のＢＦＧ２０Ａ、日東電工社製のＴＲ５９１２Ｆ等を用いることができる。なお、耐熱性の観点から、シリコーン系粘着剤からなる熱伝導接着シートが好ましい。熱伝導性接着剤としては、例えば、スリーエム社製のスコッチ・ウェルドＥＷ２０７０、アイネックス社製のＴＡ−０１、シーマ電子社製のＴＣＡ−４１０５、ＴＣＡ−４２１０、ＨＹ−９１０、薩摩総研社製のＳＳＴ２−ＲＳＭＺ、ＳＳＴ２−ＲＳＣＳＺ、Ｒ３ＣＳＺ、Ｒ３ＭＺ等を用いることができる。
熱伝導接着シートや熱伝導性接着剤を用いることで、熱源との密着性が向上して熱電変換モジュールの加熱側の表面温度が高くなる、冷却効率が向上して熱電変換モジュールの冷却側の表面温度を低くできるなどの効果により、発電量を高くすることができる。
When the thermoelectric conversion module (thermoelectric conversion element) of the present invention is bonded to a heat source and power is generated, a heat conductive adhesive sheet or a heat conductive adhesive may be used.
There are no particular limitations on the heat conductive adhesive sheet and the heat conductive adhesive that are used by being attached to the heating side or the cooling side of the thermoelectric conversion module. Therefore, commercially available heat conductive adhesive sheets and heat conductive adhesives can be used. As the heat conductive adhesive sheet, for example, TC-50TXS2 manufactured by Shin-Etsu Silicone Co., Ltd., Hypersoft heat dissipation material 5580H manufactured by Sumitomo 3M, BFG 20A manufactured by Denki Kagaku Kogyo Co., Ltd., TR5912F manufactured by Nitto Denko Corporation, etc. can be used. From the viewpoint of heat resistance, a heat conductive adhesive sheet made of a silicone pressure sensitive adhesive is preferable. As the heat conductive adhesive, for example, Scotch Weld EW2070 manufactured by 3M Co., TA-01 manufactured by INEX Co., TCA-4105 manufactured by Cima Electronics Co., Ltd., TCA-4210, HY-910, SST2 manufactured by Satsuma Soken Co., Ltd. -RSMZ, SST2-RSCSZ, R3CSZ, R3MZ etc. can be used.
By using the heat conductive adhesive sheet or the heat conductive adhesive, the adhesion to the heat source is improved to increase the surface temperature on the heating side of the thermoelectric conversion module, the cooling efficiency is improved, and the cooling side on the thermoelectric conversion module The amount of power generation can be increased by the effect that the surface temperature can be lowered.
さらに、熱電変換モジュールの冷却側の表面には、ステンレス、銅、アルミ等の公知の材料からなる放熱フィン（ヒートシンク）や放熱シートを設けてもよい。放熱フィン等を用いることで、熱電変換モジュールの低温側をより好適に冷却することができ、熱源側と冷却側との温度差が大きくなり、熱電効率がより向上する点で好ましい。
なお、本発明の熱電変換モジュール（熱電変換素子）では、通常、第２基板２０Ａ側が冷却側になる。
Furthermore, on the surface on the cooling side of the thermoelectric conversion module, a heat dissipating fin (heat sink) or a heat dissipating sheet made of a known material such as stainless steel, copper, or aluminum may be provided. Use of the heat radiation fin or the like can cool the low temperature side of the thermoelectric conversion module more suitably, and the temperature difference between the heat source side and the cooling side becomes large, which is preferable in that the thermoelectric efficiency is further improved.
In the thermoelectric conversion module (thermoelectric conversion element) of the present invention, the second substrate 20A side is usually the cooling side.
放熱フィンとしては、太陽金網社製のＴ−Ｗｉｎｇ、事業創造研究所製のＦＬＥＸＣＯＯＬや、コルゲートフィン、オフセットフィン、ウェービングフィン、スリットフィン、フォールディングフィンなどの各種フィンなどの公知のフィンを用いることができる。特に、フィン高さのあるフォールディングフィンを用いるのが好ましい。
放熱フィンのフィン高さとしては１０〜５６ｍｍ、フィンピッチとしては２〜１０ｍｍ、板厚としては０．１〜０．５ｍｍが好ましく、放熱特性が高く、モジュールの冷却ができ発電量が高くなる点で、フィン高さが２５ｍｍ以上であるのがより好ましい。また、フィンのフレキシブル性が高い、軽量である等の点で、板厚０．１〜０．３ｍｍのアルミ製を用いるのが好ましい。
また、放熱シートとしては、パナソニック社製のＰＳＧグラファイトシート、沖電線社製のクールスタッフ、セラミッション社製のセラックα等の公知の放熱シートを用いることができる。
As the heat dissipating fins, use may be made of known fins such as T-Wing manufactured by Solar Wire Mesh Co., FLEXCOOL manufactured by Business Creation Laboratory, and various fins such as corrugated fins, offset fins, waving fins, slit fins and folding fins. it can. In particular, it is preferable to use a folding fin having a fin height.
The fin height of the heat dissipating fins is 10 to 56 mm, the fin pitch is 2 to 10 mm, the plate thickness is preferably 0.1 to 0.5 mm, the heat dissipating characteristics are high, and the module can be cooled to increase power generation. More preferably, the fin height is 25 mm or more. In addition, it is preferable to use an aluminum plate having a thickness of 0.1 to 0.3 mm in terms of high flexibility and light weight of the fins.
In addition, as a heat dissipation sheet, PSG graphite sheet manufactured by Panasonic Corporation, Cool Stuff manufactured by Oki Electric Wire Co., Ltd., or known heat dissipation sheet such as Shellac α manufactured by Ceramission Co., Ltd. can be used.
このような本発明の熱電変換素子は、各種の用途に利用可能である。
一例として、温泉熱発電機、太陽熱発電機、廃熱発電機などの発電機や、腕時計用電源、半導体駆動電源、小型センサ用電源などの各種装置（デバイス）の電源等、様々な発電用途が例示される。また、本発明の熱電変換素子の用途としては、発電用途以外にも、感熱センサや熱電対などのセンサー素子用途も例示される。
Such a thermoelectric conversion element of the present invention can be used for various applications.
As an example, various power generation applications are exemplified such as generators such as hot spring thermal power generators, solar thermal power generators, waste heat power generators, power supplies for wristwatch power supplies, semiconductor drive power supplies, various devices such as small sensor power supplies, etc. Ru. Moreover, as a use of the thermoelectric conversion element of this invention, sensor element applications, such as a thermal sensor and a thermocouple, are also illustrated besides a power generation use.
以上、本発明の熱電変換素子について詳細に説明したが、本発明は上述の例に限定はされず、本発明の要旨を逸脱しない範囲において、各種の改良や変更を行ってもよいのは、もちろんである。 As mentioned above, although the thermoelectric conversion element of the present invention was explained in detail, the present invention is not limited to the above-mentioned example, and various improvements and changes may be made without departing from the scope of the present invention, Of course.
以下、本発明の具体的実施例を挙げて、本発明の熱電変換素子について、より詳細に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the thermoelectric conversion element of the present invention will be described in more detail with reference to specific examples of the present invention. However, the present invention is not limited to the following examples.
［実施例１］
（両面銅張ポリイミド基板の処理）
接着剤フリーの両面銅張ポリイミド基板（FELIOS R-F775、パナソニック電工社製）を用意した。この銅張ポリイミド基板は、サイズが１１０×８０ｍｍで、ポリイミド層の厚さが２０μｍ、Ｃｕ層の厚さが７０μｍのものである。
この両面銅張ポリイミド基板の一面の銅層を、エッチング処理により完全に除去した。
Example 1
(Treatment of double-sided copper-clad polyimide substrate)
An adhesive-free double-sided copper-clad polyimide substrate (FELIOS R-F775, manufactured by Panasonic Electric Works Co., Ltd.) was prepared. The copper-clad polyimide substrate is 110 × 80 mm in size, 20 μm in thickness of the polyimide layer, and 70 μm in thickness of the Cu layer.
The copper layer on one side of this double-sided copper-clad polyimide substrate was completely removed by etching.
（第１基板の作製）
一面の銅層を除去した銅張ポリイミド基板の残った銅層をエッチングして、厚さが７０μｍで、幅が０．７５ｍｍで、１．５ｍｍピッチの銅ストライプパターン１を形成した。
これにより、厚さが７０μｍで、幅が０．７５ｍｍの帯状の第１高熱伝導部１２ｂを、１．５ｍｍピッチで有する、図８（Ｄ）および図８（Ｅ）に示すような第１基板１２Ａを作製した。
(Preparation of the first substrate)
The remaining copper layer of the copper-clad polyimide substrate from which the one-side copper layer was removed was etched to form a copper stripe pattern 1 having a thickness of 70 μm, a width of 0.75 mm and a pitch of 1.5 mm.
Thereby, a first substrate as shown in FIGS. 8D and 8E, having a strip-like first high thermal conductivity portion 12b having a thickness of 70 μm and a width of 0.75 mm at a pitch of 1.5 mm. 12A was produced.
（第２基板の作製）
また、一面の銅層を除去した銅張ポリイミド基板の残った銅層をエッチングおよびハーフエッチングして、厚さが７０μｍで、幅が０．７５ｍｍで、間隔が０．７５ｍｍの銅ストライプパターン２を形成した。
これにより、厚さが７０μｍで、幅が０．７５ｍｍの帯状の第２高熱伝導部２０ｂを、０．７５ｍｍ間隔で有する、図８（Ａ）および図８（Ｂ）に示すような第２基板２０Ａを作製した。
(Preparation of second substrate)
In addition, the remaining copper layer of the copper-clad polyimide substrate from which the copper layer on one side has been removed is etched and half-etched to form a copper stripe pattern 2 having a thickness of 70 μm, a width of 0.75 mm and a spacing of 0.75 mm. It formed.
Thereby, a second substrate as shown in FIGS. 8A and 8B, having a strip-like second high thermal conductivity portion 20b having a thickness of 70 μm and a width of 0.75 mm at intervals of 0.75 mm. 20A was made.
（電極および熱電変換層の作製）
第１基板１２Ａの全面がポリイミドである面（平坦な面）の全面に、真空蒸着法によって、厚さ０．０５μｍのクロムからなる密着層を形成した。次いで、次に形成する熱電変換層１６の形成位置に応じて、真空蒸着法によって、厚さ０．５μｍの銅からなる電極２６を形成した。なお、電極は、メタルマスクを用いてパターン形成した。
さらに、電極２６の離間方向の端部を覆うように、真空蒸着法によって、厚さ１μｍのニッケルからなる熱電変換層１６を形成した。熱電変換層１６は、メタルマスクを用い、０．７５×１．５ｍｍのパターンを１１８５個形成した。
熱電変換層１６は、第１高熱伝導部１２ｂと低熱伝導部１２ａとの境界（銅ストライプパターン１の境界）と、０．７５×１ｍｍのパターンの０．７５ｍｍ側の中心とが一致するように形成した（図８（Ｃ）参照）。
(Preparation of electrode and thermoelectric conversion layer)
An adhesion layer made of chromium and having a thickness of 0.05 μm was formed on the entire surface (flat surface) of the first substrate 12A by the vacuum evaporation method. Next, in accordance with the formation position of the thermoelectric conversion layer 16 to be formed next, an electrode 26 made of copper and having a thickness of 0.5 μm was formed by a vacuum evaporation method. The electrodes were patterned using a metal mask.
Furthermore, a thermoelectric conversion layer 16 made of nickel and having a thickness of 1 μm was formed by vacuum evaporation so as to cover the end of the electrode 26 in the separation direction. The thermoelectric conversion layer 16 formed 1185 patterns of 0.75 × 1.5 mm using a metal mask.
In the thermoelectric conversion layer 16, the boundary between the first high thermal conductivity portion 12 b and the low thermal conductivity portion 12 a (the boundary of the copper stripe pattern 1) coincides with the center on the 0.75 mm side of the 0.75 × 1 mm pattern It formed (refer FIG. 8 (C)).
（熱電変換モジュールの作製）
一方で、第２基板２０Ａの全面がポリイミドである面（平坦な面）の全面に、粘着層１８として、厚さ３０μｍの粘着剤（両面テープＮｏ．５６３０、日東電工製）を貼着した。次いで、０．４ＭＰａ、４０℃で、２０分、オートクレーブ処理を行った。
オートクレーブ処理を行った第２基板と、熱電変換層を形成した第１基板とを、第２高熱伝導部２０ｂと、第１高熱伝導部１２ｂとの長手方向と一致させて、かつ、第２高熱伝導部２０ｂと第１高熱伝導部１２ｂとが面方向すなわち横方向に一致しないように積層、貼着した。
(Fabrication of thermoelectric conversion module)
On the other hand, a 30 μm thick adhesive (double-sided tape No. 5630, manufactured by Nitto Denko Corporation) was adhered as the adhesive layer 18 on the entire surface (flat surface) of the second substrate 20A where the entire surface is polyimide. Then, the autoclave process was performed at 0.4 MPa and 40 degreeC for 20 minutes.
The second substrate subjected to the autoclave treatment and the first substrate having the thermoelectric conversion layer formed thereon are made to coincide with the longitudinal direction of the second high thermal conductivity portion 20b and the first high thermal conductivity portion 12b, and the second high thermal conductivity The conductive portion 20 b and the first high heat conductive portion 12 b were laminated and attached so as not to coincide with the surface direction, that is, the lateral direction.
（接合部材の形成）
次に、第１高熱伝導部１２ｂの上に接合部材２２を形成した。
接合部材２２としては、フィラーとして炭素繊維を樹脂中に垂直配向した、厚さ１ｍｍの熱伝導シート（ポリマテック製ＰＴ−Ｖ）を用いた。
この熱伝導シートを幅０．７５ｍｍに切断して、第１高熱伝導部１２ｂに貼着し、厚さ１ｍｍの接合部材２２を形成することで、本発明の熱電変換素子が多数配列された熱電変換モジュールを作製した。
(Formation of bonding member)
Next, the bonding member 22 was formed on the first high thermal conductivity portion 12b.
As the bonding member 22, a thermally conductive sheet (PT-V manufactured by Polymertech) having a thickness of 1 mm, in which carbon fibers are vertically oriented in a resin, was used as a filler.
The heat conductive sheet is cut to a width of 0.75 mm and attached to the first high heat conductive portion 12b to form a bonding member 22 having a thickness of 1 mm, whereby a thermoelectric conversion element in which a large number of thermoelectric conversion elements of the present invention are arranged A conversion module was made.
［実施例２］
接合部材２２の形成材料として銀ペースト（藤倉化成社製ＦＡ−３３３）を用いた以外は、実施例１と同様にして熱電変換モジュールを作製した。
具体的には、銅層をエッチングして第１高熱伝導部１２ｂを形成した第１基板１２Ａの第１高熱伝導部１２ｂ上に、銀ペーストをメタルマスク印刷法で塗布し、焼成して接合部材２２を形成した。
Example 2
A thermoelectric conversion module was produced in the same manner as in Example 1 except that silver paste (FA-333 manufactured by Fujikura Kasei Co., Ltd.) was used as a material for forming the bonding member 22.
Specifically, silver paste is applied by metal mask printing on the first high thermal conductivity portion 12b of the first substrate 12A on which the copper layer is etched to form the first high thermal conductivity portion 12b, followed by firing and bonding members 22 were formed.
［実施例３］
接合部材２２の厚みを２ｍｍとした以外は実施例２と同様にして熱電変換モジュールを作製した。
[Example 3]
A thermoelectric conversion module was produced in the same manner as in Example 2 except that the thickness of the bonding member 22 was 2 mm.
［実施例４］
さらに、接合部材２２の、第１高熱伝導部１２ｂとは反対側の面に熱伝導シート２４を配置した以外は実施例１と同様にして熱電変換モジュールを作製した。
熱伝導シート２４としては、厚さ０．１ｍｍのグラファイトシート（パナソニック社製ＥＹＧＡ０９１２１０Ｍ）を用いた。このグラファイトシートは、面方向の熱伝導率が７００Ｗ／（ｍ・Ｋ）で、厚み方向の熱伝導率が５Ｗ／（ｍ・Ｋ）である。
Example 4
Furthermore, a thermoelectric conversion module was produced in the same manner as in Example 1 except that the heat conduction sheet 24 was disposed on the surface of the bonding member 22 opposite to the first high heat conduction portion 12b.
A 0.1 mm thick graphite sheet (EYGA 091210 M manufactured by Panasonic Corporation) was used as the heat conduction sheet 24. The graphite sheet has a thermal conductivity of 700 W / (m · K) in the surface direction and a thermal conductivity of 5 W / (m · K) in the thickness direction.
［実施例５］
さらに、接合部材２２の、第１高熱伝導部１２ｂとは反対側の面に、実施例４と同様の熱伝導シート２４を配置した以外は実施例２と同様にして熱電変換モジュールを作製した。
[Example 5]
Furthermore, a thermoelectric conversion module was produced in the same manner as in Example 2 except that a heat conductive sheet 24 similar to that in Example 4 was disposed on the surface of the bonding member 22 opposite to the first high heat conductive portion 12b.
［実施例６］
さらに、接合部材２２の、第１高熱伝導部１２ｂとは反対側の面に、実施例４と同様の熱伝導シート２４を配置した以外は実施例３と同様にして熱電変換モジュールを作製した。
[Example 6]
Furthermore, a thermoelectric conversion module was produced in the same manner as in Example 3 except that the same heat conduction sheet 24 as in Example 4 was disposed on the surface of the bonding member 22 opposite to the first high heat conduction portion 12b.
［実施例７］
以下のようにして作製した、第３高熱伝導部１２ｃを有する第１基板１２Ａを用いる構成とした以外は、実施例５と同様にして熱電変換モジュールを作製した（図４参照）。
[Example 7]
A thermoelectric conversion module was produced in the same manner as in Example 5 except that the first substrate 12A having the third high thermal conductivity portion 12c manufactured as follows was used (see FIG. 4).
（第１基板の作製）
一面の銅層を除去した銅張ポリイミド基板の残った銅層をエッチングおよびハーフエッチングして、厚さが７０μｍで、幅が０．７５ｍｍで、１．５ｍｍピッチの銅ストライプパターン１と、厚さが３０μｍで、幅が０．２ｍｍで、１．５ｍｍピッチの銅ストライプパターン２とを形成した。銅ストライプパターン１と銅ストライプパターン２とは、互いのスペースが０．２７５ｍｍの配置とした。
これにより、厚さが７０μｍで、幅が０．７５ｍｍの帯状の第１高熱伝導部１２ｂを、１．５ｍｍピッチで有し、厚さが３０μｍで、幅が０．２ｍｍの帯状の第３高熱伝導部１２ｃを、１．５ｍｍピッチで有する、図８（Ｄ）および図８（Ｅ）に示すような第１基板１２Ａを作製した。
(Preparation of the first substrate)
The remaining copper layer of the copper-clad polyimide substrate from which the entire copper layer has been removed is etched and half-etched to a thickness of 70 μm, a width of 0.75 mm, a 1.5 mm pitch copper stripe pattern 1 and a thickness of And a copper stripe pattern 2 with a width of 0.2 mm and a pitch of 1.5 mm. The copper stripe pattern 1 and the copper stripe pattern 2 were arranged such that the space between them was 0.275 mm.
Thus, a strip-like first high thermal conductive portion 12b having a thickness of 70 μm and a width of 0.75 mm is provided at a pitch of 1.5 mm, and a strip-like third high-heat transfer portion having a thickness of 30 μm and a width of 0.2 mm A first substrate 12A having conductive portions 12c at a pitch of 1.5 mm as shown in FIG. 8D and FIG. 8E was produced.
［実施例８］
第１高熱伝導部１２ｂの幅を０．４ｍｍとした以外は、実施例７と同様にして熱電変換モジュールを作製した（図６参照）。
[Example 8]
A thermoelectric conversion module was produced in the same manner as in Example 7 except that the width of the first high thermal conductivity portion 12b was 0.4 mm (see FIG. 6).
［実施例９］
第２基板２０Ａに代えて、以下のようにして作製した溝部を有する金属シートを用いる構成とした以外は、実施例７と同様にして熱電変換モジュールを作製した（図５参照）。
[Example 9]
A thermoelectric conversion module was produced in the same manner as in Example 7 except that the second substrate 20A was replaced with a metal sheet having a groove portion produced as follows (see FIG. 5).
（溝部を有する金属シートの作製）
サイズが１１０×８０ｍｍで厚さ０．２ｍｍの銅箔を用意した。
この銅箔にハーフエッチング処理を行い、深さが０．０７５ｍｍで、幅が０．８ｍｍの溝状の凹部を１．５ｍｍピッチでストライプ状に形成した。
これにより、厚さが０．２ｍｍの銅製で、深さが０．０７５ｍｍで幅が０．８ｍｍの溝部を、長手方向と直交する方向に１．５ｍｍピッチで有する、溝部を有する金属シートを作製した。
(Production of a metal sheet having a groove)
A copper foil having a size of 110 × 80 mm and a thickness of 0.2 mm was prepared.
The copper foil was half-etched to form a groove-shaped recess having a depth of 0.075 mm and a width of 0.8 mm in a stripe shape at a pitch of 1.5 mm.
This produces a metal sheet having grooves with a thickness of 0.2 mm and a groove having a depth of 0.075 mm and a width of 0.8 mm at a pitch of 1.5 mm in a direction perpendicular to the longitudinal direction. did.
（熱電変換モジュールの作製）
第２基板２０Ａに変えて、この金属シートの溝部の形成面に粘着層１８を形成して、溝部の長手方向と第１高熱伝導部１２ｂの長手方向と一致し、かつ、溝部と第１高熱伝導部１２ｂとが幅方向で重複するように、第１基板１２Ａの熱電変換層１６の形成面に貼着し、熱電変換モジュールを作製した。
従って、本例では、金属シートの溝部形成部以外の部分が第２高熱伝導部であり、第２高熱伝導部の幅は、０．７ｍｍである。また、本例では、第１基板１２Ａの第１高熱伝導部１２ｂと、金属シートの第２高熱伝導部２０ｂとは、対面する側の端部が離間方向で０．１ｍｍ離間している（離間距離０．１ｍｍ）。
(Fabrication of thermoelectric conversion module)
Instead of the second substrate 20A, the adhesive layer 18 is formed on the surface of the metal sheet on which the groove is formed, and the groove and the first high heat are aligned with the longitudinal direction of the groove and the longitudinal direction of the first high heat conduction portion 12b. It stuck on the formation side of thermoelectrical conversion layer 16 of the 1st substrate 12A so that conduction part 12b might overlap in the cross direction, and the thermoelectrical conversion module was produced.
Therefore, in the present example, the portion other than the groove forming portion of the metal sheet is the second high thermal conductivity portion, and the width of the second high thermal conductivity portion is 0.7 mm. Further, in this example, the end on the side facing the first high thermal conductivity portion 12b of the first substrate 12A and the second high thermal conductivity portion 20b of the metal sheet are separated by 0.1 mm in the separation direction (separation Distance 0.1 mm).
［実施例１０］
第２基板２０Ａに代えて、実施例９と同様の溝部を有する金属シートを用いる構成とした以外は、実施例８と同様にして熱電変換モジュールを作製した（図７参照）。
[Example 10]
A thermoelectric conversion module was produced in the same manner as in Example 8 except that a metal sheet having a groove similar to that in Example 9 was used instead of the second substrate 20A (see FIG. 7).
［実施例１１］
熱伝導シート２４として、以下のようにして形成した熱伝導シート２４を用いた以外は、実施例７と同様にして熱電変換モジュールを作製した。
[Example 11]
A thermoelectric conversion module was produced in the same manner as in Example 7, except that a heat conductive sheet 24 formed as follows was used as the heat conductive sheet 24.
実施例４の熱伝導シート２４と同様のグラファイトシートに、幅０．７５ｍｍ、深さ０．０５ｍｍの溝を１．５ｍｍピッチで形成した。溝の加工は、サンドブラスト加工で行った。
一方で、実施例２と同様にして、銀ペーストを焼成した接合部材２２を、第１高熱伝導部１２ｂ上に形成した。
グラファイトシートに形成した溝にディスペンサーで銀ペースト（藤倉化成製ＦＡ−７０５ＢＮ）を充填し、接合部材２２を嵌合して、加熱硬化することで熱電変換モジュールを作製した。
第１高熱伝導部１２ｂと熱伝導シート２４との間の間隙、すなわち、接合部材２２の実質的な厚さは、１ｍｍである。
Grooves having a width of 0.75 mm and a depth of 0.05 mm were formed on a graphite sheet similar to the heat conductive sheet 24 of Example 4 at a pitch of 1.5 mm. The grooves were processed by sand blasting.
On the other hand, in the same manner as in Example 2, a bonding member 22 obtained by firing a silver paste was formed on the first high thermal conductivity portion 12b.
The groove formed in the graphite sheet was filled with a silver paste (FA-705BN manufactured by Fujikura Kasei Co., Ltd.) with a dispenser, and the joining member 22 was fitted and heat cured to fabricate a thermoelectric conversion module.
The gap between the first high thermal conductivity portion 12 b and the thermal conductive sheet 24, that is, the substantial thickness of the bonding member 22 is 1 mm.
［実施例１２］
実施例１１と同様に、熱伝導シート２４に溝を形成して、この溝に接合部材２２を嵌合する構成とした以外は、実施例８と同様にして熱電変換モジュールを作製した。
[Example 12]
A thermoelectric conversion module was produced in the same manner as in Example 8 except that grooves were formed in the heat conductive sheet 24 and the joining members 22 were fitted in the grooves in the same manner as in Example 11.
［実施例１３］
実施例１１と同様に、熱伝導シート２４に溝を形成して、この溝に接合部材２２を嵌合する構成とした以外は、実施例９と同様にして熱電変換モジュールを作製した。
[Example 13]
A thermoelectric conversion module was produced in the same manner as in Example 9 except that a groove was formed in the heat conduction sheet 24 and the joining member 22 was fitted in this groove as in Example 11.
［実施例１４］
実施例１１と同様に、熱伝導シート２４に溝を形成して、この溝に接合部材２２を嵌合する構成とした以外は、実施例１０と同様にして熱電変換モジュールを作製した。
Example 14
A thermoelectric conversion module was produced in the same manner as in Example 10 except that grooves were formed in the heat conductive sheet 24 and the joining members 22 were fitted in the grooves in the same manner as in Example 11.
［実施例１５］
第１高熱伝導部１２ｂと熱伝導シート２４との間の間隙、すなわち、接合部材２２の実質的な厚さを２ｍｍとした以外は、実施例１１と同様にして熱電変換モジュールを作製した。
[Example 15]
A thermoelectric conversion module was produced in the same manner as in Example 11 except that the gap between the first high thermal conductivity portion 12 b and the thermal conductive sheet 24, that is, the substantial thickness of the bonding member 22 was 2 mm.
［実施例１６］
第１高熱伝導部１２ｂと熱伝導シート２４との間の間隙、すなわち、接合部材２２の実質的な厚さを２ｍｍとした以外は、実施例１２と同様にして熱電変換モジュールを作製した。
[Example 16]
A thermoelectric conversion module was produced in the same manner as in Example 12 except that the gap between the first high thermal conductivity portion 12 b and the thermal conductive sheet 24, that is, the substantial thickness of the bonding member 22 was 2 mm.
［実施例１７］
第１高熱伝導部１２ｂと熱伝導シート２４との間の間隙、すなわち、接合部材２２の実質的な厚さを２ｍｍとした以外は、実施例１３と同様にして熱電変換モジュールを作製した。
[Example 17]
A thermoelectric conversion module was produced in the same manner as in Example 13 except that the gap between the first high thermal conductivity portion 12 b and the thermal conductive sheet 24, that is, the substantial thickness of the bonding member 22 was 2 mm.
［実施例１８］
第１高熱伝導部１２ｂと熱伝導シート２４との間の間隙、すなわち、接合部材２２の実質的な厚さを２ｍｍとした以外は、実施例１４と同様にして熱電変換モジュールを作製した。
[Example 18]
A thermoelectric conversion module was produced in the same manner as in Example 14 except that the gap between the first high thermal conductive portion 12 b and the thermal conductive sheet 24, that is, the substantial thickness of the bonding member 22 was 2 mm.
［比較例１］
接合部材２２を有さない以外は、実施例１と同様にして熱電変換モジュールを作製した。
Comparative Example 1
A thermoelectric conversion module was produced in the same manner as in Example 1 except that the bonding member 22 was not provided.
［比較例２］
接合部材２２に代えて、実施例１で接合部材２２として用いた熱伝導シートをシート状のまま第１基板１２Ａの第１高熱伝導部１２ｂ側に配置した以外は、実施例１と同様にして熱電変換モジュールを作製した。
すなわち、比較例２は、接合部材が第１高熱伝導部に合わせてパターニングされていない構成とした。
Comparative Example 2
In the same manner as in Example 1 except that the heat conductive sheet used as the bonding member 22 in Example 1 is disposed in the form of a sheet on the side of the first high heat conductive portion 12b of the first substrate 12A A thermoelectric conversion module was produced.
That is, in Comparative Example 2, the bonding member was not patterned in accordance with the first high thermal conductivity portion.
［比較例３］
接合部材２２に代えて、実施例２で接合部材２２として用いた銀ペーストをシート状に焼成し、第１基板１２Ａの第１高熱伝導部１２ｂ側に配置した以外は、実施例１と同様にして熱電変換モジュールを作製した。
すなわち、比較例３は、接合部材が第１高熱伝導部に合わせてパターニングされていない構成とした。
Comparative Example 3
The same procedure as in Example 1 is carried out except that the silver paste used as the joining member 22 in Example 2 is sintered in a sheet shape instead of the joining member 22 and disposed on the first high thermal conductivity portion 12b side of the first substrate 12A. The thermoelectric conversion module was manufactured.
That is, Comparative Example 3 had a structure in which the bonding member was not patterned in accordance with the first high thermal conductivity portion.
（発電量の評価）
作製した熱電変換モジュールの第１高熱伝導部１２ｂ（接合部材２２）側を、熱伝導接着シート（信越化学工業社製、ＴＣ−５０ＴＸＳ２）を用いて、ホットプレートの加熱面に接着した。
また、熱電変換モジュールの第２高熱伝導部２０ｂの上に熱伝導接着シート（信越化学工業社製、ＴＣ−５０ＴＸＳ２）をさらに接着した。さらに、アルミ製のフォールディングフィン（サイズ５０×６０ｍｍ、高さ３０ｍｍ、ピッチ７ｍｍ、板厚０．５ｍｍ、最上インクス社製）を熱電変換モジュールの曲面に追随するように固定した。なお、フォールディングフィンは第２高熱伝導部２０ｂの形成領域上のみに固定した。
ホットプレートの温度を１２０℃、室内温度を２０℃に設定し、発電量を測定した。測定方法は、直列に接続した最上流の熱電変換層１６の電極および最下流の熱電変換層１６の電極と、ソースメーター（ケースレー社製、ソースメーター２４５０）とを接続し、開放電圧と短絡電流とを計測し、下記式から発電量を求めた。
（発電量）＝０．２５×（開放電圧）×（短絡電流）
比較例２の発電量を１として、各実施例および比較例の発電量の相対値を求めた。
結果を下記の表１に示す。
(Evaluation of power generation)
The first high thermal conductivity portion 12b (joining member 22) side of the produced thermoelectric conversion module was adhered to the heating surface of the hot plate using a thermal conductive adhesive sheet (TC-50TXS2 manufactured by Shin-Etsu Chemical Co., Ltd.).
In addition, a heat conductive adhesive sheet (TC-50TXS2, manufactured by Shin-Etsu Chemical Co., Ltd.) was further bonded onto the second high heat conductive portion 20b of the thermoelectric conversion module. Further, aluminum folding fins (size 50 × 60 mm, height 30 mm, pitch 7 mm, plate thickness 0.5 mm, manufactured by Top Inks Co., Ltd.) were fixed to follow the curved surface of the thermoelectric conversion module. In addition, the folding fin was fixed only on the formation area of the 2nd high heat conduction part 20b.
The temperature of the hot plate was set to 120 ° C., the room temperature was set to 20 ° C., and the amount of power generation was measured. The measurement method is to connect the electrode of the most upstream thermoelectric conversion layer 16 connected in series and the electrode of the most downstream thermoelectric conversion layer 16 with a source meter (source meter 2450 manufactured by Keithley), and open circuit voltage and short circuit current And the power generation amount was determined from the following equation.
(Amount of power generation) = 0.25 × (open circuit voltage) × (short circuit current)
Assuming that the amount of power generation of Comparative Example 2 is 1, the relative value of the amount of power generation of each Example and Comparative Example was determined.
The results are shown in Table 1 below.
また、実施例２と実施例３との対比、実施例５と実施例６との対比、実施例１１〜１４と実施例１５〜１８との対比から、接合部材の厚みは２ｍｍ以上が好ましいことがわかる。
また、実施例１〜３と実施例４〜６との対比から、接合部材２２上に熱伝導シート２４を配置するのが好ましいことがわかる。
また、実施例７〜１０と実施例１１〜１４との対比から、熱伝導シート２４と接合部材２２とを嵌合するのが好ましいことがわかる。
また、実施例５と実施例７との対比等から、第１基板１２が第３高熱伝導部１２ｃを有するのが好ましいことがわかる。
また、実施例７と実施例８との対比、実施例１１と実施例１２との対比、実施例１５と実施例１６との対比から、第１高熱伝導部１２ｂの幅を狭くする、すなわち、第１高熱伝導部１２ｂの熱伝導率を小さくすることが好ましいことがわかる。
また、実施例７と実施例９との対比、実施例１１と実施例１３との対比、実施例１５と実施例１７との対比から、第２基板２０として溝部を形成した金属シートを用いることが好ましいことがわかる。
以上の結果より、本発明の効果は明らかである。
Further, from the comparison between Example 2 and Example 3, the comparison between Example 5 and Example 6, and the comparison between Examples 11 to 14 and Examples 15 to 18, the thickness of the bonding member is preferably 2 mm or more. I understand.
Moreover, it turns out that it is preferable to arrange | position the heat conductive sheet 24 on the joining member 22 from contrast with Examples 1-3 and Examples 4-6.
Moreover, it turns out that it is preferable to fit the heat conductive sheet 24 and the joining member 22 from contrast with Examples 7-10 and Examples 11-14.
In addition, it is understood from the comparison between Example 5 and Example 7 that the first substrate 12 preferably includes the third high heat conduction portion 12c.
Further, from the comparison between Example 7 and Example 8, the comparison between Example 11 and Example 12, and the comparison between Example 15 and Example 16, the width of the first high heat conduction portion 12b is narrowed, that is, It is understood that it is preferable to reduce the thermal conductivity of the first high thermal conductivity portion 12b.
Further, from the comparison between Example 7 and Example 9, the comparison between Example 11 and Example 13, and the comparison between Example 15 and Example 17, using a metal sheet in which a groove is formed as the second substrate 20 It is understood that is preferable.
From the above results, the effects of the present invention are clear.
１０、４０、４６、５０、５２、５４ 熱電変換素子
１２、１２Ａ 第１基板
１２ａ 低熱伝導部
１２ｂ 第１高熱伝導部
１２ｃ 第３高熱伝導部
１６ 熱電変換層
１８ 粘着層
２０、２０Ａ 第２基板
２０ａ 低熱伝導部
２０ｂ 第２高熱伝導部
２２ 接合部材
２４ 熱伝導シート
２６、２８ 電極
３０ 熱源
３２ 放熱手段
４２ 金属シート
４２ａ 溝部
10, 40, 46, 50, 52, 54 thermoelectric conversion element 12, 12A first substrate 12a low thermal conductivity portion 12b first high thermal conductivity portion 12c third high thermal conductivity portion 16 thermoelectric conversion layer 18 adhesive layer 20, 20A second substrate 20a Low heat conducting part 20b Second high heat conducting part 22 bonding member 24 heat conducting sheet 26, 28 electrode 30 heat source 32 heat radiating means 42 metal sheet 42a groove part
Claims (9)
前記基板に設けられる熱電変換層と、
前記熱電変換層を覆う被覆層と、
前記被覆層に設けられる、前記被覆層よりも熱伝導率が高く、かつ、面方向に前記第１高熱伝導部と完全に重複しない第２高熱伝導部と、
面方向に前記熱電変換層を挟んで前記熱電変換層に接続される一対の電極と、
前記第１高熱伝導部の、前記熱電変換層とは反対側の面に設置される接合部材と、を有し、
前記接合部材は、厚み方向における熱伝導率が、面方向における熱伝導率よりも高いことを特徴とする熱電変換素子。 A substrate having a sheet-like low thermal conductivity part, and a first high thermal conductivity part provided in the low thermal conductivity part and having a thermal conductivity higher than that of the low thermal conductivity part;
A thermoelectric conversion layer provided on the substrate;
A covering layer covering the thermoelectric conversion layer;
A second high thermal conductivity portion provided in the coating layer, the second high thermal conductivity portion having a thermal conductivity higher than that of the coating layer and not completely overlapping with the first high thermal conductivity portion in the plane direction;
A pair of electrodes connected to the thermoelectric conversion layer across the thermoelectric conversion layer in a surface direction;
Of the first high thermal conductivity portion, have a, a joining member which is disposed on the opposite side to the thermoelectric conversion layer,
The thermoelectric conversion element characterized in that the thermal conductivity in the thickness direction of the joining member is higher than the thermal conductivity in the surface direction .
前記接合部材が前記熱伝導シートの凹部に嵌合している請求項３に記載の熱電変換素子。 The heat conductive sheet has a recess,
The thermoelectric conversion element according to claim 3 , wherein the joining member is fitted in the recess of the heat conduction sheet.
前記第３高熱伝導部の厚みは、前記第１高熱伝導部と前記接合部材との合計厚みよりも薄く、さらに、面方向に前記第１高熱伝導部と離間し、かつ、面方向に前記熱電変換層および第２高熱伝導部と少なくとも一部が重複する請求項１〜５のいずれか一項に記載の熱電変換素子。 The substrate includes a third high thermal conductivity portion having a thermal conductivity higher than that of the low thermal conductivity portion,
The thickness of the third high thermal conductivity portion is thinner than the total thickness of the first high thermal conductivity portion and the joining member, and further, the surface direction is separated from the first high thermal conductivity portion, and the surface direction is the thermoelectrical The thermoelectric conversion element according to any one of claims 1 to 5 , at least a portion of which overlaps the conversion layer and the second high thermal conductivity portion.
前記第２高熱伝導部が、金属製で、前記被覆層の前記熱電変換層と逆側の面に設けられる請求項１〜６のいずれか一項に記載の熱電変換素子。 The covering layer is a sheet made of resin, or further, an adhesive layer provided between the sheet made of resin and the thermoelectric conversion layer,
The thermoelectric conversion element according to any one of claims 1 to 6 , wherein the second high thermal conductivity portion is made of metal and is provided on the surface of the covering layer opposite to the thermoelectric conversion layer.
前記第２高熱伝導部が、貫通しない溝を有する金属製のシートであり、
前記金属製のシートは、前記溝の少なくとも一部が面方向に前記第１高熱伝導部と重複するように、前記溝を前記被覆層に向けて前記被覆層に設けた構成を有する請求項１〜６のいずれか一項に記載の熱電変換素子。 The covering layer has tackiness, and further,
The second high thermal conductivity portion is a metal sheet having a non-penetrating groove,
The metal sheet has a configuration in which the groove is provided in the covering layer toward the covering layer so that at least a part of the groove overlaps the first high thermal conductivity portion in the surface direction. the thermoelectric conversion device according to any one of 1-6.
前記第１高熱伝導部が、金属製で、前記低熱伝導部の前記熱電変換層と逆側の面に設けられる請求項１〜８のいずれか一項に記載の熱電変換素子。 The low thermal conductivity portion of the substrate is made of resin;
The thermoelectric conversion element according to any one of claims 1 to 8 , wherein the first high thermal conductivity portion is made of metal and is provided on the surface of the low thermal conductivity portion opposite to the thermoelectric conversion layer.
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