JP6659836B2 - Thermoelectric conversion module - Google Patents
Thermoelectric conversion module Download PDFInfo
- Publication number
- JP6659836B2 JP6659836B2 JP2018520836A JP2018520836A JP6659836B2 JP 6659836 B2 JP6659836 B2 JP 6659836B2 JP 2018520836 A JP2018520836 A JP 2018520836A JP 2018520836 A JP2018520836 A JP 2018520836A JP 6659836 B2 JP6659836 B2 JP 6659836B2
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- Prior art keywords
- thermoelectric conversion
- layer
- type thermoelectric
- conversion layer
- module
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Classifications
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
Description
本発明は、蛇腹状に折り返された熱電変換モジュールに関する。 The present invention relates to a thermoelectric conversion module folded in a bellows shape.
熱エネルギーと電気エネルギーと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。Thermoelectric conversion materials that can mutually convert thermal energy and electric energy are used for thermoelectric conversion elements such as power generation elements and Peltier elements that generate heat.
The thermoelectric conversion element has an advantage that it can directly convert heat energy into electric power and does not require a movable part. For this reason, a thermoelectric conversion module (power generation device) formed by connecting a plurality of thermoelectric conversion elements is provided at a portion where heat is exhausted, for example, in an incinerator or various facilities in a factory, so that there is no need to increase operating costs and the thermoelectric conversion module can be simplified. Power can be obtained.
熱電変換素子は、通常、複数を直列に接続した熱電変換モジュールとして使用される。熱電変換モジュールとしては、Ｂｉ−Ｔｅ等の熱電変換材料等を用いた、いわゆるπ型の熱電変換モジュールが知られている。
π型の熱電変換モジュールは、一例として、ｐ型およびｎ型の熱電変換材料をブロック状に加工して、セラミックス等の基板の上に交互に配列し、配列した熱電変換材料を直列に接続することで、作製される。The thermoelectric conversion element is usually used as a thermoelectric conversion module in which a plurality of thermoelectric conversion elements are connected in series. As a thermoelectric conversion module, a so-called π-type thermoelectric conversion module using a thermoelectric conversion material such as Bi-Te or the like is known.
As an example, a π-type thermoelectric conversion module processes p-type and n-type thermoelectric conversion materials into a block shape, alternately arranges them on a substrate such as a ceramic, and connects the arranged thermoelectric conversion materials in series. Thus, it is produced.
このようなπ型の熱電変換モジュールは、ブロック状の熱電変換材料の加工、熱電変換材料の配列、電極による熱電変換材料の接続等に手間がかかる。
これに対して、絶縁性基板として樹脂フィルム等を用い、インク状の熱電変換材料を塗布や印刷工程で絶縁性基板上に成膜した熱電変換モジュールが報告されている。この熱電変換モジュールは、製造が容易であり、しかも、印刷等によって多数の熱電変換素子を連続的に製造できる。In such a π-type thermoelectric conversion module, processing of a block-shaped thermoelectric conversion material, arrangement of the thermoelectric conversion materials, connection of the thermoelectric conversion materials by electrodes, and the like are troublesome.
On the other hand, there has been reported a thermoelectric conversion module in which a resin film or the like is used as an insulating substrate, and a thermoelectric conversion material in the form of an ink is formed on the insulating substrate in a coating or printing process. This thermoelectric conversion module is easy to manufacture, and can continuously manufacture a large number of thermoelectric conversion elements by printing or the like.
例えば、特許文献１には、蛇腹状の絶縁性基板上に、複数のｐ型薄膜パターンとｎ型薄膜パターンとが交互に配設され、隣同士の異種の薄膜パターンが接合され、二次元平面上に温度差を形成して発電する熱電薄膜素子を設けてなる熱電変換モジュール（熱電薄膜デバイス）が記載されている。
また、特許文献２には、熱電対が形成される複数の形成領域および熱電対が形成されない非形成領域を備えた、蛇腹状に折り返された可撓性を有する絶縁シートと、絶縁シートの形成領域に形成され直列に接続された複数の熱電対と、絶縁シートの非形成領域に形成され、複数の熱電対を直列に接続する接続線とを備える、熱電変換モジュール（熱発電装置）が記載されている。For example, in Patent Literature 1, a plurality of p-type thin film patterns and n-type thin film patterns are alternately arranged on a bellows-shaped insulating substrate, and different types of adjacent thin film patterns are joined to form a two-dimensional plane. There is described a thermoelectric conversion module (thermoelectric thin-film device) provided with a thermoelectric thin-film element for generating power by forming a temperature difference.
Further, Patent Document 2 discloses that a flexible insulating sheet folded in a bellows shape and having a plurality of forming regions where a thermocouple is formed and a non-forming region where a thermocouple is not formed, and a method of forming the insulating sheet A thermoelectric conversion module (thermoelectric generator) includes a plurality of thermocouples formed in a region and connected in series, and a connection line formed in a non-formation region of an insulating sheet and connecting the plurality of thermocouples in series. Have been.
前述のように、このような樹脂フィルム等を支持体として用いる熱電変換モジュールにおいては、インク状の熱電変換材料や電極材料を用いる塗布法あるいは印刷法、真空蒸着等の真空成膜法によって、熱電変換層や電極を形成できる。
そのため、この熱電変換モジュールは、ブロック状の熱電変換材料を用いるπ型の熱電変換モジュールに比して、製造が容易であり、製造コストも安くできる。
また、熱電変換素子は、一つ当たりの起電力が非常に小さいため、熱電変換モジュールは、数百以上の熱電変換素子を直列に接続して、電圧および発電量を増加させる必要が有る。これに対して、樹脂フィルム等を支持体として用いる熱電変換モジュールであれば、多数個の熱電変換素子の形成にも、印刷等での製造によって容易に対応できる。As described above, in a thermoelectric conversion module using such a resin film or the like as a support, thermoelectric conversion is performed by a coating method using an ink-like thermoelectric conversion material or an electrode material, a printing method, or a vacuum film forming method such as vacuum deposition. A conversion layer and an electrode can be formed.
Therefore, this thermoelectric conversion module is easier to manufacture and can be manufactured at lower cost than a π-type thermoelectric conversion module using a block-like thermoelectric conversion material.
In addition, since each thermoelectric conversion element has a very small electromotive force, it is necessary for the thermoelectric conversion module to increase the voltage and the amount of power generation by connecting several hundred or more thermoelectric conversion elements in series. On the other hand, if the thermoelectric conversion module uses a resin film or the like as a support, it can easily cope with the formation of a large number of thermoelectric conversion elements by manufacturing by printing or the like.
このような、可撓性を有する蛇腹状の熱電変換モジュールにおいて、発電量等の性能を向上する方法としては、各種の方法が考えられる。 In such a bellows-like thermoelectric conversion module having flexibility, various methods can be considered as a method for improving performance such as power generation.
例えば、特許文献１および特許文献２にも示されるように、従来の蛇腹状に折り返した形状を有する熱電変換モジュールは、熱電変換層等が形成される蛇腹の傾斜面は、対面する傾斜面と離間した状態となっている。
しかしながら、このような蛇腹状の熱電変換モジュールは、サイズを小型化できる、伝熱効率を向上できる、熱電変換素子の実装密度を向上できる等の点で、蛇腹状に折り返した支持体を熱電変換層の配列方向に圧縮して、可能な限り蛇腹を閉じた状態とした方が有利である。For example, as shown in Patent Literature 1 and Patent Literature 2, the conventional thermoelectric conversion module having a bellows-like folded shape has a bellows in which a thermoelectric conversion layer or the like is formed. It is in the separated state.
However, such a bellows-like thermoelectric conversion module has a thermoelectric conversion layer formed of a support that is folded in a bellows shape in that the size can be reduced, the heat transfer efficiency can be improved, and the mounting density of the thermoelectric conversion element can be improved. It is more advantageous to compress the bellows as close as possible in the arrangement direction.
ところが、従来の蛇腹状の熱電変換モジュールでは、蛇腹を閉じると、電極同士や熱電変換層同士が接触して、短絡してしまい、発電しなくなってしまう。
そのため、従来の蛇腹状の熱電変換モジュールでは、蛇腹を閉じるためには、絶縁部材を組み合わせる、電極や熱電変換層を覆って絶縁層を形成する等を施す必要があり、部品点数の増加や生産性の低下等を招く可能性がある。However, in the conventional bellows-shaped thermoelectric conversion module, when the bellows is closed, the electrodes and the thermoelectric conversion layers come into contact with each other and short-circuit, so that power is not generated.
Therefore, in the conventional bellows-like thermoelectric conversion module, in order to close the bellows, it is necessary to combine an insulating member or to form an insulating layer covering the electrodes and the thermoelectric conversion layer. This may lead to a decrease in performance.
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、絶縁部材を組み合わせる、絶縁層を形成する等を行わなくても、電極や熱電変換層の短絡を防止して蛇腹を閉じることができる熱電変換モジュールを提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to solve such problems of the related art, and it is possible to prevent a short circuit of an electrode or a thermoelectric conversion layer without combining insulating members or forming an insulating layer. To provide a thermoelectric conversion module that can close the thermoelectric conversion module.
このような目的を達成するために、本発明の熱電変換モジュールは、蛇腹状に折り返された第１層、第１層の一方の面に蛇腹状の折り返し方向に離間して交互に複数形成されるｐ型熱電変換層およびｎ型熱電変換層、ならびに、ｐ型熱電変換層を蛇腹状の折り返し方向に挟む電極対およびｎ型熱電変換層を蛇腹状の折り返し方向に挟む電極対と、
蛇腹状に折り返された第２層、第２層の一方の面に蛇腹状の折り返し方向に離間して交互に複数形成されるｐ型熱電変換層およびｎ型熱電変換層、ならびに、ｐ型熱電変換層を蛇腹状の折り返し方向に挟む電極対およびｎ型熱電変換層を蛇腹状の折り返し方向に挟む電極対と、を有し、
第１層の一方の面上に形成されたｐ型熱電変換層とｎ型熱電変換層とが電極対によって電気的に接続されており、もしくは、第２層の一方の面上に形成されたｐ型熱電変換層とｎ型熱電変換層とが電極対によって電気的に接続されており、
さらに、蛇腹状の折り返し方向に、
ｐ型熱電変換層−ｐ型熱電変換層−第１層−第１層−ｎ型熱電変換層−ｎ型熱電変換層−第２層−第２層
のパターンを、繰り返し有することを特徴とする熱電変換モジュールを提供する。In order to achieve such an object, a plurality of thermoelectric conversion modules of the present invention are formed alternately on the first layer folded in a bellows shape and on one surface of the first layer so as to be spaced apart in the bellows-like folding direction. A p-type thermoelectric conversion layer and an n-type thermoelectric conversion layer, and an electrode pair sandwiching the p-type thermoelectric conversion layer in a bellows-like folding direction and an electrode pair sandwiching the n-type thermoelectric conversion layer in a bellows-like folding direction.
A second layer folded in a bellows shape, a plurality of p-type thermoelectric conversion layers and a plurality of n-type thermoelectric conversion layers alternately formed on one surface of the second layer so as to be spaced apart in a bellows-like folding direction; An electrode pair sandwiching the conversion layer in a bellows-like folding direction and an electrode pair sandwiching the n-type thermoelectric conversion layer in a bellows-like folding direction,
The p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer formed on one surface of the first layer are electrically connected by an electrode pair, or formed on one surface of the second layer. The p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer are electrically connected by an electrode pair,
Furthermore, in the bellows-like folding direction,
It is characterized by having a pattern of p-type thermoelectric conversion layer-p-type thermoelectric conversion layer-first layer-first layer-n-type thermoelectric conversion layer-n-type thermoelectric conversion layer-second layer-second layer repeatedly. Provided is a thermoelectric conversion module.
このような本発明の熱電変換モジュールにおいて、第１層の一方の面上に形成されたｐ型熱電変換層とｎ型熱電変換層とが電極対によって電気的に接続されており、さらに、第２層の一方の面上に形成されたｐ型熱電変換層とｎ型熱電変換層とが電極対によって電気的に接続されているのが好ましい。
また、第１層が第１基板であり、第２層が第２基板であり、第１基板のｐ型熱電変換層の形成面と、第２基板のｐ型熱電変換層の形成面とを対面して、第１基板と第２基板とが積層されているのが好ましい。
また、１枚の基板を折り曲げることにより、１枚の基板が第１層および第２層となるのが好ましい。
また、第１層と第２層とを貫通して、可撓性を有する線状部材が挿通されるのが好ましい。
また、線状部材は、第１層のｐ型熱電変換層およびｎ型熱電変換層の形成部、ならびに、第２層のｐ型熱電変換層およびｎ型熱電変換層の形成部、以外の場所を貫通するのが好ましい。
また、線状部材は、第１層の一方の面上に形成された電極対および第２層の一方の面上に形成された電極対に対して、蛇腹状の折り返し方向に同位置で、かつ、蛇腹状の折り返しによる稜線の長手方向の外側において、第１層および第２層を貫通するのが好ましい。
また、熱伝導部材を有するのが好ましい。
また、熱伝導部材は、パターンにおける、第１層と第１層との間、および、第２層と第２層との間の、少なくとも一方に挿入されるのが好ましい。
また、熱伝導部材は、第１層の一方の面上に形成された電極対および第２層の一方の面上に形成された電極対の少なくとも一方に対して、蛇腹状の折り返し方向に対面する位置に挿入されるのが好ましい。
さらに、熱伝導部材として、板状の熱伝導部材および蛇腹状の熱伝導部材の少なくとも一方を有するのが好ましい。In such a thermoelectric conversion module of the present invention, the p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer formed on one surface of the first layer are electrically connected by an electrode pair. It is preferable that the p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer formed on one surface of the two layers are electrically connected by an electrode pair.
Further, the first layer is a first substrate, the second layer is a second substrate, and the p-type thermoelectric conversion layer forming surface of the first substrate and the p-type thermoelectric conversion layer forming surface of the second substrate are different from each other. It is preferable that the first substrate and the second substrate are stacked facing each other.
Further, it is preferable that one substrate be a first layer and a second layer by bending one substrate.
Further, it is preferable that a flexible linear member penetrates the first layer and the second layer.
In addition, the linear member is located at a portion other than the portion where the first p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer are formed and the portion where the second layer p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer are formed. Preferably penetrates.
The linear member is located at the same position in the bellows-like folding direction with respect to the electrode pair formed on one surface of the first layer and the electrode pair formed on one surface of the second layer. In addition, it is preferable to penetrate the first layer and the second layer on the outer side in the longitudinal direction of the ridge line formed by the bellows-like folding.
Further, it is preferable to have a heat conducting member.
Further, it is preferable that the heat conductive member is inserted between at least one of the first and second layers and between the second and second layers in the pattern.
The heat conductive member faces at least one of an electrode pair formed on one surface of the first layer and an electrode pair formed on one surface of the second layer in a bellows-like folding direction. Preferably, it is inserted at a position where it does.
Further, it is preferable that the heat conductive member has at least one of a plate-shaped heat conductive member and a bellows-shaped heat conductive member.
このような本発明によれば、蛇腹状の熱電変換モジュールにおいて、絶縁部材を組み合わせる、絶縁層を形成する等を行わなくても、電極や熱電変換層の短絡を防止して蛇腹を閉じることができる。 According to the present invention, in the bellows-like thermoelectric conversion module, it is possible to prevent the short circuit of the electrodes and the thermoelectric conversion layer and close the bellows without combining the insulating members and forming the insulating layer. it can.
以下、本発明の熱電変換モジュールについて、添付の図面に示される好適実施例を基に詳細に説明する。
なお、本明細書において、『〜』を用いて表される数値範囲は、『〜』の前後に記載される数値を下限値および上限値として含む範囲を意味する。Hereinafter, a thermoelectric conversion module according to the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
In addition, in this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.
図１に、本発明の熱電変換モジュールの一例を概念的に示す。
図１に示す熱電変換モジュール１０は、蛇腹状に折り返された第１基板１２Ａの一面に熱電変換層等を形成した第１モジュール１０Ａと、蛇腹状に折り返された第２基板１２Ｂの一面に熱電変換層等を形成した第２モジュール１０Ｂとを組み合わせたものである。FIG. 1 conceptually shows an example of the thermoelectric conversion module of the present invention.
The thermoelectric conversion module 10 shown in FIG. 1 includes a first module 10A having a thermoelectric conversion layer formed on one surface of a first substrate 12A folded in a bellows shape, and a thermoelectric conversion layer formed on one surface of a second substrate 12B folded in a bellows shape. This is a combination with a second module 10B having a conversion layer and the like.
図１は、本発明の熱電変換モジュールを蛇腹の折り返し方向すなわち第１基板１２Ａおよび第２基板１２Ｂの長手方向（図中横方向）に圧縮して、蛇腹を閉じた状態である。
ここで、図１は、熱電変換モジュール１０の構成や各部材が明瞭に示せるように、蛇腹状の折り返し部を矩形状にして示している。
しかしながら、本発明の熱電変換モジュール１０において、蛇腹を閉じた状態は、図２に示すような蛇腹状の熱電変換モジュールを蛇腹の折り返し方向に圧縮した状態である。従って、熱電変換モジュール１０の蛇腹を閉じた状態では、後述する山折りおよび谷折りされた折り返し部は、鋭角状になる。この点に関しては、後述する図３等も同様である。
さらに、図１は、あくまで概念図であり、各部材間における、厚さ、大きさ、長さ等の関係は、実際の熱電変換モジュールとは異なる。FIG. 1 shows a state in which the thermoelectric conversion module of the present invention is compressed in the bellows folding direction, that is, in the longitudinal direction (horizontal direction in the figure) of the first substrate 12A and the second substrate 12B, and the bellows is closed.
Here, FIG. 1 shows the bellows-like folded portion in a rectangular shape so that the configuration and each member of the thermoelectric conversion module 10 can be clearly shown.
However, in the thermoelectric conversion module 10 of the present invention, the state in which the bellows is closed is a state in which the bellows-like thermoelectric conversion module as shown in FIG. 2 is compressed in the folding direction of the bellows. Therefore, in a state where the bellows of the thermoelectric conversion module 10 is closed, a folded portion formed by mountain fold and valley fold described later has an acute angle. In this regard, FIG.
FIG. 1 is a conceptual diagram to the last, and the relationship between each member such as thickness, size, length, and the like is different from that of an actual thermoelectric conversion module.
前述のように、図１に示す熱電変換モジュール１０は、第１モジュール１０Ａと第２モジュール１０Ｂとを組み合わせたものである。
第１モジュール１０Ａは、第１基板１２Ａと、ｐ型熱電変換層１４ｐと、ｎ型熱電変換層１６ｎと、接続電極１８とを有する。第１基板１２Ａは、本発明の熱電変換モジュールにおける第１層である。
第２モジュール１０Ｂは、第２基板１２Ｂと、ｐ型熱電変換層１４ｐと、ｎ型熱電変換層１６ｎと、接続電極１８とを有する。第２基板１２Ｂは、本発明の熱電変換モジュールにおける第２層である。
図１においては、構成を明確に示すために、第１基板１２Ａおよび第２基板１２Ｂには斜線を付し、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎには網かけをしている。ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの網かけに関しては、図３の上段も同様である。As described above, the thermoelectric conversion module 10 shown in FIG. 1 is a combination of the first module 10A and the second module 10B.
The first module 10A includes a first substrate 12A, a p-type thermoelectric conversion layer 14p, an n-type thermoelectric conversion layer 16n, and a connection electrode 18. The first substrate 12A is a first layer in the thermoelectric conversion module of the present invention.
The second module 10B has a second substrate 12B, a p-type thermoelectric conversion layer 14p, an n-type thermoelectric conversion layer 16n, and a connection electrode 18. The second substrate 12B is a second layer in the thermoelectric conversion module of the present invention.
In FIG. 1, in order to clearly show the configuration, the first substrate 12A and the second substrate 12B are hatched, and the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n are shaded. . The shading of the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n is the same in the upper part of FIG.
図３に、本発明の熱電変換モジュール１０、熱電変換モジュール１０を第１モジュール１０Ａと第２モジュール１０Ｂとに分解した状態、および、第１モジュール１０Ａおよび第２モジュール１０Ｂを平面状に延ばした状態を、概念的に示す。
図３においては、上段が、第１モジュール１０Ａおよび第２モジュール１０Ｂを平面状に延ばした状態であり、中段が、熱電変換モジュール１０を分解した状態であり、下段が、熱電変換モジュール１０である。
図３の上段は、第１モジュール１０Ａおよび第２モジュール１０Ｂを平面状に延ばして、図３中段および下段の図中上方（第２モジュール１０Ｂ）および下方（第１モジュール１０Ａ）から見た図である。すなわち、図３の中段および下段（図１および図２）は、図３の上段に示す平面状に延ばした第１モジュール１０Ａおよび第２モジュール１０Ｂを、蛇腹状に折り返して、図３の上段における図中上下方向に見た図である。FIG. 3 shows a thermoelectric conversion module 10 of the present invention, a state where the thermoelectric conversion module 10 is disassembled into a first module 10A and a second module 10B, and a state where the first module 10A and the second module 10B are extended in a plane. Is shown conceptually.
In FIG. 3, the upper part is a state where the first module 10A and the second module 10B are extended in a plane, the middle part is a state where the thermoelectric conversion module 10 is disassembled, and the lower part is the thermoelectric conversion module 10. .
The upper part of FIG. 3 is a view in which the first module 10A and the second module 10B are extended in a plane and viewed from above (the second module 10B) and below (the first module 10A) in the middle and lower parts of FIG. is there. That is, the middle and lower stages of FIG. 3 (FIGS. 1 and 2) are obtained by folding the first module 10A and the second module 10B extended in a planar shape shown in the upper stage of FIG. It is the figure seen in the up-down direction in the figure.
なお、第１モジュール１０Ａおよび第２モジュール１０Ｂ、第１基板１２Ａの蛇腹状の折り返し方向と、第２基板１２Ｂの蛇腹状の折り返し方向とが異なる以外は、基本的に同じ構成を有する。従って、両者を区別する必要が有る場合を除いて、説明は第１モジュール１０Ａを代表例として行う。 The first module 10A, the second module 10B, and the first substrate 12A have basically the same configuration except that the bellows-like folding direction of the first substrate 12A is different from the bellows-like folding direction of the second substrate 12B. Therefore, the description will be made using the first module 10A as a representative example, except when it is necessary to distinguish the two.
図３に示すように、第１モジュール１０Ａ（第２モジュール１０Ｂ）は、長尺な第１基板１２Ａ（第２基板１２Ｂ）の一方の面に、第１基板１２Ａの長手方向に一定間隔で一定長さの接続電極１８を形成し、第１基板１２Ａの同じ面に、第１基板１２Ａの長手方向に一定間隔で一定長さのｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎを、交互に形成している。
以下の説明では、『第１基板１２Ａの長手方向』すなわち蛇腹状の折り返し方向を『長手方向』とも言う。また、以下の説明では、第１基板１２Ａの幅の方向、すなわち長手方向と直交する方向を『幅方向』とも言う。従って、幅方向は、図１（図２）および図３の中段および下段では、紙面に垂直な方向となる。
また、本発明において、長手方向の長さや間隔とは、第１モジュール１０Ａ（第１基板１２Ａ）を平面状に延ばした状態における、長さおよび間隔である。As shown in FIG. 3, the first module 10A (the second module 10B) is provided on one surface of the long first substrate 12A (the second substrate 12B) at regular intervals in the longitudinal direction of the first substrate 12A. A connection electrode 18 having a length is formed, and a p-type thermoelectric conversion layer 14p and an n-type thermoelectric conversion layer 16n having a certain length are alternately provided on the same surface of the first substrate 12A at a certain interval in a longitudinal direction of the first substrate 12A. Is formed.
In the following description, the “longitudinal direction of the first substrate 12A”, that is, the bellows-like folded direction is also referred to as the “longitudinal direction”. In the following description, the direction of the width of the first substrate 12A, that is, the direction orthogonal to the longitudinal direction, is also referred to as “width direction”. Therefore, the width direction is a direction perpendicular to the paper surface in the middle and lower tiers of FIGS. 1 (2) and 3.
In the present invention, the length and the interval in the longitudinal direction are the length and the interval in a state where the first module 10A (the first substrate 12A) is extended in a plane.
第１モジュール１０Ａは、接続電極１８の長手方向の中心において、第１基板１２Ａの幅方向に平行な折れ線（図３上段の破線）によって、山折りおよび谷折りに、交互に折り返した、蛇腹状になっている。従って、第１モジュール１０Ａは、蛇腹状の折り返しによって、長手方向に山折り部と谷折り部とを交互に有し、かつ、頂部と底部とを交互に有する。従って、長手方向とは、蛇腹状の折り返しによる傾斜面の傾斜方向と一致する。
なお、本例においては、蛇腹状の折り返しによって、第１基板１２Ａが内側すなわち接続電極１８が凸になる側を山折り、第１基板１２Ａが外側すなわち接続電極１８が凹になる側を谷折りとする。The first module 10A has a bellows shape that is alternately folded in a mountain-fold and a valley-fold at a center in the longitudinal direction of the connection electrode 18 by a polygonal line parallel to the width direction of the first substrate 12A (dashed line in the upper part of FIG. 3). It has become. Therefore, the first module 10A alternately has mountain folds and valley folds in the longitudinal direction and alternately has tops and bottoms by bellows-like folding. Therefore, the longitudinal direction coincides with the inclination direction of the inclined surface due to the bellows-like folding.
In the present example, the first substrate 12A is folded in an inward direction, that is, the side where the connection electrode 18 is convex, and the outer side of the first substrate 12A, that is, the side in which the connection electrode 18 is concave is folded by bellows. And
第１モジュール１０Ａは、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを離間して長手方向に交互に配置し、長手方向に隣接するｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを、接続電極１８によって直列に接続する。
また、前述のように、第１モジュール１０Ａは、接続電極１８の長手方向の中心で山折りおよび谷折りで折り返されて蛇腹状にされる。
このような第１モジュール１０Ａは、例えば、図１（図３下段）の下側に高温熱源を、上側に放熱フィンなどの放熱手段を設けて、図１における上下方向に温度差を生じさせられることで、発電する。言い換えれば、第１基板１２Ａの傾斜面に形成されたｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎに対して、長手方向に熱電変換層に温度差を生じさせることで、発電する。In the first module 10A, the p-type thermoelectric conversion layers 14p and the n-type thermoelectric conversion layers 16n are arranged alternately in the longitudinal direction while being separated from each other, and the p-type thermoelectric conversion layers 14p and the n-type thermoelectric conversion layers 16n adjacent in the longitudinal direction are arranged. Are connected in series by the connection electrode 18.
In addition, as described above, the first module 10A is folded at the center of the connection electrode 18 in the longitudinal direction by mountain folds and valley folds to form a bellows shape.
Such a first module 10A is provided with, for example, a high-temperature heat source on the lower side of FIG. 1 (lower part of FIG. 3) and a radiator such as a radiating fin on the upper side, so that a temperature difference is generated in the vertical direction in FIG. That generates electricity. In other words, power is generated by generating a temperature difference between the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n formed on the inclined surface of the first substrate 12A in the longitudinal direction.
第１基板１２Ａ（第２基板１２Ｂ）は、長尺で、可撓性を有し、かつ、絶縁性を有するものである。
本発明のモジュールにおいて、第１基板１２Ａは、可撓性および絶縁性を有するものであれば、可撓性支持体を用いる公知の熱電変換モジュールで利用されている長尺なシート状物（フィルム）が、各種、利用可能である。
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からなるシート状物が例示される。
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シート状物は、好適に利用される。The first substrate 12A (second substrate 12B) is long, flexible, and insulative.
In the module of the present invention, as long as the first substrate 12A has flexibility and insulating properties, a long sheet-like material (film) used in a known thermoelectric conversion module using a flexible support is used. ) Are available.
Specifically, polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate, poly (1,4-cyclohexylene dimethylene terephthalate), polyethylene-2,6-phthalenedicarboxylate, polyimide, Examples of the sheet-like material include polycarbonate, polypropylene, polyethersulfone, cycloolefin polymer, resins such as polyetheretherketone (PEEK) and triacetylcellulose (TAC), glass epoxy, and liquid crystalline polyester.
Among them, a sheet made of polyimide, polyethylene terephthalate, polyethylene naphthalate, or the like is preferably used in terms of thermal conductivity, heat resistance, solvent resistance, availability, economy, and the like.
第１基板１２Ａの厚さは、第１基板１２Ａの形成材料等に応じて、十分な可撓性を得られ、また、第１基板１２Ａとして機能する厚さを、適宜、設定すればよい。
なお、第１基板１２Ａの長さや幅は、第１モジュール１０Ａの大きさや用途等に応じて、適宜、設定すればよい。The thickness of the first substrate 12A may be set as appropriate so that sufficient flexibility can be obtained and the thickness functioning as the first substrate 12A can be obtained according to the material for forming the first substrate 12A.
Note that the length and width of the first substrate 12A may be appropriately set according to the size and use of the first module 10A.
第１基板１２Ａの一方の面には、長手方向に、一定間隔で、一定長さのｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎを、交互に有している。
以下の説明では、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを区別する必要がない場合には、両者をまとめて『熱電変換層』とも言う。On one surface of the first substrate 12A, p-type thermoelectric conversion layers 14p and n-type thermoelectric conversion layers 16n having a certain length are alternately provided at a certain interval in a longitudinal direction.
In the following description, when there is no need to distinguish between the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n, both are collectively referred to as a “thermoelectric conversion layer”.
本発明の第１モジュール１０Ａにおいて、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎは、公知の熱電変換材料からなるものが、各種、利用可能である。
ｐ型熱電変換層１４ｐやｎ型熱電変換層１６ｎを構成する熱電変換材料としては、例えば、ニッケルまたはニッケル合金がある。
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、または２成分以上と混合したニッケル合金等が例示される。
ｐ型熱電変換層１４ｐやｎ型熱電変換層１６ｎにニッケルまたはニッケル合金を用いる場合、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎは、ニッケルの含有量が９０原子％以上であるのが好ましく、ニッケルの含有量が９５原子％以上であるのがより好ましく、ニッケルからなるのが特に好ましい。ニッケルからなるｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎは、不可避的不純物を有するものも含む。In the first module 10A of the present invention, the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n can be made of various types of known thermoelectric conversion materials.
As a thermoelectric conversion material forming the p-type thermoelectric conversion layer 14p or the n-type thermoelectric conversion layer 16n, for example, nickel or a nickel alloy is used.
As the nickel alloy, various nickel alloys that generate power by generating a temperature difference can be used. Specifically, a nickel alloy mixed with one or more components such as vanadium, chromium, silicon, aluminum, titanium, molybdenum, manganese, zinc, tin, copper, cobalt, iron, magnesium, and zirconium is exemplified. You.
When nickel or a nickel alloy is used for the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n, the content of nickel in the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n is 90 atomic% or more. More preferably, the content of nickel is 95 atomic% or more, and particularly preferably, it is composed of nickel. The p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n made of nickel include those having unavoidable impurities.
ｐ型熱電変換層１４ｐの熱電変換材料としてニッケル合金を用いる場合には、ニッケルおよびクロムを主成分とするクロメルが典型的なものである。また、ｎ型熱電変換層１６ｎの熱電材料としてはニッケル合金を用いる場合には、銅およびニッケルを主成分とするコンスタンタンが典型的なものである。
ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとしてニッケルまたはニッケル合金を用いる場合に、接続電極１８としてもニッケルまたはニッケル合金を用いる場合には、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎと接続電極１８とを一体的に形成してもよい。When a nickel alloy is used as the thermoelectric conversion material of the p-type thermoelectric conversion layer 14p, chromel containing nickel and chromium as main components is typical. When a nickel alloy is used as the thermoelectric material of the n-type thermoelectric conversion layer 16n, constantan containing copper and nickel as main components is typical.
When nickel or a nickel alloy is used as the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n, and when nickel or a nickel alloy is also used as the connection electrode 18, the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer are used. 16n and the connection electrode 18 may be integrally formed.
ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎに利用可能な熱電変換材料としては、ニッケルおよびニッケル合金以外にも、以下の材料が例示される。なお、括弧内が材料組成を示す。
ＢｉＴｅ系（ＢｉＴｅ、ＳｂＴｅ、ＢｉＳｅおよびこれらの化合物）、ＰｂＴｅ系（ＰｂＴｅ、ＳｎＴｅ、ＡｇＳｂＴｅ、ＧｅＴｅおよびこれらの化合物）、Ｓｉ−Ｇｅ系（Ｓｉ、Ｇｅ、ＳｉＧｅ）、シリサイド系（ＦｅＳｉ、ＭｎＳｉ、ＣｒＳｉ）、スクッテルダイト系（ＭＸ3、若しくはＲＭ4Ｘ12と記載される化合物、ここでＭ＝Ｃｏ、Ｒｈ、Ｉｒを表し、Ｘ＝Ａｓ、Ｐ、Ｓｂを表し、Ｒ＝Ｌａ、Ｙｂ、Ｃｅを表す）、遷移金属酸化物系（ＮａＣｏＯ、ＣａＣｏＯ、ＺｎＩｎＯ、ＳｒＴｉＯ、ＢｉＳｒＣｏＯ、ＰｂＳｒＣｏＯ、ＣａＢｉＣｏＯ、ＢａＢｉＣｏＯ）、亜鉛アンチモン系（ＺｎＳｂ）、ホウ素化合物（ＣｅＢ、ＢａＢ、ＳｒＢ、ＣａＢ、ＭｇＢ、ＶＢ、ＮｉＢ、ＣｕＢ、ＬｉＢ）、クラスター固体（Ｂクラスター、Ｓｉクラスター、Ｃクラスター、ＡｌＲｅ、ＡｌＲｅＳｉ）、酸化亜鉛系（ＺｎＯ）などが挙げられる。Examples of the thermoelectric conversion material that can be used for the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n include the following materials in addition to nickel and a nickel alloy. The composition in parentheses indicates the material composition.
BiTe system (BiTe, SbTe, BiSe and their compounds), PbTe system (PbTe, SnTe, AgSbTe, GeTe and their compounds), Si-Ge system (Si, Ge, SiGe), silicide system (FeSi, MnSi, CrSi) ), Skutterudite (a compound described as MX 3 or RM 4 X 12 , where M = Co, Rh, Ir, X = As, P, Sb, R = La, Yb, Ce ), Transition metal oxides (NaCoO, CaCoO, ZnInO, SrTiO, BiSrCoO, PbSrCoO, CaBiCoO, BaBiCoO), zinc antimony (ZnSb), boron compounds (CeB, BaB, SrB, CaB, MgB, VB, NiB) , CuB, LiB), cluster solid (B cluster, Si Star, C cluster, AlRe, AlReSi), and the like zinc oxide based (ZnO).
ｐ型熱電変換層１４ｐやｎ型熱電変換層１６ｎに用いられる熱電変換材料には、塗布または印刷で膜形成可能なペースト化可能な材料も利用可能である。
このような熱電変換材料としては、具体的には、導電性高分子または導電性ナノ炭素材料等の有機系熱電変換材料が例示される。
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、ポリフェニレン等の公知の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。
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。中でも、熱電特性がより良好となる理由から、カーボンナノチューブが好ましく利用される。以下の説明では、『カーボンナノチューブ』を『ＣＮＴ』とも言う。As the thermoelectric conversion material used for the p-type thermoelectric conversion layer 14p or the n-type thermoelectric conversion layer 16n, a paste-form material that can be formed into a film by coating or printing can be used.
As such a thermoelectric conversion material, specifically, an organic thermoelectric conversion material such as a conductive polymer or a conductive nanocarbon material is exemplified.
Examples of the conductive polymer include a polymer compound having a conjugated molecular structure (conjugated polymer). Specific examples include known π-conjugated polymers such as polyaniline, polyphenylenevinylene, polypyrrole, polythiophene, polyfluorene, acetylene, and polyphenylene. In particular, polydioxythiophene can be suitably used.
Specific examples of the conductive nanocarbon material include carbon nanotubes, carbon nanofibers, graphite, graphene, and carbon nanoparticles. These may be used alone or in combination of two or more. Among them, carbon nanotubes are preferably used because the thermoelectric properties become better. In the following description, “carbon nanotube” is also referred to as “CNT”.
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、およ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、導電性およ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を用いるのが好ましく、単層ＣＮＴを用いるのがより好ましい。
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、両者の含有比率は、適宜調整することができる。また、ＣＮＴには金属等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。The CNT includes a single-layer CNT in which one carbon film (graphene sheet) is wound in a cylindrical shape, a two-layer CNT in which two graphene sheets are wound concentrically, and a plurality of graphene sheets in concentric circles There is a multilayer CNT wound in a shape. In the present invention, single-walled CNTs, double-walled CNTs, and multilayered CNTs may be used alone or in combination of two or more. In particular, it is preferable to use single-walled CNTs and double-walled CNTs having excellent properties in conductivity and semiconductor characteristics, and it is more preferable to use single-walled CNTs.
The single-walled CNTs may be semiconductor-based or metal-based, and may be used in combination. When using both semiconductor CNT and metallic CNT, the content ratio of both can be adjusted suitably. Further, the CNT may include a metal or the like, or may use a CNT including a molecule such as fullerene.
ＣＮＴの平均長さは特に限定されず、適宜選択することができる。具体的には、電極間距離にもよるが、製造容易性、成膜性、導電性等の観点から、ＣＮＴの平均長さが０．０１〜２０００μｍが好ましく、０．１〜１０００μｍがより好ましく、１〜１０００μｍが特に好ましい。
また、ＣＮＴの直径は特に限定されないが、耐久性、透明性、成膜性、導電性等の観点から、０．４〜１００ｎｍが好ましく、５０ｎｍ以下がより好ましく、１５ｎｍ以下が特に好ましい。特に、単層ＣＮＴを用いる場合には、ＣＮＴの直径は、０．５〜２．２ｎｍが好ましく、１．０〜２．２ｎｍがより好ましく、１．５〜２．０ｎｍが特に好ましい。
ＣＮＴには、欠陥のあるＣＮＴが含まれていることがある。このようなＣＮＴの欠陥は、熱電変換層の導電性を低下させるため、低減化することが好ましい。ＣＮＴの欠陥の量は、ラマンスペクトルのＧ−バンドとＤ−バンドの比率Ｇ／Ｄで見積もることができる。Ｇ／Ｄ比が高いほど欠陥の量が少ないＣＮＴ材料であると推定できる。ＣＮＴは、Ｇ／Ｄ比が１０以上であるのが好ましく、３０以上であるのがより好ましい。The average length of the CNT is not particularly limited and can be appropriately selected. Specifically, the average length of the CNT is preferably 0.01 to 2000 μm, more preferably 0.1 to 1000 μm from the viewpoints of ease of production, film formability, conductivity and the like, although it depends on the distance between the electrodes. , 1 to 1000 μm are particularly preferred.
The diameter of the CNT is not particularly limited, but is preferably 0.4 to 100 nm, more preferably 50 nm or less, particularly preferably 15 nm or less, from the viewpoints of durability, transparency, film formability, conductivity and the like. In particular, when a single-walled CNT is used, the diameter of the CNT is preferably 0.5 to 2.2 nm, more preferably 1.0 to 2.2 nm, and particularly preferably 1.5 to 2.0 nm.
The CNT may include a defective CNT. Such CNT defects are preferably reduced to reduce the conductivity of the thermoelectric conversion layer. The amount of CNT defects can be estimated by the ratio G / D of G-band and D-band of the Raman spectrum. It can be estimated that the higher the G / D ratio, the smaller the amount of defects in the CNT material. The CNT preferably has a G / D ratio of 10 or more, and more preferably 30 or more.
また、ＣＮＴを修飾または処理したＣＮＴも利用可能である。修飾または処理方法としては、フェロセン誘導体または窒素置換フラーレン（アザフラーレン）を内包する方法、イオンドーピング法によりアルカリ金属（カリウム等）または金属元素（インジウム等）をＣＮＴにドープする方法、真空中でＣＮＴを加熱する方法等が例示される。
また、ＣＮＴを利用する場合には、単層ＣＮＴおよび多層ＣＮＴの他に、カーボンナノホーン、カーボンナノコイル、カーボンナノビーズ、グラファイト、グラフェン、アモルファスカーボン等のナノカーボンが含まれてもよい。CNTs obtained by modifying or treating CNTs can also be used. Modification or treatment methods include a method of encapsulating a ferrocene derivative or a nitrogen-substituted fullerene (azafullerene), a method of doping CNTs with an alkali metal (eg, potassium) or a metal element (eg, indium) by ion doping, And the like.
When CNT is used, nanocarbon such as carbon nanohorn, carbon nanocoil, carbon nanobeads, graphite, graphene, and amorphous carbon may be included in addition to single-walled CNT and multilayered CNT.
ｐ型熱電変換層１４ｐやｎ型熱電変換層１６ｎにＣＮＴを利用する場合、熱電変換層にはｐ型ドーパントまたはｎ型ドーパントを含むことが好ましい。
（ｐ型ドーパント）
ｐ型ドーパントとしては、ハロゲン（ヨウ素、臭素等）、ルイス酸（ＰＦ5、ＡｓＦ5等）、プロトン酸（塩酸、硫酸等）、遷移金属ハロゲン化物（ＦｅＣｌ3、ＳｎＣｌ4等）、金属酸化物（酸化モリブデン、酸化バナジウム等）、有機の電子受容性物質等が例示される。有機の電子受容性物質としては、例えば、２，３，５，６−テトラフルオロ−７，７，８，８−テトラシアノキノジメタン、２，５−ジメチル−７，７，８，８−テトラシアノキノジメタン、２−フルオロ−７，７，８，８−テトラシアノキノジメタン、２，５−ジフルオロ−７，７，８，８−テトラシアノキノジメタン等のテトラシアノキノジメタン（ＴＣＮＱ）誘導体、２，３−ジクロロ−５，６−ジシアノ−ｐ−ベンゾキノン、テトラフルオロ−１，４−ベンゾキノン等のベンゾキノン誘導体等、５，８Ｈ−５，８−ビス（ジシアノメチレン）キノキサリン、ジピラジノ［２，３−ｆ：２’，３’−ｈ］キノキサリン−２，３，６，７，１０，１１−ヘキサカルボニトリル等が好適に例示される。
中でも、材料の安定性、ＣＮＴとの相溶性等の点で、ＴＣＮＱ（テトラシアノキノジメタン）誘導体またはベンゾキノン誘導体等の有機の電子受容性物質は好適に例示される。
ｐ型ドーパントおよびｎ型ドーパントは、いずれも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。When CNT is used for the p-type thermoelectric conversion layer 14p or the n-type thermoelectric conversion layer 16n, the thermoelectric conversion layer preferably contains a p-type dopant or an n-type dopant.
(P-type dopant)
The p-type dopant, a halogen (iodine, bromine, etc.), Lewis acids (PF 5, AsF 5 and the like), protonic acid (hydrochloric and sulfuric), transition metal halide (FeCl 3, SnCl 4 and the like), metal oxides (Molybdenum oxide, vanadium oxide, etc.), organic electron-accepting substances, and the like. Examples of the organic electron accepting substance include 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane and 2,5-dimethyl-7,7,8,8- Tetracyanoquinodimethane such as tetracyanoquinodimethane, 2-fluoro-7,7,8,8-tetracyanoquinodimethane and 2,5-difluoro-7,7,8,8-tetracyanoquinodimethane 5,8H-5,8-bis (dicyanomethylene) quinoxaline, such as (TCNQ) derivatives, benzoquinone derivatives such as 2,3-dichloro-5,6-dicyano-p-benzoquinone and tetrafluoro-1,4-benzoquinone; Dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile is preferably exemplified.
Among them, organic electron accepting substances such as a TCNQ (tetracyanoquinodimethane) derivative or a benzoquinone derivative are preferably exemplified in terms of material stability, compatibility with CNT, and the like.
Each of the p-type dopant and the n-type dopant may be used alone, or two or more of them may be used in combination.
（ｎ型ドーパント）
ｎ型ドーパントとしては、（１）ナトリウム、カリウム等のアルカリ金属、（２）トリフェニルホスフィン、エチレンビス(ジフェニルホスフィン)等のホスフィン類、（３）ポリビニルピロリドン、ポリエチレンイミン等のポリマー類等の公知の材料を用いることができる。
また、例えば、ポリエチレングリコール型の高級アルコールエチレンオキサイド付加物、フェノールまたはナフトール等のエチレンオキサイド付加物、脂肪酸エチレンオキサイド付加物、多価アルコール脂肪酸エステルエチレンオキサイド付加物、高級アルキルアミンエチレンオキサイド付加物、脂肪酸アミドエチレンオキサイド付加物、油脂のエチレンオキサイド付加物、ポリプロピレングリコールエチレンオキサイド付加物、ジメチルシロキサン−エチレンオキサイドブロックコポリマー、ジメチルシロキサン−（プロピレンオキサイド−エチレンオキサイド）ブロックコポリマー等、または多価アルコール型のグリセロールの脂肪酸エステル、ペンタエリスリトールの脂肪酸エステル、ソルビトールおよびソルビタンの脂肪酸エステル、ショ糖の脂肪酸エステル、多価アルコールのアルキルエーテル、アルカノールアミン類の脂肪酸アミド等が挙げられる。また、アセチレングリコール系とアセチレンアルコール系のオキシエチレン付加物、フッ素系、シリコーン系等の界面活性剤も同様に使用することができる。(N-type dopant)
Known n-type dopants include (1) alkali metals such as sodium and potassium, (2) phosphines such as triphenylphosphine and ethylenebis (diphenylphosphine), and (3) polymers such as polyvinylpyrrolidone and polyethyleneimine. Can be used.
Further, for example, polyethylene glycol type higher alcohol ethylene oxide adduct, ethylene oxide adduct such as phenol or naphthol, fatty acid ethylene oxide adduct, polyhydric alcohol fatty acid ester ethylene oxide adduct, higher alkylamine ethylene oxide adduct, fatty acid Amide ethylene oxide adduct, ethylene oxide adduct of fats and oils, polypropylene glycol ethylene oxide adduct, dimethylsiloxane-ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, etc., or polyhydric alcohol type glycerol Fatty acid esters, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan Fatty acid esters of sucrose, alkyl ethers of polyhydric alcohols, fatty acid amides of alkanolamines. In addition, surfactants such as acetylene glycol-based and acetylene alcohol-based oxyethylene adducts, fluorine-based and silicone-based surfactants can also be used.
ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎとしては、樹脂材料（バインダ）に、熱電変換材料を分散してなる熱電変換層も好適に利用される。
中でも、樹脂材料に導電性ナノ炭素材料を分散してなる熱電変換層は、より好適に例示される。その中でも、高い導電性が得られる等の点で、樹脂材料にＣＮＴを分散してなる熱電変換層は、特に好適に例示される。
樹脂材料は、公知の各種の非導電性の樹脂材料（高分子材料）が利用可能である。
具体的には、ビニル化合物、（メタ）アクリレート化合物、カーボネート化合物、エステル化合物、エポキシ化合物、シロキサン化合物、ゼラチン等が例示される。As the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n, a thermoelectric conversion layer obtained by dispersing a thermoelectric conversion material in a resin material (binder) is also preferably used.
Among them, a thermoelectric conversion layer formed by dispersing a conductive nanocarbon material in a resin material is more preferably exemplified. Among them, a thermoelectric conversion layer formed by dispersing CNTs in a resin material is particularly preferably exemplified in that high conductivity is obtained.
As the resin material, various known non-conductive resin materials (polymer materials) can be used.
Specific examples include vinyl compounds, (meth) acrylate compounds, carbonate compounds, ester compounds, epoxy compounds, siloxane compounds, gelatin, and the like.
より具体的には、ビニル化合物としては、ポリスチレン、ポリビニルナフタレン、ポリ酢酸ビニル、ポリビニルフェノール、ポリビニルブチラール等が例示される。（メタ）アクリレート化合物としては、ポリメチル（メタ）アクリレート、ポリエチル（メタ）アクリレート、ポリフェノキシ（ポリ）エチレングリコール（メタ）アクリレート、ポリベンジル（メタ）アクリレート等が例示される。カーボネート化合物としては、ビスフェノールＺ型ポリカーボネート、ビスフェノールＣ型ポリカーボネート等が例示される。エステル化合物としては、非晶性ポリエステルが例示される。 More specifically, examples of the vinyl compound include polystyrene, polyvinyl naphthalene, polyvinyl acetate, polyvinyl phenol, and polyvinyl butyral. Examples of the (meth) acrylate compound include polymethyl (meth) acrylate, polyethyl (meth) acrylate, polyphenoxy (poly) ethylene glycol (meth) acrylate, and polybenzyl (meth) acrylate. Examples of the carbonate compound include bisphenol Z-type polycarbonate and bisphenol C-type polycarbonate. As the ester compound, an amorphous polyester is exemplified.
好ましくは、ポリスチレン、ポリビニルブチラール、（メタ）アクリレート化合物、カーボネート化合物、エステル化合物が例示され、より好ましくは、ポリビニルブチラール、ポリフェノキシ（ポリ）エチレングリコール（メタ）アクリレート、ポリベンジル（メタ）アクリレート、非晶性ポリエステルが例示される。
樹脂材料に熱電変換材料を分散してなる熱電変換層において、樹脂材料と熱電変換材料との量比は、用いる材料、要求される熱電変換効率、印刷に影響する溶液の粘度または固形分濃度等に応じて、適宜設定すればよい。Preferably, polystyrene, polyvinyl butyral, (meth) acrylate compounds, carbonate compounds and ester compounds are exemplified. More preferably, polyvinyl butyral, polyphenoxy (poly) ethylene glycol (meth) acrylate, polybenzyl (meth) acrylate, amorphous The polyester is exemplified.
In the thermoelectric conversion layer in which the thermoelectric conversion material is dispersed in the resin material, the amount ratio between the resin material and the thermoelectric conversion material depends on the material used, the required thermoelectric conversion efficiency, the viscosity of the solution or the solid content concentration that affects printing, and the like. May be set appropriately according to the conditions.
また、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎにＣＮＴを利用する場合には、主にＣＮＴと界面活性剤とからなる熱電変換層も好適に利用される。
熱電変換層をＣＮＴと界面活性剤とで構成することにより、熱電変換層を界面活性剤を添加した塗布組成物で形成できる。そのため、熱電変換層の形成を、ＣＮＴを無理なく分散した塗布組成物で行うことができる。その結果、長くて欠陥が少ないＣＮＴを多く含む熱電変換層によって、良好な熱電変換性能が得られる。When CNT is used for the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n, a thermoelectric conversion layer mainly composed of CNT and a surfactant is also preferably used.
By configuring the thermoelectric conversion layer with CNT and a surfactant, the thermoelectric conversion layer can be formed with a coating composition to which a surfactant is added. Therefore, the thermoelectric conversion layer can be formed with a coating composition in which CNTs are dispersed without difficulty. As a result, good thermoelectric conversion performance can be obtained by the thermoelectric conversion layer containing many CNTs that are long and have few defects.
界面活性剤は、ＣＮＴを分散させる機能を有するものであれば、公知の界面活性剤を使用することができる。より具体的には、界面活性剤は、水、極性溶媒、水と極性溶媒との混合物に溶解し、ＣＮＴを吸着する基を有するものであれば、各種の界面活性剤が利用可能である。
従って、界面活性剤は、イオン性でも非イオン性でもよい。また、イオン性の界面活性剤は、カチオン性、アニオン性および両性のいずれでもよい。
一例として、アニオン性界面活性剤としては、ドデシルベンゼンスルホン酸等のアルキルベンゼンスルホン酸塩、ドデシルフェニルエーテルスルホン酸塩等の芳香族スルホン酸系界面活性剤、モノソープ系アニオン性界面活性剤、エーテルサルフェート系界面活性剤、フォスフェート系界面活性剤およびでデオキシコール酸ナトリウムまたはコール酸ナトリウム等のカルボン酸系界面活性剤、カルボキシメチルセルロースおよびその塩（ナトリウム塩、アンモニウム塩等）、ポリスチレンスルホン酸アンモニウム塩、ポリスチレンスルホン酸ナトリウム塩等の水溶性ポリマー等が例示される。As the surfactant, a known surfactant can be used as long as it has a function of dispersing CNTs. More specifically, various surfactants can be used as long as they have a group that dissolves in water, a polar solvent, or a mixture of water and a polar solvent and adsorbs CNT.
Thus, the surfactant may be ionic or non-ionic. The ionic surfactant may be cationic, anionic or amphoteric.
As an example, anionic surfactants include alkyl benzene sulfonic acid salts such as dodecyl benzene sulfonic acid, aromatic sulfonic acid type surfactants such as dodecyl phenyl ether sulfonic acid salt, monosoap type anionic surfactant, ether sulfate Surfactants, phosphate surfactants and carboxylic acid surfactants such as sodium deoxycholate or sodium cholate, carboxymethylcellulose and its salts (sodium salt, ammonium salt, etc.), ammonium polystyrene sulfonate, Examples thereof include water-soluble polymers such as polystyrene sulfonic acid sodium salt.
カチオン性界面活性剤としては、アルキルアミン塩、第四級アンモニウム塩等が例示される。両性界面活性剤としては、アルキルベタイン系界面活性剤、アミンオキサイド系界面活性剤等が例示される。
さらに、非イオン性界面活性剤としては、ソルビタン脂肪酸エステル等の糖エステル系界面活性剤、ポリオキシエチレン樹脂酸エステルどの脂肪酸エステル系界面活性剤、ポリオキシエチレンアルキルエーテル等のエーテル系界面活性剤等が例示される。
中でも、イオン性の界面活性剤は好適に利用され、その中でも、コール酸塩またはデオキシコール酸塩は好適に利用される。Examples of the cationic surfactant include an alkylamine salt and a quaternary ammonium salt. Examples of the amphoteric surfactant include an alkyl betaine-based surfactant and an amine oxide-based surfactant.
Examples of nonionic surfactants include sugar ester surfactants such as sorbitan fatty acid esters, fatty acid ester surfactants such as polyoxyethylene resin acid esters, and ether surfactants such as polyoxyethylene alkyl ether. Is exemplified.
Among them, ionic surfactants are preferably used, and among them, cholate or deoxycholate is preferably used.
ＣＮＴと界面活性剤とを有する熱電変換層においては、界面活性剤／ＣＮＴの質量比が５以下であるのが好ましく、３以下であるのがより好ましい。
界面活性剤／ＣＮＴの質量比を５以下とすることにより、より高い熱電変換性能が得られる等の点で好ましい。In the thermoelectric conversion layer having CNT and surfactant, the mass ratio of surfactant / CNT is preferably 5 or less, more preferably 3 or less.
The surfactant / CNT mass ratio of 5 or less is preferable in that higher thermoelectric conversion performance can be obtained.
なお、有機材料からなる熱電変換層は、必要に応じて、ＳｉＯ2、ＴｉＯ2、Ａｌ2Ｏ3、ＺｒＯ2等の無機材料を有してもよい。
なお、熱電変換層が、無機材料を含有する場合には、その含有量は２０質量％以下であるのが好ましく、１０質量％以下であるのがより好ましい。Note that the thermoelectric conversion layer made of an organic material may have an inorganic material such as SiO 2 , TiO 2 , Al 2 O 3 , or ZrO 2 as necessary.
In addition, when the thermoelectric conversion layer contains an inorganic material, the content is preferably 20% by mass or less, more preferably 10% by mass or less.
このようなｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎは、公知の方法で形成すればよい。一例として、以下の方法が例示される。
まず、熱電変換材料と、界面活性剤などの必要な成分とを含有する、熱電変換層を形成するための塗布組成物を調製する。
次いで、調製した熱電変換層となる塗布組成物を、形成する熱電変換層に応じてパターンニングして塗布する。この塗布組成物の塗布は、マスクを使う方法、印刷法等、公知の方法で行えばよい。
塗布組成物を塗布したら、樹脂材料に応じた方法で塗布組成物を乾燥して、熱電変換層を形成する。なお、必要に応じて、塗布組成物を乾燥した後に、紫外線照射等による塗布組成物（樹脂材料）の硬化を行ってもよい。
また、絶縁性の支持体の表面全面に、調製した熱電変換層となる塗布組成物を塗布し、乾燥した後、エッチング等によって、熱電変換層をパターン形成してもよい。Such a p-type thermoelectric conversion layer 14p and an n-type thermoelectric conversion layer 16n may be formed by a known method. As an example, the following method is exemplified.
First, a coating composition for forming a thermoelectric conversion layer containing a thermoelectric conversion material and necessary components such as a surfactant is prepared.
Next, the prepared coating composition to be the thermoelectric conversion layer is applied by patterning according to the thermoelectric conversion layer to be formed. The application of the coating composition may be performed by a known method such as a method using a mask or a printing method.
After applying the coating composition, the coating composition is dried by a method appropriate for the resin material to form a thermoelectric conversion layer. If necessary, after the coating composition is dried, the coating composition (resin material) may be cured by ultraviolet irradiation or the like.
Alternatively, the prepared coating composition to be a thermoelectric conversion layer may be applied to the entire surface of the insulating support, dried, and then the thermoelectric conversion layer may be patterned by etching or the like.
なお、主にＣＮＴと界面活性剤とからなる熱電変換層を形成する場合には、塗布組成物によって熱電変換層を形成した後、熱電変換層を界面活性剤を溶解する溶剤に浸漬するか、または熱電変換層を界面活性剤を溶解する溶剤で洗浄し、その後、乾燥することで、熱電変換層を形成するのが好ましい。
これにより、熱電変換層から界面活性剤を除去して、界面活性剤／ＣＮＴの質量比が極めて小さい、より好ましくは界面活性剤が存在しない、熱電変換層を形成できる。熱電変換層は、印刷によってパターン形成することが好ましい。In the case of forming a thermoelectric conversion layer mainly composed of CNT and a surfactant, after forming the thermoelectric conversion layer with the coating composition, the thermoelectric conversion layer is immersed in a solvent that dissolves the surfactant, Alternatively, it is preferable to form the thermoelectric conversion layer by washing the thermoelectric conversion layer with a solvent that dissolves a surfactant and then drying the same.
Thereby, the surfactant can be removed from the thermoelectric conversion layer to form a thermoelectric conversion layer in which the mass ratio of surfactant / CNT is extremely small, more preferably, no surfactant is present. The thermoelectric conversion layer is preferably formed in a pattern by printing.
印刷方法は、スクリーン印刷、メタルマスク印刷、インクジェット等の公知の各種の印刷法が利用可能である。なお、ＣＮＴを含有する塗布組成物を用いて熱電変換層をパターン形成する場合は、メタルマスク印刷を用いるのがより好ましい。
印刷条件は、用いる塗布組成物の物性（固形分濃度、粘度、粘弾性物性）、印刷版の開口サイズ、開口数、開口形状、印刷面積等により、適宜設定すればよい。As a printing method, various known printing methods such as screen printing, metal mask printing, and inkjet can be used. In the case where the thermoelectric conversion layer is patterned using a coating composition containing CNT, it is more preferable to use metal mask printing.
Printing conditions may be appropriately set depending on the physical properties (solid content, viscosity, viscoelastic physical properties) of the coating composition to be used, the opening size, the number of openings, the opening shape, the printing area, and the like of the printing plate.
なお、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎを、前述のニッケルやニッケル合金、ＢｉＴｅ系材料等の無機材料で形成する場合には、このような塗布組成物を用いる形成方法以外にも、スパッタリング法、ＣＶＤ(Chemical Vapor Deposition)法、蒸着法、メッキ法またはエアロゾルデポジッション法等の成膜方法を用いて、熱電変換層を形成することも可能である。 In the case where the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n are formed of the above-described inorganic material such as nickel, a nickel alloy, and a BiTe-based material, other than the formation method using the coating composition, Also, the thermoelectric conversion layer can be formed by a film forming method such as a sputtering method, a CVD (Chemical Vapor Deposition) method, a vapor deposition method, a plating method, or an aerosol deposition method.
ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの大きさは、第１モジュール１０Ａの大きさ、第１基板１２Ａの幅、接続電極１８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、大きさとは、第１基板１２Ａの面方向の大きさである。
なお、前述のように、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎは、長手方向には同じ長さである。また、熱電変換層は、一定間隔で形成されるので、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎは、同間隔で交互に形成される。The size of the p-type thermoelectric conversion layer 14p and the size of the n-type thermoelectric conversion layer 16n may be appropriately set according to the size of the first module 10A, the width of the first substrate 12A, the size of the connection electrode 18, and the like. . In the present invention, the size is a size in the plane direction of the first substrate 12A.
Note that, as described above, the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n have the same length in the longitudinal direction. Since the thermoelectric conversion layers are formed at regular intervals, the p-type thermoelectric conversion layers 14p and the n-type thermoelectric conversion layers 16n are alternately formed at the same intervals.
ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの厚さは、熱電変換層の形成材料等に応じて、適宜、設定すればよいが、１〜２０μｍが好ましく、３〜１５μｍがより好ましい。
ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの厚さを、この範囲とすることにより、良好な電気伝導性が得られる、良好な印刷適性が得られる等の点で好ましい。
なお、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとは、厚さが同じでも異なってもよいが、基本的に、同じ厚さである。The thickness of the p-type thermoelectric conversion layer 14p and the thickness of the n-type thermoelectric conversion layer 16n may be appropriately set according to the material for forming the thermoelectric conversion layer, but are preferably 1 to 20 μm, more preferably 3 to 15 μm.
By setting the thickness of the p-type thermoelectric conversion layer 14p and the thickness of the n-type thermoelectric conversion layer 16n within this range, it is preferable in that good electric conductivity is obtained, good printability is obtained, and the like.
The p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n may have the same or different thicknesses, but have basically the same thickness.
第１モジュール１０Ａにおいて、第１基板１２Ａのｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの形成面には、接続電極１８が形成される。接続電極１８は、本発明における電極対である。
接続電極１８は、長手方向に交互に形成されたｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを直列で電気的に接続するものである。前述のように、図示例において、熱電変換層は、長手方向に一定長さのものが一定間隔で形成される。従って、接続電極１８も、一定長さのものが一定間隔で形成される。また、第１モジュール１０Ａは、接続電極１８の長手方向の中心で、幅方向に平行な折り返し線で山折りおよび谷折りで折り返される。In the first module 10A, a connection electrode 18 is formed on a surface of the first substrate 12A on which the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n are formed. The connection electrode 18 is an electrode pair in the present invention.
The connection electrode 18 electrically connects the p-type thermoelectric conversion layers 14p and the n-type thermoelectric conversion layers 16n alternately formed in the longitudinal direction in series. As described above, in the illustrated example, the thermoelectric conversion layers are formed at a constant length in the longitudinal direction at a constant interval. Therefore, the connection electrodes 18 having a fixed length are formed at fixed intervals. Further, the first module 10A is folded at the center of the connection electrode 18 in the longitudinal direction by a folding line parallel to the width direction in a mountain fold and a valley fold.
接続電極１８の形成材料は、必要な導電率を有するものであれば、各種の導電性材料で形成可能である。
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。
また、接続電極１８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 material for forming the connection electrode 18 can be formed of various conductive materials as long as the material has a necessary conductivity.
Specifically, various materials such as metal materials such as copper, silver, gold, platinum, nickel, aluminum, constantan, chromium, indium, iron, and copper alloy, indium tin oxide (ITO) and zinc oxide (ZnO). Materials used as transparent electrodes are exemplified. Among them, copper, gold, silver, platinum, nickel, copper alloy, aluminum, constantan and the like are preferably exemplified, and copper, gold, silver, platinum and nickel are more preferably exemplified.
Further, the connection electrode 18 may be a laminated electrode such as a configuration in which a copper layer is formed on a chromium layer.
接続電極１８は、熱電変換層の形成と同様、真空蒸着やスパッタリング等の気相成膜法や印刷等の塗布法など、接続電極１８の形成材料に応じた公知の方法でパターン形成すればよい。 Similar to the formation of the thermoelectric conversion layer, the connection electrode 18 may be patterned by a known method according to the material for forming the connection electrode 18, such as a vapor deposition method such as vacuum evaporation or sputtering, or a coating method such as printing. .
接続電極１８の大きさは、第１モジュール１０Ａの大きさ、第１基板１２Ａの幅、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの大きさ、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとの間隔等に応じて、適宜、設定すればよい。
また、接続電極１８の厚さは、形成材料に応じて、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを十分な導電性を確保できる厚さを、適宜、設定すればよい。The size of the connection electrode 18 is the size of the first module 10A, the width of the first substrate 12A, the size of the p-type thermoelectric conversion layer 14p and the size of the n-type thermoelectric conversion layer 16n, the p-type thermoelectric conversion layer 14p and the n-type thermoelectric What is necessary is just to set suitably according to the space | interval with the conversion layer 16n, etc.
In addition, the thickness of the connection electrode 18 may be appropriately set to a thickness that can secure sufficient conductivity between the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n according to the material to be formed.
第１モジュール１０Ａ（第２モジュール１０Ｂ）は、公知の方法で作製できる。
一例として、平板状の長尺な第１基板１２Ａに、印刷法等の形成材料に応じた公知の方法で熱電変換層および接続電極１８をパターニングして形成する。その後、プレス加工や突起を用いるロールによる加工など、公知のシート状物の折り曲げ加工を行って、蛇腹状に折り返して、蛇腹状の第１モジュール１０Ａとする。
また、これらの操作は、第１基板１２Ａ（被処理基板）を長手方向に搬送しつつ各種の処理を連続的に行う、いわゆるロール・トゥ・ロールで行うのが好ましい。The first module 10A (the second module 10B) can be manufactured by a known method.
As an example, the thermoelectric conversion layer and the connection electrode 18 are formed by patterning on a long plate-like first substrate 12A by a known method according to a forming material such as a printing method. Thereafter, a known sheet-like material is bent, such as pressing or processing using a roll using projections, and folded into a bellows shape to obtain a bellows-like first module 10A.
In addition, it is preferable that these operations be performed by a so-called roll-to-roll process in which various processes are continuously performed while the first substrate 12A (substrate to be processed) is transported in the longitudinal direction.
図１〜図３に示す本発明の熱電変換モジュール１０は、このような第１モジュール１０Ａと第２モジュール１０Ｂとを組み合わせたものである。
ここで、図示例の熱電変換モジュール１０においては、第１モジュール１０Ａと第２モジュール１０Ｂとで、蛇腹状の折り返しの方向が逆になる。すなわち、山折りと谷折りとの順番が、逆になる。
具体的には、図３の上段から中段に示すように、右側の第１モジュール１０Ａでは、熱電変換層間の接続電極１８における蛇腹状の折り返しは、図中左側から、谷折り−山折り−谷折り−山折り−谷折り、となる。これに対し、左側の第２モジュール１０Ｂでは、熱電変換層間の接続電極１８における蛇腹状の折り返しは、図中左側から、山折り−谷折り−山折り−谷折り−山折り、となる。The thermoelectric conversion module 10 of the present invention shown in FIGS. 1 to 3 is a combination of such a first module 10A and a second module 10B.
Here, in the thermoelectric conversion module 10 of the illustrated example, the bellows-like folded direction is reversed between the first module 10A and the second module 10B. That is, the order of the mountain fold and the valley fold is reversed.
Specifically, as shown from the upper stage to the middle stage in FIG. 3, in the first module 10A on the right side, the bellows-like fold of the connection electrode 18 between the thermoelectric conversion layers is performed from the left side in the figure, namely, valley fold-mountain fold-valley. Fold-mountain fold-valley fold. On the other hand, in the second module 10B on the left side, the bellows-like fold at the connection electrodes 18 between the thermoelectric conversion layers is, from the left side in the figure, mountain fold-valley fold-mountain fold-valley fold-mountain fold.
次いで、図３の中段に示すように、右側の第１モジュール１０Ａを上下反転して、第１基板１２Ａを図中上方とする。
さらに、図３の下段（図１および図２）に示すように、第１モジュール１０Ａのｐ型熱電変換層１４ｐと第２モジュール１０Ｂのｐ型熱電変換層１４ｐとが対面し、第１モジュール１０Ａのｎ型熱電変換層１６ｎと第２モジュール１０Ｂのｎ型熱電変換層１６ｎとが対面した状態にして、第１モジュール１０Ａの谷折り部（谷部）と、第２モジュール１０Ｂの山折り部（頂部）とを一致し、第１モジュール１０Ａの山折り部（頂部）と、第２モジュール１０Ｂの谷折り部（谷部）とを一致して、第１モジュール１０Ａと第２モジュール１０Ｂとを積層する。Next, as shown in the middle part of FIG. 3, the first module 10A on the right is turned upside down to make the first substrate 12A upward in the figure.
Further, as shown in the lower part of FIG. 3 (FIGS. 1 and 2), the p-type thermoelectric conversion layer 14p of the first module 10A and the p-type thermoelectric conversion layer 14p of the second module 10B face each other, and the first module 10A The n-type thermoelectric conversion layer 16n of the second module 10B and the n-type thermoelectric conversion layer 16n of the second module 10B face each other, and a valley fold (valley) of the first module 10A and a valley fold (valley) of the second module 10B ( The first module 10A and the second module 10B are stacked by matching the crests (tops) of the first module 10A and the crests (valleys) of the second module 10B. I do.
これにより、本発明の熱電変換モジュール１０が形成される。
このような本発明の熱電変換モジュールは、図４の等価回路に示すような、交互に並列の熱電変換素子が接続された、熱電変換モジュールとなる。
なお、本発明の熱電変換モジュール１０は、第１モジュール１０Ａと第２モジュール１０Ｂとを重ねた状態で、幅方向の端部を、ガスバリア性の高い公知の材料によって封止するのが好ましい。これにより、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎを、大気中の水分、硫化物ガス、窒素酸化物等に起因する劣化から防ぐことができ、熱電変換モジュール１０の耐久性を向上させることができる。Thereby, the thermoelectric conversion module 10 of the present invention is formed.
Such a thermoelectric conversion module of the present invention is a thermoelectric conversion module in which parallel thermoelectric conversion elements are alternately connected as shown in the equivalent circuit of FIG.
In the thermoelectric conversion module 10 of the present invention, it is preferable that the first module 10 </ b> A and the second module 10 </ b> B are overlapped with each other, and the end in the width direction is sealed with a known material having high gas barrier properties. Thereby, the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n can be prevented from deterioration caused by moisture, sulfide gas, nitrogen oxide, and the like in the atmosphere, and the durability of the thermoelectric conversion module 10 is improved. Can be done.
従って、本発明の熱電変換モジュール１０は、『ｐ型熱電変換層１４ｐ−ｐ型熱電変換層１４ｐ−第１基板１２Ａ（第１層）−第１基板１２Ａ（第１層）−ｎ型熱電変換層１６ｎ−ｎ型熱電変換層１６ｎ−第２基板１２Ｂ（第２層）−第２基板１２Ｂ（第２層）』のパターンを、繰り返し有する構成となる。
より具体的には、本発明の熱電変換モジュール１０は、『第２モジュール１０Ｂのｐ型熱電変換層１４ｐ−第１モジュール１０Ａのｐ型熱電変換層１４ｐ−第１基板１２Ａ−第１基板１２Ａ−第１モジュール１０Ａのｎ型熱電変換層１６ｎ−第２モジュール１０Ｂのｎ型熱電変換層１６ｎ−第２基板１２Ｂ−第２基板１２Ｂ』のパターンを、繰り返し有する構成となる。Therefore, the thermoelectric conversion module 10 according to the present invention is configured as follows: “p-type thermoelectric conversion layer 14p-p-type thermoelectric conversion layer 14p-first substrate 12A (first layer) -first substrate 12A (first layer) -n-type thermoelectric conversion Layer 16n-n type thermoelectric conversion layer 16n-second substrate 12B (second layer) -second substrate 12B (second layer) "pattern is repeated.
More specifically, the thermoelectric conversion module 10 of the present invention is configured such that "the p-type thermoelectric conversion layer 14p of the second module 10B-the p-type thermoelectric conversion layer 14p of the first module 10A-the first substrate 12A-the first substrate 12A- The pattern of “the n-type thermoelectric conversion layer 16n of the first module 10A-the n-type thermoelectric conversion layer 16n of the second module 10B-the second substrate 12B-the second substrate 12B” is repeated.
図１〜図３に示されるように、本発明の熱電変換モジュール１０は、外側が第１基板１２Ａおよび第２基板１２Ｂとなった状態で、ｐ型熱電変換層１４ｐ同士を対面し、かつ、ｎ型熱電変換層１６ｎ同士を対面して第１モジュール１０Ａと第２モジュール１０Ｂとを積層している。そのため、絶縁シート等の絶縁部材および絶縁層など、絶縁のための部材を別途設けなくても、蛇腹を長手方向に圧縮して閉じた際に、熱電変換層および接続電極１８の短絡を防止でき、基板の利用効率も向上できる。
また、基本的に蛇腹状に折り返された第１モジュール１０Ａおよび第２モジュール１０Ｂのみで構成されるので、すなわち、発電に寄与しない余分な部材がない、効率の良い熱電変換モジュールを実現できる。
また、外側が第１基板１２Ａおよび第２基板１２Ｂであるので、これが保護部材として作用するため、ｐ型熱電変換層１４ｐ、ｎ型熱電変換層１６ｎおよび接続電極１８の損傷も防止できる。
さらに、第１モジュール１０Ａと第２モジュール１０Ｂとで、熱電変換材同士や接続電極同士を接触した状態にできるので、一方のモジュールで断線等が生じた場合でも、電気は他方を流れることができるので、断線故障等も大幅に低減できる。As shown in FIGS. 1 to 3, the thermoelectric conversion module 10 of the present invention faces the p-type thermoelectric conversion layers 14 p in a state where the outside is the first substrate 12 </ b> A and the second substrate 12 </ b> B, and The first module 10A and the second module 10B are stacked with the n-type thermoelectric conversion layers 16n facing each other. Therefore, without separately providing an insulating member such as an insulating member such as an insulating sheet and an insulating layer, a short circuit of the thermoelectric conversion layer and the connection electrode 18 can be prevented when the bellows is compressed in the longitudinal direction and closed. Also, the utilization efficiency of the substrate can be improved.
In addition, since it is basically composed only of the first module 10A and the second module 10B folded in a bellows shape, an efficient thermoelectric conversion module having no extra members that do not contribute to power generation can be realized.
Further, since the outside is the first substrate 12A and the second substrate 12B, which act as a protection member, damage to the p-type thermoelectric conversion layer 14p, the n-type thermoelectric conversion layer 16n, and the connection electrode 18 can also be prevented.
Furthermore, since the thermoelectric conversion materials and the connection electrodes can be brought into contact with each other in the first module 10A and the second module 10B, even if a disconnection or the like occurs in one module, electricity can flow through the other module. Therefore, disconnection failures and the like can be greatly reduced.
しかも、熱電変換モジュール１０は、可撓性を有する第１基板１２Ａおよび第２基板１２Ｂを用いて形成されるので、良好な可撓性を有する。そのため、長手方向に折り曲げることが可能であり、例えば、曲面状に湾曲させた状態にして管状の熱源に装着する等、様々な形状の熱源に装着することが可能である。
加えて、熱電変換層等をロール・トゥ・ロールを利用して印刷等によって形成できるので、生産性も良好である。Moreover, since the thermoelectric conversion module 10 is formed using the flexible first substrate 12A and second substrate 12B, the thermoelectric conversion module 10 has good flexibility. Therefore, it can be bent in the longitudinal direction, and can be attached to various shapes of heat sources, for example, can be attached to a tubular heat source in a curved state.
In addition, since the thermoelectric conversion layer and the like can be formed by printing or the like using roll-to-roll, productivity is good.
図１〜図３に示す熱電変換モジュール１０は、２枚の基板を用いて本発明の第１層および第２層としたが、本発明は、これに限定はされない。
一例として、図５に示す構成が例示される。Although the thermoelectric conversion module 10 shown in FIGS. 1 to 3 uses the two substrates as the first layer and the second layer of the present invention, the present invention is not limited to this.
As an example, the configuration shown in FIG. 5 is exemplified.
この構成は、図５の上段に示すように、１枚の基板２０に、幅方向（蛇腹状の折り返しと直交する方向）に並べて、第１モジュール１０Ａおよび第２モジュール１０Ｂと同様のｐ型熱電変換層１４ｐ、接続電極１８およびｎ型熱電変換層１６ｎの配列を形成する。
次いで、図５の中段に示すように、ｐ型熱電変換層１４ｐ、接続電極１８およびｎ型熱電変換層１６ｎの配列の中間（一点鎖線）を折り線として、熱電変換層の形成面を内側に、基板２０を折り曲げる。これにより、１枚の基板２０が、図中上側の第１層２０Ａおよび図中下側の第２層２０Ｂとなる。
最後に、図５の下段に示すように、折り曲げた基板２０すなわち第１層２０Ａおよび第２層２０Ｂを交互に折り返して蛇腹状にすることにより、第１層２０Ａおよび第２層２０Ｂが折り曲げた１枚の基板２０からなる以外は、図１〜図３に示す熱電変換モジュール１０と同様の構成を有する熱電変換モジュール２４とする。This configuration is similar to the p-type thermoelectric module of the first module 10A and the second module 10B arranged in the width direction (direction orthogonal to the bellows-like folding) on one substrate 20, as shown in the upper part of FIG. An array of the conversion layer 14p, the connection electrode 18, and the n-type thermoelectric conversion layer 16n is formed.
Next, as shown in the middle part of FIG. 5, the middle of the arrangement of the p-type thermoelectric conversion layer 14p, the connection electrode 18 and the n-type thermoelectric conversion layer 16n (dashed line) is taken as a folding line, and the surface on which the thermoelectric conversion layer is formed faces inward Then, the substrate 20 is bent. Thus, one substrate 20 becomes the first layer 20A on the upper side in the figure and the second layer 20B on the lower side in the figure.
Finally, as shown in the lower part of FIG. 5, the bent substrate 20, that is, the first layer 20A and the second layer 20B are alternately turned into a bellows shape, whereby the first layer 20A and the second layer 20B are bent. A thermoelectric conversion module 24 having the same configuration as the thermoelectric conversion module 10 shown in FIGS.
なお、図５に示す熱電変換モジュール２４において、基板２０は、前述の第１基板１２Ａ等と同様の、可撓性および絶縁性を有するシート状物が、各種、利用可能である。 In the thermoelectric conversion module 24 illustrated in FIG. 5, as the substrate 20, various kinds of flexible and insulating sheet-like materials similar to the above-described first substrate 12 </ b> A and the like can be used.
本発明の熱電変換モジュール１０（熱電変換モジュール２４）は、図６に概念的に示すように、第１基板１２Ａおよび第２基板１２Ｂに形成される貫通孔２８を貫通して、可撓性を有するワイヤー（線状部材）２６を有してもよい。 As shown conceptually in FIG. 6, the thermoelectric conversion module 10 (thermoelectric conversion module 24) of the present invention penetrates through holes 28 formed in the first substrate 12A and the second substrate 12B to increase flexibility. May be provided.
このようなワイヤー２６を有することにより、第１モジュール１０Ａと第２モジュール１０Ｂとが解離すること防止できる。すなわち、このようなワイヤー２６を有することにより、第１層２０Ａと第２層２０Ｂとが不要に離間すること防止できる。
また、熱電変換モジュール１０のみならず、ワイヤー２６も可撓性を有するので、長手方向に折り曲げることが可能であり、例えば、曲面状に湾曲させた状態にして管状の熱源に装着する等、様々な形状の熱源に装着することが可能である。
第１基板１２Ａおよび第２基板１２Ｂを挿通するのが、ワイヤー２６であるので、長手方向に押圧して容易に蛇腹を閉じることができ、さらに、押圧状態による圧縮の程度すなわち蛇腹の凹凸の間隔（蛇腹の間隔）も、全体的あるいは部分的に、容易に変更できる。
そのため、ワイヤー２６を有することにより、取り扱いが良好であり、曲面や屈折している面などの様々な形状の熱源に装着する際にも、良好な作業性で装着を行うことができる熱電変換モジュールが得られる。By having such a wire 26, the first module 10A and the second module 10B can be prevented from being dissociated. That is, having such a wire 26 can prevent the first layer 20A and the second layer 20B from being unnecessarily separated.
In addition, since not only the thermoelectric conversion module 10 but also the wire 26 has flexibility, it can be bent in the longitudinal direction. For example, the wire 26 can be bent in a curved shape and attached to a tubular heat source. It can be attached to a heat source of various shapes.
Since the wire 26 penetrates the first substrate 12A and the second substrate 12B, the bellows can be easily closed by pressing in the longitudinal direction, and the degree of compression due to the pressed state, that is, the interval between the unevenness of the bellows (The interval between bellows) can also be easily or wholly or partially changed.
Therefore, by having the wire 26, the thermoelectric conversion module is excellent in handling and can be mounted with good workability even when mounted on a heat source having various shapes such as a curved surface or a curved surface. Is obtained.
本発明の熱電変換モジュール１０において、ワイヤー２６は、可撓性を有する線状部材が、各種、利用可能である。具体的には、糸（紐）、針金などの金属線、絶縁材料で被覆された金属線などが例示される。 In the thermoelectric conversion module 10 of the present invention, various types of flexible linear members can be used for the wire 26. Specifically, a metal wire such as a thread (string) or a wire, a metal wire covered with an insulating material, and the like are exemplified.
本発明の熱電変換モジュールにおいて、第１基板１２Ａおよび第２基板１２Ｂにおけるワイヤー２６の挿通位置、すなわち、ワイヤー２６を挿通する貫通孔２８の位置には特に限定はない。
しかしながら、第１基板１２Ａおよび第２基板１２Ｂ（第１モジュール１０Ａおよび第２モジュール１０Ｂ）共に、貫通孔２８の位置は、ｐ型熱電変換層１４ｐおよびｎ型熱電変換層１６ｎの形成部以外であるのが好ましく、さらに、接続電極１８の形成部以外であるのがより好ましい。これにより、熱電変換層や電極の面積が低減することを防止し、また、熱電変換モジュール１０の強度も確保できる。さらに、電気伝導性を有するワイヤー２６を用いた場合でも、熱電変換層や電極とワイヤーとの間で短絡が生じることを防止できる。In the thermoelectric conversion module of the present invention, there is no particular limitation on the position where the wire 26 is inserted in the first substrate 12A and the second substrate 12B, that is, the position of the through hole 28 where the wire 26 is inserted.
However, in both the first substrate 12A and the second substrate 12B (the first module 10A and the second module 10B), the position of the through hole 28 is other than the formation part of the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n. It is more preferable that the portion is other than the portion where the connection electrode 18 is formed. This prevents the areas of the thermoelectric conversion layer and the electrodes from being reduced, and also ensures the strength of the thermoelectric conversion module 10. Furthermore, even when the wire 26 having electric conductivity is used, it is possible to prevent a short circuit from occurring between the thermoelectric conversion layer or the electrode and the wire.
特に、ワイヤー２６の挿通位置すなわちワイヤー２６を挿通する貫通孔２８は、図７に概念的に示すように、幅方向には接続電極１８の外側で、かつ、長手方向には接続電極１８と同じ位置とするのが好ましい。幅方向とは、すなわち、蛇腹状の折り返しにおける稜線の長手方向である。また、長手方向とは、すなわち、蛇腹状の折り返し方向である。
熱電変換モジュール１０を長手方向に押圧して、図１等に示すように蛇腹を閉じた場合（蛇腹を畳んだ場合）には、ワイヤー２６で縛って、蛇腹を閉じた状態を維持することが考えられる。そのため、図示例のように、幅方向に接続電極１８の外側で、長手方向に接続電極１８と同じ位置にワイヤー２６を挿通することにより、蛇腹を閉じた際に、通常、金属材料で形成される接続電極１８を密着させることができ、幅方向および長手方向における熱電変換層の温度ムラを小さくして、効率の良い発電を行うことができる。In particular, the insertion position of the wire 26, that is, the through hole 28 through which the wire 26 is inserted is, as conceptually shown in FIG. 7, outside the connection electrode 18 in the width direction and the same as the connection electrode 18 in the longitudinal direction. It is preferable to set the position. The width direction is the longitudinal direction of the ridgeline in the bellows-like folding. The longitudinal direction is, in other words, a bellows-like folding direction.
When the thermoelectric conversion module 10 is pressed in the longitudinal direction and the bellows is closed as shown in FIG. 1 and the like (when the bellows is folded), it is possible to keep the bellows closed by binding with the wire 26. Conceivable. Therefore, when the bellows is closed by inserting the wire 26 at the same position as the connection electrode 18 in the longitudinal direction outside the connection electrode 18 in the width direction, as shown in the illustrated example, it is usually formed of a metal material. The connection electrodes 18 can be brought into close contact with each other, the temperature unevenness of the thermoelectric conversion layer in the width direction and the longitudinal direction can be reduced, and efficient power generation can be performed.
ワイヤー２６を挿通する貫通孔２８は、好ましくは、第１基板１２Ａおよび第２基板１２Ｂを蛇腹状に折り返した際に、長手方向に直線状になる位置に形成するのが好ましい。すなわち、貫通孔２８は、好ましくは、第１基板１２Ａを蛇腹状に折り返した際に、長手方向に長尺な一本の直線が挿通できる位置に形成するのが好ましい。
さらに、貫通孔２８は、第１モジュール１０Ａと第２モジュール１０Ｂとを積層した際に、第１基板１２Ａの貫通孔２８と第２基板１２Ｂの貫通孔２８とが長手方向に直線状になる位置に形成するのが好ましい。The through hole 28 through which the wire 26 is inserted is preferably formed at a position where the first substrate 12A and the second substrate 12B become linear in the longitudinal direction when the second substrate 12B is folded in a bellows shape. That is, it is preferable that the through hole 28 is formed at a position where a single long straight line can be inserted in the longitudinal direction when the first substrate 12A is folded back in a bellows shape.
Further, the through hole 28 is a position where the through hole 28 of the first substrate 12A and the through hole 28 of the second substrate 12B become linear in the longitudinal direction when the first module 10A and the second module 10B are stacked. It is preferable to form it.
なお、図７において、符号２８ａは、必要に応じて設けられる貫通孔２８を補強するための補強部材である。補強部材２８ａは、例えば金属や樹脂材料等の公知の孔部の補強部材を用いて形成すればよい。
また、図７において、第１基板１２Ａと第２基板１２Ｂとでは、貫通孔２８が形成された位置における山折りと谷折りとが逆になる。In FIG. 7, reference numeral 28a is a reinforcing member for reinforcing the through-hole 28 provided as needed. The reinforcing member 28a may be formed using a well-known reinforcing member having a hole, such as a metal or a resin material.
In FIG. 7, the first substrate 12A and the second substrate 12B have the mountain fold and the valley fold at the positions where the through holes 28 are formed reversed.
本発明の熱電変換モジュール１０（熱電変換モジュール２４）は、放熱フィンなどの、熱伝導部材を有しても良い。
熱伝導部材は、図８に概念的に示すような板状の熱伝導部材３２でもよく、あるいは、図９に概念的に示すような蛇腹状の熱伝導部材３６でもよい。あるいは、板状の熱伝導部材３２と蛇腹状の熱伝導部材３６とを、併用してもよい。The thermoelectric conversion module 10 (thermoelectric conversion module 24) of the present invention may have a heat conducting member such as a radiation fin.
The heat conducting member may be a plate-like heat conducting member 32 as conceptually shown in FIG. 8 or a bellows-like heat conducting member 36 as conceptually shown in FIG. Alternatively, the plate-shaped heat conductive member 32 and the bellows-shaped heat conductive member 36 may be used in combination.
熱伝導部材３２および熱伝導部材３６の形成材料は、いわゆる放熱フィン等で利用されている各種の物が利用可能である。具体的には、銅やアルミニウムなどの各種の金属材料、アルミナ、窒化ホウ素、窒化アルミニウムなどの無機化合物、グラファイトなどのカーボン材等が例示される。中でも、銅やアルミニウムなどの金属材料は好適に利用される。
また、蛇腹状の熱伝導部材３６は、プレス加工や突起を用いるロールによる加工など、公知のシート状物の折り曲げ加工で作製すればよい。As a material for forming the heat conductive member 32 and the heat conductive member 36, various materials used for so-called heat radiation fins or the like can be used. Specific examples include various metal materials such as copper and aluminum, inorganic compounds such as alumina, boron nitride, and aluminum nitride, and carbon materials such as graphite. Among them, metal materials such as copper and aluminum are preferably used.
In addition, the bellows-like heat conducting member 36 may be manufactured by bending a known sheet-like material such as press working or working with a roll using projections.
熱伝導部材３２および熱伝導部材３６は、放熱側に設けてもよく、高温熱源側に設けてもよく、放熱側および高温熱伝導側の両方に設けてもよい。
ここで、板状の熱伝導部材３２および蛇腹状の熱伝導部材３６は、共に、図８および図９に示すように、第１基板１２Ａと第１基板１２Ａとの間、および／または、第２基板１２Ｂと第２基板１２Ｂとの間に挿入して設けるのが好ましい。特に、板状の熱伝導部材３２および／または蛇腹状の熱伝導部材３６は、共に、長手方向（蛇腹状の折り返し方向）に、接続電極１８と対面する位置に設けられるのが好ましい。
熱伝導部材を、第１基板１２Ａと第１基板１２Ａとの間、および／または、第２基板１２Ｂと第２基板１２Ｂとの間に挿入して設けることにより、熱電変換モジュール１０と熱伝導部材との間における熱伝導（熱交換）の効率を向上して、熱源からの熱の利用効率や放熱効率を向上できる。さらに、前述のように、接続電極１８は、通常、金属性であるので、熱伝導部材を接続電極１８と長手方向に対面して設けることで、大幅に熱伝導効率を向上して、熱源からの熱の利用効率や放熱効率を、大幅に向上できる。The heat conductive member 32 and the heat conductive member 36 may be provided on the heat radiating side, may be provided on the high temperature heat source side, or may be provided on both the heat radiating side and the high temperature heat conductive side.
Here, the plate-shaped heat conductive member 32 and the bellows-shaped heat conductive member 36 are both disposed between the first substrate 12A and the first substrate 12A and / or as shown in FIGS. It is preferable to insert and provide between the second substrate 12B and the second substrate 12B. In particular, it is preferable that both the plate-like heat conductive member 32 and / or the bellows-like heat conductive member 36 are provided at positions facing the connection electrode 18 in the longitudinal direction (the bellows-like folding direction).
By providing the heat conducting member between the first substrate 12A and the first substrate 12A and / or between the second substrate 12B and the second substrate 12B, the thermoelectric conversion module 10 and the heat conducting member are provided. The efficiency of heat conduction (heat exchange) between the heat source and the heat source can be improved, and the efficiency of using and radiating heat from the heat source can be improved. Further, as described above, since the connection electrode 18 is usually made of metal, by providing a heat conductive member facing the connection electrode 18 in the longitudinal direction, the heat conduction efficiency is greatly improved, and the connection from the heat source is improved. The heat use efficiency and heat dissipation efficiency of the heat can be greatly improved.
以上の熱電変換モジュールは、好ましい態様として、第１モジュール１０Ａおよび第２モジュール１０Ｂ（第１層および第２層）共に、接続電極１８がｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを接続している。
しかしながら、本発明は、これに限定はされず、第１モジュール１０Ａおよび第２モジュール１０Ｂのいずれか一方において、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを接続する接続電極１８ではなく、ｐ型熱電変換層１４ｐを挟む電極対と、ｎ型熱電変換層１６ｎとを挟む電極対とを有する構成であってもよい。In a preferred embodiment of the above-described thermoelectric conversion module, the connection electrodes 18 of both the first module 10A and the second module 10B (the first and second layers) include the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n. Connected.
However, the present invention is not limited to this, and instead of the connection electrode 18 for connecting the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n in one of the first module 10A and the second module 10B. , An electrode pair sandwiching the p-type thermoelectric conversion layer 14p and an electrode pair sandwiching the n-type thermoelectric conversion layer 16n.
例えば、図１０に示す熱電変換モジュール１０ａのように、第２モジュール１０Ｂａが、ｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを接続する接続電極を有さず、長手方向（蛇腹状の折り返し方向）にｐ型熱電変換層１４ｐを挟んで電極対を構成する電極３８と、長手方向にｎ型熱電変換層１６ｎを挟んで電極対を構成する電極３８とを有する構成であってもよい。
本発明においては、このように、第２モジュール１０Ｂａにおいてｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとが接続されていなくても、第１モジュール１０Ａの接続電極１８と第２モジュール１０Ｂａにおいて電極対を構成する電極３８とを接触させることで、第２モジュール１０Ｂａのｐ型熱電変換層１４ｐとｎ型熱電変換層１６ｎとを電気的に接続できる。For example, like the thermoelectric conversion module 10a shown in FIG. 10, the second module 10Ba does not have a connection electrode for connecting the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n, and has a longitudinal direction (bellows shape). The electrode 38 may be configured to form an electrode pair with the p-type thermoelectric conversion layer 14p interposed therebetween (in the folding direction) and the electrode 38 may be formed as an electrode pair with the n-type thermoelectric conversion layer 16n interposed in the longitudinal direction. .
In the present invention, as described above, even if the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n are not connected in the second module 10Ba, the connection electrode 18 of the first module 10A and the second module 10Ba By bringing the electrodes 38 that make up the electrode pair into contact, the p-type thermoelectric conversion layer 14p and the n-type thermoelectric conversion layer 16n of the second module 10Ba can be electrically connected.
以上の本発明の熱電変換モジュールは、いずれも、対面するｐ型熱電変換層１４ｐ同士、ｎ型熱電変換層１６ｎ同士、および、接続電極１８同士は、全面的に接触していたが、本発明は、これに限定はされず、各種の構成が利用可能である。
例えば、本発明の熱電変換モジュールにおいて、対面するｐ型熱電変換層１４ｐ同士、ｎ型熱電変換層１６ｎ同士、および、接続電極１８同士は、少なくとも１組が、完全に離間していてもよく、あるいは、部分的に接触していてもよい。また、本発明の熱電変換モジュールは、対面するｐ型熱電変換層１４ｐ同士およびｎ型熱電変換層１６ｎ同士は接触し、対面する接続電極１８同士は離間する構成、あるいは、対面するｎ型熱電変換層１６ｎ同士は接触し、対面するｐ型熱電変換層１４ｐ同士および接続電極１８同士は離間する構成、あるいは、対面するｐ型熱電変換層１４ｐ同士は接触し、対面するｎ型熱電変換層１６ｎ同士および接続電極１８同士は離間する構成等であってもよい。In each of the thermoelectric conversion modules of the present invention described above, the facing p-type thermoelectric conversion layers 14p, the n-type thermoelectric conversion layers 16n, and the connection electrodes 18 are entirely in contact with each other. However, the present invention is not limited to this, and various configurations can be used.
For example, in the thermoelectric conversion module of the present invention, at least one pair of facing p-type thermoelectric conversion layers 14p, n-type thermoelectric conversion layers 16n, and connection electrodes 18 may be completely separated, Alternatively, they may be in partial contact. In addition, the thermoelectric conversion module of the present invention has a configuration in which the facing p-type thermoelectric conversion layers 14p and the n-type thermoelectric conversion layers 16n are in contact with each other, and the facing connection electrodes 18 are separated from each other, or the facing n-type thermoelectric conversion The layers 16n are in contact with each other, and the facing p-type thermoelectric conversion layers 14p and the connection electrodes 18 are separated from each other, or the facing p-type thermoelectric conversion layers 14p are in contact with each other and the facing n-type thermoelectric conversion layers 16n are The connection electrodes 18 may be separated from each other.
以上、本発明の熱電変換モジュールについて説明したが、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良いのは、もちろんである。 Although the thermoelectric conversion module of the present invention has been described above, the present invention is not limited to the above-described example, and various improvements and changes may be made without departing from the spirit of the present invention. It is.
発電装置等に、好適に利用可能である。 The present invention can be suitably used for power generation devices and the like.
１０，１０ａ，２４ 熱電変換モジュール
１０Ａ 第１モジュール
１０Ｂ，１０Ｂａ 第２モジュール
１２Ａ 第１基板
１２Ｂ 第２基板
１４ｐ ｐ型熱電変換層
１６ｎ ｎ型熱電変換層
１８ 接続電極
２０ 基板
２０Ａ 第１層
２０Ｂ 第２層
２６ ワイヤー
２８ 貫通孔
２８ａ 補強部材
３２，３６ 熱伝導部材
３８ 電極10, 10a, 24 thermoelectric conversion module 10A first module 10B, 10Ba second module 12A first substrate 12B second substrate 14p p-type thermoelectric conversion layer 16n n-type thermoelectric conversion layer 18 connection electrode 20 substrate 20A first layer 20B second Layer 26 wire 28 through hole 28a reinforcing member 32, 36 heat conducting member 38 electrode
Claims (11)
蛇腹状に折り返された第２層、前記第２層の一方の面に前記蛇腹状の折り返し方向に離間して交互に複数形成されるｐ型熱電変換層およびｎ型熱電変換層、ならびに、前記ｐ型熱電変換層を前記蛇腹状の折り返し方向に挟む電極対および前記ｎ型熱電変換層を前記蛇腹状の折り返し方向に挟む電極対と、を有し、
前記第１層の一方の面上に形成された前記ｐ型熱電変換層と前記ｎ型熱電変換層とが前記電極対によって電気的に接続されており、もしくは、前記第２層の一方の面上に形成された前記ｐ型熱電変換層と前記ｎ型熱電変換層とが前記電極対によって電気的に接続されており、
さらに、前記蛇腹状の折り返し方向に、
前記ｐ型熱電変換層−前記ｐ型熱電変換層−前記第１層−前記第１層−前記ｎ型熱電変換層−前記ｎ型熱電変換層−前記第２層−前記第２層
のパターンを、繰り返し有することを特徴とする熱電変換モジュール。A first layer folded in a bellows shape, a plurality of p-type thermoelectric conversion layers and a plurality of n-type thermoelectric conversion layers alternately formed on one surface of the first layer so as to be spaced apart in the bellows-like folding direction, and an electrode pair sandwiching the p-type thermoelectric conversion layer in the bellows-like folding direction and an electrode pair sandwiching the n-type thermoelectric conversion layer in the bellows-like folding direction;
A second layer folded in a bellows shape, a plurality of p-type thermoelectric conversion layers and a plurality of n-type thermoelectric conversion layers alternately formed on one surface of the second layer so as to be spaced apart in the bellows-like folding direction, and an electrode pair that sandwiches the p-type thermoelectric conversion layer in the bellows-like folding direction and an electrode pair that sandwiches the n-type thermoelectric conversion layer in the bellows-like folding direction,
The p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer formed on one surface of the first layer are electrically connected by the electrode pair, or one surface of the second layer. The p-type thermoelectric conversion layer and the n-type thermoelectric conversion layer formed thereon are electrically connected by the electrode pair,
Furthermore, in the bellows-like folding direction,
The pattern of the p-type thermoelectric conversion layer-the p-type thermoelectric conversion layer-the first layer-the first layer-the n-type thermoelectric conversion layer-the n-type thermoelectric conversion layer-the second layer-the second layer A thermoelectric conversion module characterized by having a repetition.
前記第１基板の前記ｐ型熱電変換層の形成面と、前記第２基板の前記ｐ型熱電変換層の形成面とを対面して、前記第１基板と前記第２基板とが積層されている請求項１または２に記載の熱電変換モジュール。The first layer is a first substrate, the second layer is a second substrate,
The first substrate and the second substrate are stacked with the surface of the first substrate on which the p-type thermoelectric conversion layer is formed and the surface of the second substrate on which the p-type thermoelectric conversion layer is formed facing each other. The thermoelectric conversion module according to claim 1.
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