JP4867388B2 - Thermoelectric generator - Google Patents

Thermoelectric generator Download PDF

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JP4867388B2
JP4867388B2 JP2006044118A JP2006044118A JP4867388B2 JP 4867388 B2 JP4867388 B2 JP 4867388B2 JP 2006044118 A JP2006044118 A JP 2006044118A JP 2006044118 A JP2006044118 A JP 2006044118A JP 4867388 B2 JP4867388 B2 JP 4867388B2
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heat
point metal
melting point
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thermoelectric power
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JP2007227458A (en
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善樹 深田
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Toyota Motor Corp
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Description

本発明は、熱エネルギーを電気エネルギーに直接変換する熱電発電モジュールを備えた熱電発電装置に関するものである。   The present invention relates to a thermoelectric power generation apparatus including a thermoelectric power generation module that directly converts thermal energy into electric energy.

熱電発電モジュールは、ゼーベック効果により温度差に応じた熱起電力を発生するｎ型熱電発電素子およびｐ型熱電発電素子が高温側の受熱部と低温側の放熱部との間に複数個設置された構造を有し、熱エネルギーを電気エネルギーに直接変換することができる。そして、このような熱電発電モジュールの受熱部に高温熱源である適宜の熱回収部材を接触させ、その放熱部に適宜の熱放出部材を接触させることで熱電発電装置が構成される。   In the thermoelectric power generation module, a plurality of n-type thermoelectric power generation elements and p-type thermoelectric power generation elements that generate a thermoelectromotive force according to a temperature difference by the Seebeck effect are installed between a high-temperature side heat receiving part and a low-temperature side heat dissipation part. And can directly convert heat energy into electrical energy. Then, an appropriate heat recovery member, which is a high-temperature heat source, is brought into contact with the heat receiving portion of such a thermoelectric power generation module, and an appropriate heat release member is brought into contact with the heat radiating portion, thereby forming a thermoelectric generator.

この種の熱電発電モジュールを備えた熱電発電装置においては、熱回収部材から熱電発電モジュールの受熱部への熱伝導性が発電性能に大きく影響するため、一般には、熱回収部材と熱電発電モジュールの受熱部との接触面を高い平面度に仕上げ、あるいは、両者に圧力を掛けてその接触面を均一に圧接させている。   In a thermoelectric generator equipped with this type of thermoelectric power generation module, the heat conductivity from the heat recovery member to the heat receiving part of the thermoelectric power generation module greatly affects the power generation performance. The contact surface with the heat receiving part is finished with high flatness, or pressure is applied to both to bring the contact surface into uniform pressure contact.

この種の熱電発電装置として、特許文献１には、熱回収部材としてのインナシェルの集熱面と熱電発電モジュールの受熱部としての高温側の端面との間に緩衝部材を挟持した例が開示されている。そして、この特許文献１には、ステンレスなどの金属ワイヤをメッシュ状に編み込んだ金属織布を積層ないし折り畳んだものや、波板形状の金属板、金属コイルなどが緩衝部材として使用できると記載されている。
特開平１０−２３４１９４号公報（段落番号４５、４６） As this type of thermoelectric generator, Patent Document 1 discloses an example in which a buffer member is sandwiched between a heat collecting surface of an inner shell as a heat recovery member and an end surface on a high temperature side as a heat receiving portion of a thermoelectric generator module. Has been. And in this patent document 1, it describes that what laminated | stacked or folded the metal woven fabric which woven metal wires, such as stainless steel, in mesh shape, a corrugated metal plate, a metal coil, etc. can be used as a buffer member. ing.
JP-A-10-234194 (paragraph numbers 45 and 46)

ところで、特許文献１に記載された熱電発電装置においては、高温の熱がインナシェルの集熱面から金属メッシュ等で構成された緩衝部材を介して熱電発電モジュールの高温側の端面に伝導されるため、その熱伝導性が大きく損なわれて発電性能が低下する恐れがある。   By the way, in the thermoelectric power generation device described in Patent Document 1, high-temperature heat is conducted from the heat collecting surface of the inner shell to the end surface on the high-temperature side of the thermoelectric power generation module through a buffer member made of a metal mesh or the like. For this reason, the thermal conductivity is greatly impaired, and the power generation performance may be reduced.

そこで、本発明は、熱回収部材と熱電発電モジュールの受熱部との接触面を高い平面度に仕上げ、あるいはその接触面を均一に圧接させることなく、長期にわたって極めて良好に熱回収部材から熱電発電モジュールの受熱部に熱伝導できる熱電発電装置を提供することを課題とする。   In view of this, the present invention provides a very good contact between the heat recovery member and the heat receiving portion of the thermoelectric power generation module with a high degree of flatness, or the contact surface is uniformly pressed against the thermoelectric power generation from the heat recovery member over a long period of time. It is an object of the present invention to provide a thermoelectric generator that can conduct heat to a heat receiving portion of a module.

本発明に係る熱電発電装置は、熱回収手段に接触する受熱部と熱放出手段に接触する放熱部との間に複数の熱電発電素子が配置された熱電発電モジュールを備える熱電発電装置であって、熱電発電モジュールの受熱部は、高融点金属被覆で覆われた低融点金属体を介して熱回収手段に接触しており、低融点金属体中への金属成分の溶解を防止する保護膜が低融点金属体の全面を覆っていることを特徴とする。   A thermoelectric power generation device according to the present invention is a thermoelectric power generation device including a thermoelectric power generation module in which a plurality of thermoelectric power generation elements are arranged between a heat receiving portion that contacts the heat recovery means and a heat dissipation portion that contacts the heat release means. The heat receiving part of the thermoelectric power module is in contact with the heat recovery means through the low melting point metal body covered with the high melting point metal coating, and a protective film for preventing the dissolution of the metal component in the low melting point metal body is provided. It covers the entire surface of the low melting point metal body.

本発明に係る熱電発電装置では、使用状態において熱回収手段が高温となると、高融点金属被覆で覆われた低融点金属体が溶融し、この溶融した低融点金属体の柔軟性により高融点金属被覆が熱電発電モジュールの受熱部に均一な面圧で密着する。その結果、熱回収手段から熱電発電モジュールの受熱部への熱伝導が極めて良好に行われる。   In the thermoelectric generator according to the present invention, when the heat recovery means becomes high temperature in use, the low melting point metal body covered with the high melting point metal coating melts, and the high melting point metal body is melted by the flexibility of the melted low melting point metal body. The coating adheres to the heat receiving part of the thermoelectric power generation module with a uniform surface pressure. As a result, heat conduction from the heat recovery means to the heat receiving portion of the thermoelectric power generation module is performed extremely well.

そして、このような使用状態においては、低融点金属体の全面を覆っている保護膜により、溶融した低融点金属体中に高融点金属被覆や熱回収手段の金属成分が溶解するのが未然に防止されるため、低融点金属体の融点などの物性の変化および高融点金属被覆の損傷が長期にわたって防止される。従って、熱回収手段から熱電発電モジュールの受熱部への熱伝導が長期にわたって極めて良好に行われる。   In such a use state, the protective film covering the entire surface of the low-melting-point metal body causes the high-melting-point metal coating and the metal component of the heat recovery means to dissolve in the molten low-melting-point metal body. Therefore, changes in physical properties such as the melting point of the low melting point metal body and damage to the high melting point metal coating can be prevented over a long period of time. Therefore, heat conduction from the heat recovery means to the heat receiving portion of the thermoelectric power generation module is performed extremely well over a long period of time.

本発明の熱電発電装置において、高温の使用環境で溶融した低融点金属体中に高融点金属被覆や熱回収手段の金属成分が溶解するのを確実に防止するためには、低融点金属体を覆う保護膜を粘土セラミックス膜またはセラミックス溶射膜とするのが好ましい。   In the thermoelectric generator of the present invention, in order to reliably prevent the metal component of the high melting point metal coating or heat recovery means from dissolving in the low melting point metal body melted in a high temperature use environment, The covering protective film is preferably a clay ceramic film or a ceramic sprayed film.

また、本発明の熱電発電装置において、低融点金属体を覆う保護膜が粘土セラミックス膜またはセラミックス溶射膜である場合には、その焼成時における低融点金属体の形状を保持するため、低融点金属体に予め高融点金属のメッキ層を形成し、このメッキ層上に保護膜を形成するのが好ましい。   Further, in the thermoelectric power generator of the present invention, when the protective film covering the low melting point metal body is a clay ceramic film or a ceramic sprayed film, the low melting point metal body is maintained in order to maintain the shape of the low melting point metal body during firing. It is preferable to form a refractory metal plating layer on the body in advance and form a protective film on the plating layer.

本発明の熱電発電装置において、高融点金属被覆は板金により構成することができる。この場合、板金の内面は保護膜で被覆されているのが好ましい。   In the thermoelectric generator of the present invention, the refractory metal coating can be made of sheet metal. In this case, the inner surface of the sheet metal is preferably covered with a protective film.

本発明に係る熱電発電装置では、使用状態において高融点金属被覆で覆われた低融点金属体が溶融すると、この溶融した低融点金属体の柔軟性により高融点金属皮膜が熱電発電モジュールの受熱部に均一な面圧で密着する。その際、低融点金属体の全面を覆っている保護膜により、溶融した低融点金属体中に高融点金属被覆やフィン部材の金属成分が溶解するのが未然に防止されるため、低融点金属体の融点などの物性の変化および高融点金属被覆の損傷が長期にわたって防止される。   In the thermoelectric generator according to the present invention, when the low-melting point metal body covered with the high-melting point metal coating is melted in use, the high-melting point metal film is formed by the flexibility of the molten low-melting point metal body. It adheres with uniform surface pressure. At that time, the protective film covering the entire surface of the low melting point metal body prevents the metal component of the high melting point metal coating or the fin member from being dissolved in the molten low melting point metal body. Changes in physical properties such as the melting point of the body and damage to the refractory metal coating are prevented over time.

従って、本発明によれば、熱回収部材と熱電発電モジュールの受熱部との接触面を高い平面度に仕上げ、あるいはその接触面を均一に圧接させることなく、長期にわたって極めて良好に熱回収部材から熱電発電モジュールの受熱部に熱伝導できる。その結果、長期にわたって高い発電性能を発揮することができる。   Therefore, according to the present invention, the contact surface between the heat recovery member and the heat receiving portion of the thermoelectric power generation module is finished with a high flatness, or the contact surface is uniformly pressed from the heat recovery member over a long period of time. Heat can be transferred to the heat receiving part of the thermoelectric generator module. As a result, high power generation performance can be exhibited over a long period of time.

本発明の熱電発電装置において、低融点金属体を覆うが粘土セラミックス膜またはセラミックス溶射膜である場合、高温の使用環境で溶融した低融点金属体中に高融点金属被覆や熱回収手段の金属成分が溶解するのを保護膜によって確実に防止することができる。   In the thermoelectric generator of the present invention, when the low melting point metal body is covered but is a clay ceramic film or a ceramic sprayed film, the high melting point metal coating or the metal component of the heat recovery means in the low melting point metal body melted in a high temperature use environment It is possible to reliably prevent the dissolution by the protective film.

また、本発明の熱電発電装置において、低融点金属体に予め高融点金属のメッキ層が形成され、このメッキ層上に保護膜が形成されていると、粘土セラミックス膜またはセラミックス溶射膜からなる保護膜の焼成時に低融点金属体の形状を高融点金属のメッキ層で保持することができる。   In the thermoelectric generator of the present invention, when a high melting point metal plating layer is previously formed on the low melting point metal body and a protective film is formed on the plating layer, the protection made of a clay ceramic film or a ceramic sprayed film is provided. The shape of the low-melting-point metal body can be held by the high-melting-point metal plating layer when the film is fired.

以下、図面を参照して本発明に係る熱電発電装置の実施の形態を説明する。参照する図面において、図１は一実施形態に係る熱電発電装置を構成する熱電発電モジュールの概略構造を示す斜視図、図２は一実施形態に係る熱電発電装置の概略構造を示す縦断面図である。   Embodiments of a thermoelectric generator according to the present invention will be described below with reference to the drawings. In the drawings to be referred to, FIG. 1 is a perspective view showing a schematic structure of a thermoelectric power generation module constituting a thermoelectric power generation apparatus according to one embodiment, and FIG. 2 is a longitudinal sectional view showing a schematic structure of the thermoelectric power generation apparatus according to one embodiment. is there.

一実施形態に係る熱電発電装置は、例えば図１に示すような構造の熱電発電モジュール１を備えている。この熱電発電モジュール１は、高温側の受熱部を構成する絶縁セラミックス製の受熱基板１Ａと、低温側の放熱部を構成する絶縁セラミックス製の放熱基板１Ｂとの間に、ゼーベック効果により温度差に応じた熱起電力を発生するｎ型熱電発電素子Ｎおよびｐ型熱電発電素子Ｐが複数個設置され、これらのｎ型熱電発電素子Ｎおよびｐ型熱電発電素子Ｐが電極板１Ｃを介して交互に直列に接続された基本構造を有する。   A thermoelectric generator according to an embodiment includes a thermoelectric generator module 1 having a structure as shown in FIG. This thermoelectric power generation module 1 has a temperature difference due to the Seebeck effect between a heat-receiving board 1A made of insulating ceramics that constitutes a heat-receiving part on the high temperature side and a heat-radiating board 1B made of insulating ceramics that forms the heat-radiating part on the low temperature side. A plurality of n-type thermoelectric power generation elements N and p-type thermoelectric power generation elements P that generate the corresponding thermoelectromotive force are installed, and these n-type thermoelectric power generation elements N and p-type thermoelectric power generation elements P are alternately arranged via the electrode plate 1C. Have a basic structure connected in series.

このような構造の熱電発電モジュール１は、図２に示すように、熱回収手段としてのフィン部材２と熱放出手段としての放熱ブロック３との間に配置される。ここで、熱電発電モジュール１は、受熱部である受熱基板１Ａの外面の受熱面１Ａ１が高融点金属被覆４で覆われた低融点金属体５を介してフィン部材２に接触し、放熱部である放熱基板１Ｂの外面が放熱ブロック３に直接接触している。   As shown in FIG. 2, the thermoelectric power generation module 1 having such a structure is disposed between a fin member 2 as heat recovery means and a heat dissipation block 3 as heat release means. Here, the thermoelectric generator module 1 is in contact with the fin member 2 via the low melting point metal body 5 in which the heat receiving surface 1A1 of the outer surface of the heat receiving substrate 1A that is the heat receiving portion is covered with the refractory metal coating 4, The outer surface of a certain heat radiating board 1B is in direct contact with the heat radiating block 3.

フィン部材２は、例えば熱伝導性の高い銅合金やアルミニウム合金の押出し型材からなり、熱電発電モジュール１の受熱面１Ａ１に対面する対向面２Ａの反対側には、熱回収用の複数のフィン２Ｂが一体に突出成形されている。そして、このフィン部材２の対向面２Ａには、低融点金属体５を収容する凹部２Ｃが形成されている。この凹部２Ｃは、熱電発電モジュール１の受熱面１Ａ１より大きい例えば四角形の開口面を有する。   The fin member 2 is made of, for example, an extruded mold material of copper alloy or aluminum alloy having high thermal conductivity. On the opposite side of the facing surface 2A facing the heat receiving surface 1A1 of the thermoelectric power generation module 1, a plurality of fins 2B for heat recovery are provided. Are integrally formed by protruding. A recess 2 </ b> C for accommodating the low melting point metal body 5 is formed on the facing surface 2 </ b> A of the fin member 2. The recess 2C has, for example, a rectangular opening surface larger than the heat receiving surface 1A1 of the thermoelectric power generation module 1.

放熱ブロック３は、熱電発電モジュール１の放熱基板１Ｂとの間の熱交換により放熱基板１Ｂから吸熱できるように、熱伝導性の高い銅合金やアルミニウム合金製の本体内部（図示省略）に冷却水の流通路が形成されている。   The heat dissipating block 3 has cooling water in the main body (not shown) made of copper alloy or aluminum alloy having high heat conductivity so that heat can be absorbed from the heat dissipating substrate 1B by heat exchange with the heat dissipating substrate 1B of the thermoelectric power generation module 1. The flow path is formed.

低融点金属体５は、錫（Ｓｎ）、鉛（Ｐｂ）、亜鉛（Ｚｎ）などの金属材料からなり、例えば、フィン部材２が２５０℃以上の温度雰囲気に晒される使用状態において確実に溶融する錫（Ｓｎ）を成分として構成されている。この低融点金属体５は、フィン部材２の対向面２Ａに形成された凹部２Ｃ内に収容されており、その表面は低い台形をなして凹部２Ｃの開口面から盛り上がっている。この盛上り部５Ａは、熱電発電モジュール１の受熱面１Ａ１の周縁部を除いた内側の領域に対面している。   The low-melting-point metal body 5 is made of a metal material such as tin (Sn), lead (Pb), or zinc (Zn). For example, the fin member 2 is reliably melted in a usage state where the fin member 2 is exposed to a temperature atmosphere of 250 ° C. or higher. It is composed of tin (Sn) as a component. The low-melting-point metal body 5 is accommodated in a recess 2C formed on the opposing surface 2A of the fin member 2, and the surface thereof forms a low trapezoid and rises from the opening surface of the recess 2C. The swelled portion 5A faces the inner region excluding the peripheral edge portion of the heat receiving surface 1A1 of the thermoelectric power generation module 1.

高融点金属被覆４は、モリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属の板金からなり、低融点金属体５の盛上り部５Ａの表面およびその周囲のフィン部材２の対向面２Ａを覆っている。なお、この高融点金属被覆４は、モリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属をメッキ、蒸着あるいは溶射することで皮膜状に形成されていてもよい。   The refractory metal coating 4 is made of a sheet metal of a refractory metal such as molybdenum (Mo) or nickel (Ni), and the surface of the raised portion 5A of the low melting point metal body 5 and the opposing surface 2A of the surrounding fin member 2 are formed. Covering. The refractory metal coating 4 may be formed into a film by plating, vapor deposition, or thermal spraying a refractory metal such as molybdenum (Mo) or nickel (Ni).

ここで、低融点金属体５の盛上り部５Ａの表面には、モリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属のメッキ層６が形成されている。そして、このような低融点金属体５の全面は、フィン部材２の凹部２Ｃの内面からその周囲の対向面２Ａにわたって形成された保護膜７Ａと、この保護膜７Ａの周縁部からメッキ層６上にわたって形成された保護膜７Ｂとによって密封状態に覆われている。   Here, a plating layer 6 of a high melting point metal such as molybdenum (Mo) or nickel (Ni) is formed on the surface of the rising portion 5A of the low melting point metal body 5. The entire surface of the low-melting-point metal body 5 is formed on the protective layer 7A formed from the inner surface of the concave portion 2C of the fin member 2 to the surrounding opposing surface 2A, and on the plating layer 6 from the peripheral portion of the protective film 7A. And a protective film 7B formed over the cover.

保護膜７Ａは、溶融した低融点金属体５中にフィン部材２の金属成分が溶解して低融点金属体５の融点などの物性が変化するのを防止するための皮膜である。また、保護膜７Ｂは、溶融した低融点金属体５中に高融点金属被覆４の金属成分が溶解して低融点金属体５の融点などの物性が変化するのを防止すると共に、金属成分の溶出によって高融点金属被覆４が損傷するのを防止するための皮膜である。   The protective film 7 </ b> A is a film for preventing the metal component of the fin member 2 from being dissolved in the molten low melting point metal body 5 to change the physical properties such as the melting point of the low melting point metal body 5. The protective film 7B prevents the metal component of the high melting point metal coating 4 from being dissolved in the molten low melting point metal body 5 to change the physical properties such as the melting point of the low melting point metal body 5, and This is a film for preventing the refractory metal coating 4 from being damaged by elution.

このような保護膜７Ａおよび保護膜７Ｂは、例えば２５０℃以上の高温下において優れた気体バリアー性を発揮する厚さ０．１〜２ｍｍ程度の粘土セラミックス膜（粘土配向皮膜）からなり、低融点金属体５の酸化を防止する。この粘土セラミックス膜は、粘土粒子の積層を高度に配向させた皮膜であって、例えば、均一な粘土分散液を静置して粘土粒子を沈積させた後、分散媒である液体を遠心分離、ろ過、真空乾燥、凍結真空乾燥、又は加熱蒸発法などによって分離し、この皮膜素材を１１０〜３００℃の高温下で乾燥することで焼成される。なお、保護膜７Ａおよび保護膜７Ｂは、粘土セラミックス膜と同様の機能を有するセラミックス溶射膜で構成されていてもよい。   The protective film 7A and the protective film 7B are made of a clay ceramic film (clay oriented film) having a thickness of about 0.1 to 2 mm that exhibits excellent gas barrier properties at a high temperature of, for example, 250 ° C. or higher, and has a low melting point. The oxidation of the metal body 5 is prevented. This clay ceramic film is a film in which the lamination of clay particles is highly oriented, for example, after leaving a uniform clay dispersion and depositing clay particles, the liquid as a dispersion medium is centrifuged, It isolate | separates by filtration, vacuum drying, freeze vacuum drying, a heating evaporation method, etc., and this film | membrane raw material is baked by drying at 110-300 degreeC high temperature. The protective film 7A and the protective film 7B may be formed of a ceramic sprayed film having the same function as the clay ceramic film.

図３および図４は、図２に示したフィン部材２の凹部２Ｃ内に低融点金属体５を収容し、その表面を高融点金属被覆４で覆う製造工程の一例を示している。まず、図３の（ａ）に示す第１工程では、フィン部材２の凹部２Ｃの内面からその周囲の対向面２Ａにわたる部分を粘土セラミックス膜からなる焼成前の保護膜７Ａで被覆する。なお、この保護膜７Ａに代えて、フィン部材２の凹部２Ｃの内面からその周囲の対向面２Ａにわたる部分にセラミックス溶射膜を形成しても良い。   3 and 4 show an example of a manufacturing process in which the low melting point metal body 5 is accommodated in the recess 2C of the fin member 2 shown in FIG. 2 and the surface thereof is covered with the high melting point metal coating 4. FIG. First, in the first step shown in FIG. 3A, a portion extending from the inner surface of the concave portion 2C of the fin member 2 to the surrounding opposing surface 2A is covered with a protective film 7A before firing made of a clay ceramic film. In place of the protective film 7A, a ceramic sprayed film may be formed on a portion extending from the inner surface of the recess 2C of the fin member 2 to the surrounding facing surface 2A.

図３の（ｂ）に示す第２工程では、焼成前の保護膜７Ａで被覆されたフィン部材２の凹部２Ｃ内に溶融した低融点金属体５を盛り上がり状態で鋳込み、これを冷却して固化させた後、低融点金属体５の表面を機械加工して低い台形状の盛上り部５Ａを形成する。   In the second step shown in FIG. 3 (b), the molten low melting point metal body 5 is cast in a raised state into the recess 2C of the fin member 2 covered with the protective film 7A before firing, and is cooled and solidified. Then, the surface of the low melting point metal body 5 is machined to form a low trapezoidal raised portion 5A.

図４の（ａ）に示す第３工程では、つぎの第４工程で焼成前の保護膜７Ａおよび保護膜７Ｂを焼成する際に溶融する低融点金属体５の形状を保持できるように、低融点金属体５の盛上り部５Ａの表面にモリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属のメッキ層６を形成する。   In the third step shown in FIG. 4 (a), the low melting point metal body 5 that is melted when the protective film 7A and the protective film 7B before firing in the next fourth step are fired is kept low. A plating layer 6 of a refractory metal such as molybdenum (Mo) or nickel (Ni) is formed on the surface of the rising portion 5A of the melting point metal body 5.

図４の（ｂ）に示す第４工程では、焼成前の保護膜７Ａの周縁部からメッキ層６上にわたる部分を粘土セラミックス膜からなる焼成前の保護膜７Ｂで被覆し、その後、保護膜７Ａおよび保護膜７Ｂを２５０〜３００℃の高温下で焼成して低融点金属体５を密封する。なお、この保護膜７Ｂに代えて、焼成前の保護膜７Ａの周縁部からメッキ層６上にわたる部分にセラミックス溶射膜を形成しても良い。   In the fourth step shown in FIG. 4B, a portion extending from the peripheral edge of the protective film 7A before firing to the plating layer 6 is covered with the protective film 7B before firing made of a clay ceramic film, and then the protective film 7A. The protective film 7B is fired at a high temperature of 250 to 300 ° C. to seal the low melting point metal body 5. Instead of the protective film 7B, a ceramic sprayed film may be formed on a portion extending from the peripheral edge of the protective film 7A before firing to the plated layer 6.

図４の（ｃ）に示す第５工程では、焼成された保護膜７Ｂに沿う所定の断面形状に形成されたモリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属材料の板金を高融点金属被覆４として用意し、この板金からなる高融点金属被覆４を保護膜７Ｂ上に被せて低融点金属体５の盛上り部５Ａの表面およびその周囲のフィン部材２の対向面２Ａを覆う。   In the fifth step shown in FIG. 4C, a sheet metal of a refractory metal material such as molybdenum (Mo) or nickel (Ni) formed in a predetermined cross-sectional shape along the fired protective film 7B is used as a refractory metal. Prepared as a coating 4, the refractory metal coating 4 made of sheet metal is placed on the protective film 7 </ b> B to cover the surface of the rising portion 5 </ b> A of the low melting metal body 5 and the opposing surface 2 </ b> A of the fin member 2 around it.

以上の工程により、焼成された保護膜７Ａおよび保護膜７Ｂで全面が密封状態に覆われた低融点金属体５がフィン部材２の凹部２Ｃ内に収容され、この低融点金属体５の盛上り部５Ａが高融点金属被覆４で覆われる。そして、図２に示すように、熱電発電モジュール１の受熱面１Ａ１が高融点金属皮膜４で覆われた低融点金属体５を介してフィン部材２に接触する。   Through the above steps, the low melting point metal body 5 whose whole surface is covered with the fired protective film 7A and the protective film 7B is accommodated in the recess 2C of the fin member 2, and the low melting point metal body 5 rises. The part 5A is covered with the refractory metal coating 4. As shown in FIG. 2, the heat receiving surface 1 </ b> A <b> 1 of the thermoelectric power generation module 1 comes into contact with the fin member 2 through the low melting point metal body 5 covered with the high melting point metal film 4.

このような構造を有する本実施形態の熱電発電装置は、例えば自動車の排気系の熱を回収して発電するように、フィン部材２のフィン２Ｂが図示しない排気ガスの流通経路に臨んで設置される。そして、フィン２Ｂにより回収された排気ガスの熱がフィン部材２から低融点金属体５および高融点金属被覆４を介して熱電発電モジュール１の受熱基板１Ａに伝熱され、熱電発電モジュール１の放熱基板１Ｂから放熱ブロック３へ放熱されることにより、熱電発電モジュール１の各ｎ型熱電発電素子Ｎおよびｐ型熱電発電素子Ｐ（図１参照）が起電力を発生して発電する。   The thermoelectric generator of this embodiment having such a structure is installed with the fins 2B of the fin member 2 facing an exhaust gas distribution path (not shown) so as to generate heat by collecting the heat of the exhaust system of the automobile, for example. The Then, the heat of the exhaust gas recovered by the fins 2B is transferred from the fin member 2 to the heat receiving substrate 1A of the thermoelectric power generation module 1 through the low melting point metal body 5 and the high melting point metal coating 4, and the heat dissipation of the thermoelectric generation module 1 is performed. By radiating heat from the substrate 1B to the heat dissipation block 3, each n-type thermoelectric power generation element N and p-type thermoelectric power generation element P (see FIG. 1) of the thermoelectric power generation module 1 generates electromotive force to generate power.

このような本実施形態の熱電発電装置の使用状態において、フィン部材２のフィン２Ｂが排気ガスの熱を吸収して例えば２５０℃以上の高温になると、例えば錫（Ｓｎ）を成分とする低融点金属体５がフィン部材２の凹部２Ｃ内で確実に溶融し、この溶融した低融点金属体４の柔軟性により、例えばモリブデン（Ｍｏ）やニッケル（Ｎｉ）を成分とする高融点金属皮膜４が熱電発電モジュール１の受熱基板１Ａの受熱面１Ａ１に密着する。   When the fin 2B of the fin member 2 absorbs the heat of the exhaust gas and reaches a high temperature of, for example, 250 ° C. or higher in the usage state of the thermoelectric generator of this embodiment, for example, a low melting point containing, for example, tin (Sn) as a component The metal body 5 is surely melted in the recess 2C of the fin member 2, and due to the flexibility of the melted low-melting-point metal body 4, for example, the refractory metal film 4 containing molybdenum (Mo) or nickel (Ni) as a component is formed. The thermoelectric generator module 1 is in close contact with the heat receiving surface 1A1 of the heat receiving substrate 1A.

この場合、高融点金属皮膜４の中央部は、受熱基板１Ａの受熱面１Ａ１における周縁部を除いた内側の領域に対面する低融点金属体５の盛上り部５Ａに沿って盛り上がっている。すなわち、高融点金属皮膜４の中央部は、受熱面１Ａ１の外周より若干内側の領域に対面しているため、受熱基板１Ａの受熱面１Ａ１に均一な面圧で確実に密着する。その結果、フィン部材２から熱電発電モジュール１の受熱基板１Ａへの熱伝導が極めて良好に行われる。   In this case, the central portion of the refractory metal coating 4 swells along the raised portion 5A of the low-melting-point metal body 5 facing the inner region excluding the peripheral edge portion of the heat receiving surface 1A1 of the heat receiving substrate 1A. That is, since the central portion of the refractory metal film 4 faces a region slightly inside the outer periphery of the heat receiving surface 1A1, it reliably adheres to the heat receiving surface 1A1 of the heat receiving substrate 1A with a uniform surface pressure. As a result, heat conduction from the fin member 2 to the heat receiving substrate 1A of the thermoelectric power generation module 1 is performed extremely well.

ここで、本実施形態の熱電発電装置では、例えば２５０℃以上の高温下において優れた気体バリアー性を発揮する粘土セラミックス膜（粘土配向皮膜）で構成された保護膜７Ａおよび保護膜７Ｂにより低融点金属体５の全面が密封状態に覆われている。このため、２５０℃以上の高温の使用環境で溶融した低融点金属体５中にフィン部材２の金属成分や高融点金属被覆４の金属成分が溶解して低融点金属体５の融点などの物性が変化する事態が長期にわたって確実に防止される。また、金属成分の溶出によって高融点金属被覆４が損傷する事態が長期にわたって確実に防止される。   Here, in the thermoelectric generator of the present embodiment, for example, the protective film 7A and the protective film 7B made of a clay ceramic film (clay alignment film) exhibiting excellent gas barrier properties at a high temperature of 250 ° C. or higher have a low melting point. The entire surface of the metal body 5 is covered in a sealed state. For this reason, the metal component of the fin member 2 and the metal component of the refractory metal coating 4 are dissolved in the low melting point metal body 5 melted in a high temperature use environment of 250 ° C. or higher, and the physical properties such as the melting point of the low melting point metal body 5. The situation that changes is reliably prevented for a long time. Moreover, the situation where the refractory metal coating 4 is damaged by the elution of the metal component is reliably prevented over a long period of time.

なお、低融点金属体５の盛上り部５Ａの表面に形成されたメッキ層６のモリブデン（Ｍｏ）やニッケル（Ｎｉ）などの金属成分は、溶融した低融点金属体５中へ溶解してゆくが、その溶解量は極めて微量であるため、低融点金属体５の融点などの物性変化に殆ど影響を与えない。   It should be noted that metal components such as molybdenum (Mo) and nickel (Ni) of the plating layer 6 formed on the surface of the raised portion 5A of the low melting point metal body 5 are dissolved into the molten low melting point metal body 5. However, since the dissolved amount is extremely small, it hardly affects the change in physical properties such as the melting point of the low melting point metal body 5.

従って、本実施形態の熱電発電装置によれば、フィン部材２と熱電発電モジュール１の受熱基板１Ａとの接触面を高い平面度に仕上げ、あるいはその接触面を均一に圧接させることなく、フィン部材２から熱電発電モジュール１の受熱基板１Ａへの熱伝導を長期にわたって極めて良好に行うことができ、長期にわたって高い発電性能を発揮することができる。   Therefore, according to the thermoelectric power generation device of the present embodiment, the fin member 2 and the heat receiving substrate 1A of the thermoelectric power generation module 1 are finished with a high flatness, or the fin member is not pressed uniformly. Heat conduction from 2 to the heat receiving substrate 1A of the thermoelectric power generation module 1 can be performed extremely well over a long period of time, and high power generation performance can be exhibited over a long period of time.

本発明は前述した一実施形態に限定されるものではない。例えば図２に示した高融点金属被覆４は、モリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属のメッキ、蒸着、溶射などの適宜の手段で形成してもよい。また、図４の（ａ）〜（ｃ）に示した第３工程〜第５工程は、図５の（ａ）〜（ｂ）に示す第３工程および第４工程に変更することができる。   The present invention is not limited to the above-described embodiment. For example, the refractory metal coating 4 shown in FIG. 2 may be formed by an appropriate means such as plating, vapor deposition, or thermal spraying of a refractory metal such as molybdenum (Mo) or nickel (Ni). Moreover, the 3rd process-5th process shown to (a)-(c) of FIG. 4 can be changed into the 3rd process and 4th process shown to (a)-(b) of FIG.

ここで、図５の（ａ）に示す第３工程では、焼成前の保護膜７Ａの周縁部から低融点金属体５の盛上り部５Ａに沿う所定の断面形状に形成され、かつ、内面が焼成前の保護膜７Ｂで被覆されたモリブデン（Ｍｏ）やニッケル（Ｎｉ）などの高融点金属材料の板金を高融点金属被覆４として用意し、この板金からなる高融点金属被覆４を保護膜７Ａの周縁部から低融点金属体５の盛上り部５Ａにわたって被せる。   Here, in the third step shown in FIG. 5A, a predetermined cross-sectional shape is formed from the peripheral portion of the protective film 7A before firing along the rising portion 5A of the low melting point metal body 5, and the inner surface is formed. A sheet metal of a refractory metal material such as molybdenum (Mo) or nickel (Ni) coated with the protective film 7B before firing is prepared as the refractory metal coating 4, and the refractory metal coating 4 made of this sheet metal is used as the protective film 7A. Of the low melting point metal body 5 from the peripheral part of the swelled portion 5A.

そして、図５の（ｂ）に示す第４工程では、板金からなる高融点金属被覆４の周縁部に押さえ枠８を重ね、この押さえ枠８および高融点金属被覆４の周縁部を貫通する複数のボルト９により押さえ枠８をフィン部材２の対向面２Ａの周縁部に止め付ける。そして、この状態で焼成前の保護膜７Ａおよび保護膜７Ｂを２５０〜３００℃の高温下で焼成した後、ボルト９および押さえ枠８を取り外す。   In the fourth step shown in FIG. 5 (b), a pressing frame 8 is stacked on the peripheral edge of the refractory metal coating 4 made of sheet metal, and a plurality of penetrating through the peripheral edge of the pressing frame 8 and the refractory metal coating 4. The holding frame 8 is fastened to the peripheral edge portion of the facing surface 2 </ b> A of the fin member 2 with the bolt 9. And after baking the protective film 7A and the protective film 7B before baking in this state at the high temperature of 250-300 degreeC, the volt | bolt 9 and the press frame 8 are removed.

このような製造工程の一部変更によっても、保護膜７Ａおよび保護膜７Ｂで全面が密封状態に覆われた低融点金属体５がフィン部材２の凹部２Ｃ内に収容され、この低融点金属体５の盛上り部５Ａが高融点金属被覆４で覆われる。そして、図２に示すように、熱電発電モジュール１の受熱面１Ａ１が高融点金属皮膜４で覆われた低融点金属体５を介してフィン部材２に接触する。   Even with such a partial change in the manufacturing process, the low-melting-point metal body 5 whose entire surface is covered with the protective film 7A and the protective film 7B is accommodated in the recess 2C of the fin member 2, and this low-melting-point metal body. 5 swelled portions 5 </ b> A are covered with a refractory metal coating 4. As shown in FIG. 2, the heat receiving surface 1 </ b> A <b> 1 of the thermoelectric power generation module 1 comes into contact with the fin member 2 through the low melting point metal body 5 covered with the high melting point metal film 4.

本発明の一実施形態に係る熱電発電装置を構成する熱電発電モジュールの概略構造を示す斜視図である。It is a perspective view showing the schematic structure of the thermoelectric power generation module which constitutes the thermoelectric power generation device concerning one embodiment of the present invention. 一実施形態に係る熱電発電装置の概略構造を示す縦断面図である。It is a longitudinal section showing the schematic structure of the thermoelectric power generator concerning one embodiment. 図２に示したフィン部材の凹部内に低融点金属体を収容し、その表面を高融点金属被覆で覆う製造工程の一例における第１工程および第２工程を示す縦断面図である。It is a longitudinal cross-sectional view which shows the 1st process and 2nd process in an example of the manufacturing process which accommodates the low melting-point metal body in the recessed part of the fin member shown in FIG. 2, and covers the surface with a high-melting-point metal coating. 図３に示した第２工程に続く第３工程〜第５工程を示す縦断面図である。It is a longitudinal cross-sectional view which shows the 3rd process-5th process following the 2nd process shown in FIG. 図４に示した第３工程〜第５工程の変形例を示す縦断面図である。It is a longitudinal cross-sectional view which shows the modification of the 3rd process-5th process shown in FIG.

符号の説明Explanation of symbols

１…熱電発電モジュール、１Ａ…受熱基板、１Ａ１…受熱面、１Ｂ…放熱基板、２…フィン部材、２Ａ…対向面、２Ｂ…フィン、２Ｃ…凹部、３…放熱ブロック、４…高融点金属被覆、５…低融点金属体、５Ａ…盛上り部、６…メッキ層、７Ａ，７Ｂ…保護膜。
DESCRIPTION OF SYMBOLS 1 ... Thermoelectric power generation module, 1A ... Heat receiving board, 1A1 ... Heat receiving surface, 1B ... Heat sink board, 2 ... Fin member, 2A ... Opposing surface, 2B ... Fin, 2C ... Recessed part, 3 ... Heat sink block, 4 ... High melting point metal coating 5 ... Low melting point metal body, 5A ... Swelling part, 6 ... Plating layer, 7A, 7B ... Protective film.

Claims (5)

熱回収手段に接触する受熱部と熱放出手段に接触する放熱部との間に複数の熱電発電素子が配置された熱電発電モジュールを備える熱電発電装置であって、
前記熱電発電モジュールは、受熱部が高融点金属被覆で覆われた低融点金属体を介して前記熱回収手段に接触しており、前記放熱部の外面が前記熱放出手段に直接接触しており、
前記低融点金属体中への金属成分の溶解を防止する保護膜が前記低融点金属体の全面を覆っており、
前記熱回収手段には、前記受熱部の受熱面に対面する対向面に凹部が形成されており、
前記低融点金属体は、前記凹部に収容され、当該凹部の開口面から盛り上がる盛上り部を有し、
前記盛上り部が前記受熱面の周縁部を除いた内側の領域に対面していることを特徴とする熱電発電装置。 A thermoelectric power generation apparatus comprising a thermoelectric power generation module in which a plurality of thermoelectric power generation elements are arranged between a heat receiving part in contact with a heat recovery means and a heat dissipation part in contact with a heat release means,
The thermoelectric power generation module through the low melting metal member which heat receiving portion is covered with a high melting point metal covering is in contact with the heat recovery means, the outer surface of the heat radiating portion is in direct contact with the heat dissipation means ,
A protective film that prevents dissolution of the metal component in the low-melting-point metal body covers the entire surface of the low-melting-point metal body,
In the heat recovery means, a concave portion is formed on the facing surface facing the heat receiving surface of the heat receiving portion,
The low-melting-point metal body is accommodated in the concave portion, and has a rising portion that rises from the opening surface of the concave portion,
2. The thermoelectric generator according to claim 1, wherein the swelled portion faces an inner region excluding the peripheral portion of the heat receiving surface. 前記保護膜が粘土セラミックス膜またはセラミックス溶射膜であることを特徴とする請求項１に記載の熱電発電装置。   The thermoelectric generator according to claim 1, wherein the protective film is a clay ceramic film or a ceramic sprayed film. 前記低融点金属体に高融点金属のメッキ層が形成され、このメッキ層上に前記保護膜が形成されていることを特徴とする請求項１または２に記載の熱電発電装置。   The thermoelectric power generator according to claim 1 or 2, wherein a plating layer of a high melting point metal is formed on the low melting point metal body, and the protective film is formed on the plating layer. 前記高融点金属被覆が板金により構成されていることを特徴とする請求項１または２に記載の熱電発電装置。   The thermoelectric power generator according to claim 1 or 2, wherein the refractory metal coating is made of sheet metal. 前記板金の内面が前記保護膜で被覆されていることを特徴とする請求項４に記載の熱電発電装置。   The thermoelectric generator according to claim 4, wherein an inner surface of the sheet metal is covered with the protective film.
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JP2011011366A (en) * 2009-06-30 2011-01-20 Sumitomo Electric Ind Ltd Method of manufacturing metal laminated structure
JP5583985B2 (en) 2010-02-19 2014-09-03 住友電気工業株式会社 Metal laminated structure
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DE102011007395A1 (en) * 2011-04-14 2012-10-18 Behr Gmbh & Co. Kg Thermoelectric module for use in thermoelectric generator, for producing electrical energy, has device for generating electrical energy from heat, where contact surface of device is in thermal or electrical contact with connector
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Family Cites Families (10)

* Cited by examiner, † Cited by third party
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JPH088567A (en) * 1994-06-23 1996-01-12 Fujitsu Ltd Cooling device and heat conducting mechanism section of part
JP3573448B2 (en) * 2000-12-18 2004-10-06 財団法人電力中央研究所 Thermoelectric conversion element
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JP4014549B2 (en) * 2003-09-18 2007-11-28 富士電機システムズ株式会社 Heat sink and manufacturing method thereof
JP4165405B2 (en) * 2003-10-06 2008-10-15 トヨタ自動車株式会社 Exhaust gas purification device
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