JP2017135309A - Thermoelectric conversion module and method of manufacturing the same - Google Patents
Thermoelectric conversion module and method of manufacturing the same Download PDFInfo
- Publication number
- JP2017135309A JP2017135309A JP2016015339A JP2016015339A JP2017135309A JP 2017135309 A JP2017135309 A JP 2017135309A JP 2016015339 A JP2016015339 A JP 2016015339A JP 2016015339 A JP2016015339 A JP 2016015339A JP 2017135309 A JP2017135309 A JP 2017135309A
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric conversion
- conversion module
- conversion element
- stress relaxation
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- H10N10/01—Manufacture or treatment
-
- 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
-
- 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
- H10N10/80—Constructional details
- H10N10/81—Structural details of the junction
- H10N10/817—Structural details of the junction the junction being non-separable, e.g. being cemented, sintered or soldered
Abstract
Description
本発明は、熱電変換モジュールおよびその製造方法に関する。 The present invention relates to a thermoelectric conversion module and a manufacturing method thereof.
本技術分野の背景技術として、特開２０１２−２３５０８８号公報（特許文献１）がある。この公報には、「交互に配列する複数のＰ型熱電変換素子および複数のＮ型熱電変換素子が、Ｐ型熱電変換素子の一端面とＮ型熱電変換素子の一端面とを接続する編線と、Ｐ型熱電変換素子の他端面とＮ型熱電変換素子の他端面とを接続する編線とによって、電気的に直列に接続されてなる直鎖状の小モジュールを含む熱電変換モジュール」が記載されている。 As a background art in this technical field, there is JP 2012-235088 A (Patent Document 1). This publication states that “a plurality of P-type thermoelectric conversion elements and a plurality of N-type thermoelectric conversion elements arranged alternately connect the one end face of the P-type thermoelectric conversion element and the one end face of the N-type thermoelectric conversion element. And a thermoelectric conversion module including a linear small module electrically connected in series by the braided wire connecting the other end face of the P-type thermoelectric conversion element and the other end face of the N-type thermoelectric conversion element " Have been described.
熱電変換モジュールでは、熱電変換素子と電極との熱膨張差により、熱電変換素子と電極との接合部に熱応力が発生する。そのため、この熱応力に起因した接合部または熱電変換素子自体の破壊が懸念される。さらに、この熱応力に振動または衝撃が加わることにより、接合部または熱電変換素子自体の破壊はさらに深刻なものとなる。また、熱電変換素子または電極に高さバラツキがあると、熱電変換モジュールの組立時の接合性の低下が生じ、これと合わせて、熱電変換モジュールに熱源体からの熱が均一に伝わり難くなり、発電性能が低下するという課題もある。 In the thermoelectric conversion module, thermal stress is generated at the joint between the thermoelectric conversion element and the electrode due to a difference in thermal expansion between the thermoelectric conversion element and the electrode. Therefore, there is a concern about the destruction of the joint portion or the thermoelectric conversion element itself due to the thermal stress. Furthermore, vibrations or impacts are applied to the thermal stress, so that the destruction of the joint portion or the thermoelectric conversion element itself becomes more serious. In addition, if the thermoelectric conversion element or electrode has a height variation, the bonding property during assembly of the thermoelectric conversion module is deteriorated. Together with this, the heat from the heat source body is not easily transmitted to the thermoelectric conversion module. There is also a problem that power generation performance is reduced.
上記課題を解決するために、本発明による熱電変換モジュールは、電極を、Ｐ型熱電変換素子およびＮ型熱電変換素子を搭載する応力緩和部と、Ｐ型熱電変換素子およびＮ型熱電変換素子を搭載しない金属封止部とから構成し、応力緩和部の厚さを、金属封止部の厚さよりも厚くする。そして、応力緩和部を、第１金属材および第２金属材により封止した金属繊維、発泡金属または金属粉末からなる応力緩和材により形成する。 In order to solve the above-described problems, a thermoelectric conversion module according to the present invention includes an electrode, a stress relaxation portion on which a P-type thermoelectric conversion element and an N-type thermoelectric conversion element are mounted, a P-type thermoelectric conversion element, and an N-type thermoelectric conversion element. It is comprised from the metal sealing part which is not mounted, and the thickness of a stress relaxation part is made thicker than the thickness of a metal sealing part. And a stress relaxation part is formed with the stress relaxation material which consists of a metal fiber, foam metal, or metal powder sealed with the 1st metal material and the 2nd metal material.
本発明によれば、熱応力が発生する環境下、および振動または衝撃が負荷される環境下においても、高い信頼性および発電性能が確保できる熱電変換モジュールを提供することができる。また、熱電変換モジュールの組立時の接合性を向上させることができる。 ADVANTAGE OF THE INVENTION According to this invention, the thermoelectric conversion module which can ensure high reliability and electric power generation performance can be provided also in the environment where a thermal stress generate | occur | produces, and the environment where a vibration or an impact is loaded. Moreover, the joining property at the time of the assembly of a thermoelectric conversion module can be improved.
上記した以外の課題、構成および効果は、以下の実施の形態の説明により明らかにされる。 Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.
以下の実施の形態において、便宜上その必要があるときは、複数のセクションまたは実施の形態に分割して説明するが、特に明示した場合を除き、それらはお互いに無関係なものではなく、一方は他方の一部または全部の変形例、詳細、補足説明等の関係にある。 In the following embodiments, when necessary for the sake of convenience, the description will be divided into a plurality of sections or embodiments. However, unless otherwise specified, they are not irrelevant to each other, and one is the other. There are some or all of the modifications, details, supplementary explanations, and the like.
また、以下の実施の形態において、要素の数等（個数、数値、量、範囲等を含む）に言及する場合、特に明示した場合および原理的に明らかに特定の数に限定される場合等を除き、その特定の数に限定されるものではなく、特定の数以上でも以下でも良い。 Further, in the following embodiments, when referring to the number of elements (including the number, numerical value, quantity, range, etc.), especially when clearly indicated and when clearly limited to a specific number in principle, etc. Except, it is not limited to the specific number, and may be more or less than the specific number.
また、以下の実施の形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合および原理的に明らかに必須であると考えられる場合等を除き、必ずしも必須のものではないことは言うまでもない。 Further, in the following embodiments, the constituent elements (including element steps) are not necessarily indispensable unless otherwise specified and clearly considered essential in principle. Needless to say.
また、「Ａからなる」、「Ａよりなる」、「Ａを有する」、「Ａを含む」と言うときは、特にその要素のみである旨明示した場合等を除き、それ以外の要素を排除するものでないことは言うまでもない。同様に、以下の実施の形態において、構成要素等の形状、位置関係等に言及するときは、特に明示した場合および原理的に明らかにそうでないと考えられる場合等を除き、実質的にその形状等に近似または類似するもの等を含むものとする。このことは、上記数値および範囲についても同様である。 In addition, when referring to “consisting of A”, “consisting of A”, “having A”, and “including A”, other elements are excluded unless specifically indicated that only that element is included. It goes without saying that it is not what you do. Similarly, in the following embodiments, when referring to the shapes, positional relationships, etc. of the components, etc., the shapes are substantially the same unless otherwise specified, or otherwise apparent in principle. And the like are included. The same applies to the above numerical values and ranges.
また、以下の実施の形態を説明するための全図において、同一機能を有するものは原則として同一の符号を付し、その繰り返しの説明は省略する。以下、本実施の形態を図面に基づいて詳細に説明する。 In all the drawings for explaining the following embodiments, components having the same function are denoted by the same reference numerals in principle, and repeated description thereof is omitted. Hereinafter, the present embodiment will be described in detail with reference to the drawings.
ゼーベック効果を利用して熱エネルギーを電気エネルギーに変換する熱電変換モジュールは、駆動部がない、構造が単純およびメンテナンスが不要などの特長を有するが、これまではエネルギー変換効率が低いという理由から、宇宙用電源などの限られた製品のみで使用されてきた。しかし、近年、環境調和型社会の実現に向けて、排熱を回収し、これを熱エネルギーとして有効利用する手法が注目を浴びている。 The thermoelectric conversion module that converts thermal energy into electrical energy using the Seebeck effect has features such as no drive unit, simple structure and no maintenance, but until now, because of its low energy conversion efficiency, It has been used only in limited products such as space power supplies. However, in recent years, methods for recovering exhaust heat and effectively using it as thermal energy have attracted attention for the realization of an environmentally harmonious society.
現在検討が進んでいる熱電変換モジュールは、ビスマス−テルル系が主であり、使用温度域が３００℃以下と低温に限られる。排熱をさらに有効利用するためには、ビスマス−テルル系よりも高温で動作が可能なシリコン−ゲルマニウム系、マグネシウムシリサイド系、マンガンシリサイド系、コバルト−アンチモン系をベースとしたスクッテルダイト系またはホイスラー系などを用いた中高温用の熱電変換モジュールが必要となる。 The thermoelectric conversion modules that are currently under investigation are mainly bismuth-tellurium, and the operating temperature range is limited to 300 ° C. or lower and low temperatures. In order to make more effective use of exhaust heat, a skutterudite system or Heusler based on silicon-germanium system, magnesium silicide system, manganese silicide system, cobalt-antimony system that can operate at higher temperatures than bismuth-tellurium system. A thermoelectric conversion module for medium and high temperatures using a system is required.
ところで、熱電変換モジュールでは、熱電変換素子内に温度差を与えることにより、熱エネルギーを電気エネルギーに変換する。そのため、熱電変換モジュールの稼働環境下において、熱電変換素子と電極との熱膨張差により、熱電変換素子と電極との接合部に熱応力が発生し、接合部または熱電変換素子自体の破壊が懸念される。発生する熱応力は、使用環境温度が高いほど、または、熱電変換素子と接合材または電極との線膨張係数差が大きいほど高くなる。特に、３００℃以上の環境温度で使用が想定される中高温用の熱電変換モジュールでは大きな課題となる。 By the way, in a thermoelectric conversion module, thermal energy is converted into electric energy by giving a temperature difference in the thermoelectric conversion element. Therefore, in the operating environment of the thermoelectric conversion module, thermal stress is generated at the joint between the thermoelectric conversion element and the electrode due to a difference in thermal expansion between the thermoelectric conversion element and the electrode, and there is a concern about the destruction of the joint or the thermoelectric conversion element itself. Is done. The generated thermal stress increases as the use environment temperature increases or as the difference in linear expansion coefficient between the thermoelectric conversion element and the bonding material or electrode increases. In particular, it becomes a big problem in a medium to high temperature thermoelectric conversion module which is assumed to be used at an environmental temperature of 300 ° C. or higher.
さらに、熱電変換モジュールの設置箇所によっては、振動または衝撃を伴う可能性もあり、熱電変換モジュールに生じる熱応力に振動または衝撃が加わることで接合部または熱電変換素子自体の破壊が懸念される。熱電変換素子と電極との接合には、硬ろう、またははんだなどの軟ろうが接合材として用いられることが多い。しかし、硬ろうの場合は、接合温度が４５０〜１,０００℃程度と高く、接合プロセスの冷却過程で接合部に熱応力が発生しやすい。このため、熱電変換モジュールには、この熱応力を低減する構造が必要となる。一方、軟ろうの場合は、接合温度が３００℃以下と低く、接合部に発生する熱応力は低減できる。しかし、融点も低いため低温用の熱電変換モジュールのみに用途が限られてしまう。また、接合材が硬ろうであるか軟ろうであるかに係わらず、熱電変換素子または電極に高さバラツキがあると、熱電変換モジュールの組立時の接合性が低下し、これと合わせて、熱電変換モジュールに熱源体からの熱が均一に伝わり難くなり、発電性能が低下するという課題もある。 Furthermore, depending on the installation location of the thermoelectric conversion module, there is a possibility of accompanying vibration or impact, and there is a concern about the destruction of the joint or the thermoelectric conversion element itself due to the addition of vibration or impact to the thermal stress generated in the thermoelectric conversion module. For joining the thermoelectric conversion element and the electrode, hard solder or soft solder such as solder is often used as a joining material. However, in the case of a hard solder, the joining temperature is as high as about 450 to 1,000 ° C., and thermal stress is likely to occur at the joint during the cooling process of the joining process. For this reason, the thermoelectric conversion module requires a structure for reducing this thermal stress. On the other hand, in the case of soft solder, the joining temperature is as low as 300 ° C. or lower, and the thermal stress generated at the joint can be reduced. However, since the melting point is low, the use is limited only to the thermoelectric conversion module for low temperature. In addition, regardless of whether the bonding material is hard or soft, if the thermoelectric conversion element or electrode has a height variation, the bonding property during assembly of the thermoelectric conversion module is reduced. There is also a problem that heat from the heat source body is not easily transmitted to the thermoelectric conversion module, and power generation performance is reduced.
本発明による熱電変換モジュールは、熱電変換素子が搭載される電極の構造に特徴を有する。すなわち、エネルギー変換効率を損なうことなく、熱応力、さらに振動または衝撃に対する耐性を高めた信頼性の高い熱電変換モジュールを実現することのできる技術に関するものである。また、熱電変換素子と電極との接合性が向上した熱電変換モジュールを実現することのできる技術に関するものである。 The thermoelectric conversion module according to the present invention is characterized by the structure of an electrode on which a thermoelectric conversion element is mounted. That is, the present invention relates to a technique that can realize a highly reliable thermoelectric conversion module with improved resistance to thermal stress and vibration or impact without impairing energy conversion efficiency. Further, the present invention relates to a technique that can realize a thermoelectric conversion module with improved bonding between a thermoelectric conversion element and an electrode.
［第1実施形態］
≪熱電変換モジュールの構造≫
本第１実施形態による熱電変換モジュールの構造を、図１を用いて説明する。図１は、本第１実施形態による熱電変換モジュールの一部を拡大して示す要部断面図である。図１中に示す符号１００は熱電変換モジュール、符号１１はＰ型熱電変換素子、符号１２はＮ型熱電変換素子、符号２１は第１金属材、符号２２は応力緩和材、符号２３は第２金属材、符号２４は金属封止部、符号２０１は下部応力緩和電極、符号２０２は上部応力緩和電極である。
[First embodiment]
≪The structure of thermoelectric conversion module≫
The structure of the thermoelectric conversion module according to the first embodiment will be described with reference to FIG. FIG. 1 is an enlarged cross-sectional view showing a part of the thermoelectric conversion module according to the first embodiment. In FIG. 1, reference numeral 100 is a thermoelectric conversion module, reference numeral 11 is a P-type thermoelectric conversion element, reference numeral 12 is an N-type thermoelectric conversion element, reference numeral 21 is a first metal material, reference numeral 22 is a stress relaxation material, and reference numeral 23 is a second. Reference numeral 24 denotes a metal sealing portion, reference numeral 201 denotes a lower stress relaxation electrode, and reference numeral 202 denotes an upper stress relaxation electrode.
Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２は、シリコン−ゲルマニウム系、鉄−シリコン系、ビスマス−テルル系、マグネシウム−シリコン系、マンガン−シリコン系、鉛−テルル系、コバルト−アンチモンなどのスクッテルダイト系、ビスマス−アンチモン系、ホイスラー合金系またはハーフホイスラー合金系などのいずれかの組み合わせからなる熱電変換素子が望ましい。 P-type thermoelectric conversion element 11 and N-type thermoelectric conversion element 12 are made of silicon-germanium, iron-silicon, bismuth-tellurium, magnesium-silicon, manganese-silicon, lead-tellurium, cobalt-antimony, etc. A thermoelectric conversion element made of any combination of skutterudite, bismuth-antimony, Heusler alloy, or half-Heusler alloy is desirable.
また、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２の表面（下部応力緩和電極２０１または上部応力緩和電極２０２との接合面）にニッケル、アルミニウム、チタン、モリブデン、タングステン、パラジウム、クロム、金、銀、銅または錫からなる金属層、あるいはこれらの金属のうちのいずれかを主成分とする金属層が形成されていてもよい。ここで主成分とは、複数の元素を含有する部材において、含有率が一番多い成分をいう。また、本第１実施形態においての主成分とは、部材に含有される複数の元素のうち、主成分とされる元素の合計値が他の元素より多い場合も含む概念である。 Further, nickel, aluminum, titanium, molybdenum, tungsten, palladium, chromium, gold are formed on the surfaces of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 (bonding surfaces with the lower stress relaxation electrode 201 or the upper stress relaxation electrode 202). In addition, a metal layer made of silver, copper or tin, or a metal layer mainly composed of any of these metals may be formed. Here, the main component refers to a component having the highest content rate in a member containing a plurality of elements. In addition, the main component in the first embodiment is a concept that includes a case where the total value of the main components among the plurality of elements contained in the member is larger than that of other elements.
例えば金属層が銅とニッケルとアルミニウムとの合金である場合に、銅が３４％、ニッケルが３３％、アルミニウムが３３％であれば、銅が主成分といえる。その他、銅が６０％、ニッケルが２１％、アルミニウムが１９％であれば、銅とニッケルが主成分である。合金または接合後の構造であっても主成分の概念は同様である。 For example, when the metal layer is an alloy of copper, nickel, and aluminum, if copper is 34%, nickel is 33%, and aluminum is 33%, copper can be said to be the main component. In addition, if copper is 60%, nickel is 21%, and aluminum is 19%, copper and nickel are the main components. The concept of the main component is the same even in an alloy or a structure after joining.
金属層の厚さは、０．５μｍ〜５００μｍ程度の範囲が望ましい。金属層の形成方法としては、クラッド法、めっき法、エアロゾルデポジション法、溶射法、スパッタ法、蒸着法、イオンプレーティング法または同時一体焼結法などであればよい。金属層が薄すぎると電極（下部応力緩和電極２０１または上部応力緩和電極２０２）と接合する際に使用する接合材が拡散することで金属層が消失し、接合強度の低下および発電性能の低下が懸念される。逆に、金属層が厚すぎると金属層を形成する際の応力によるＰ型熱電変換素子１１およびＮ型熱電変換素子１２の割れが懸念される。そのため、金属層の厚さのよりよい範囲は、０．２μｍ〜２０μｍ程度である。本第１実施形態では、Ｐ型熱電変換素子１１をマンガン−シリコン系素子、Ｎ型熱電変換素子１２をマグネシウム−シリコン系素子とし、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２のそれぞれの表面にニッケルからなる金属層を形成した。 The thickness of the metal layer is preferably in the range of about 0.5 μm to 500 μm. The metal layer may be formed by any method such as a cladding method, a plating method, an aerosol deposition method, a thermal spraying method, a sputtering method, a vapor deposition method, an ion plating method, or a simultaneous integral sintering method. If the metal layer is too thin, the metal layer disappears due to the diffusion of the bonding material used when bonding to the electrode (lower stress relaxation electrode 201 or upper stress relaxation electrode 202), resulting in a decrease in bonding strength and power generation performance. Concerned. On the contrary, if the metal layer is too thick, there is a concern that the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 may be cracked due to stress when the metal layer is formed. Therefore, the better range of the thickness of the metal layer is about 0.2 μm to 20 μm. In the first embodiment, the P-type thermoelectric conversion element 11 is a manganese-silicon element, the N-type thermoelectric conversion element 12 is a magnesium-silicon element, and each of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 is used. A metal layer made of nickel was formed on the surface.
下部応力緩和電極２０１および上部応力緩和電極２０２はそれぞれ、第１金属材２１、応力緩和材２２、第２金属材２３および金属封止部２４により構成されている。下部応力緩和電極２０１および上部応力緩和電極２０２は、銅、ニッケル、アルミニウム、チタン、モリブデン、タングステン、鉄、またはこれらの金属のうちのいずれかを主成分とする合金であることが望ましい。主成分の概念は上述した通りである。これらの金属を選択することにより、熱伝導性が高い応力緩和部を得ることができる。さらに、これらの金属を選択することにより、塑性変形を利用して薄く形成することにより柔軟性を向上させた金属封止部２４、および第１金属材２１と第２金属材２３とに挟持された応力緩和材２２からなる応力緩和部を得ることができる。 The lower stress relaxation electrode 201 and the upper stress relaxation electrode 202 are configured by the first metal material 21, the stress relaxation material 22, the second metal material 23, and the metal sealing portion 24, respectively. The lower stress relaxation electrode 201 and the upper stress relaxation electrode 202 are preferably made of copper, nickel, aluminum, titanium, molybdenum, tungsten, iron, or an alloy mainly containing any one of these metals. The concept of the main component is as described above. By selecting these metals, a stress relaxation part with high thermal conductivity can be obtained. Furthermore, by selecting these metals, they are sandwiched between the metal sealing part 24 and the first metal material 21 and the second metal material 23, which are made thin by using plastic deformation and have improved flexibility. Thus, a stress relaxation part made of the stress relaxation material 22 can be obtained.
応力緩和材２２として、例えば直径１００μｍの銅からなる細線を編み込んで作製した柔軟な金属繊維を使用した。使用する金属線の直径については編み込み可能な太さであれば、特に限定されず、１μｍ〜５００μｍ程度の範囲であればよい。ただし、金属線の直径が小さすぎると、後述する加圧加熱工程において金属繊維が破壊する恐れがある。逆に、金属線の直径が大きすぎると、後述する金属封止部２４の形成過程において、金属線が塑性変形し難くなり、金属封止部２４を得ることが難しくなる。そのため、使用する金属線の直径のよりよい範囲は、４０μｍ〜１５０μｍ程度である。金属繊維の編み方は一重編組、二重編組または三重編組などであればよく、特に編み方は限定されない。すなわち、応力緩和材２２が、１枚の金属板で形成した場合と比べて柔軟性を備えていればよい。 As the stress relaxation material 22, for example, a flexible metal fiber produced by braiding a thin wire made of copper having a diameter of 100 μm was used. The diameter of the metal wire to be used is not particularly limited as long as the thickness can be knitted, and may be in the range of about 1 μm to 500 μm. However, if the diameter of the metal wire is too small, the metal fiber may be destroyed in the pressurizing and heating process described later. On the contrary, if the diameter of the metal wire is too large, the metal wire is difficult to be plastically deformed in the process of forming the metal sealing portion 24 described later, and it is difficult to obtain the metal sealing portion 24. Therefore, the better range of the diameter of the metal wire to be used is about 40 μm to 150 μm. The metal fiber may be knitted in a single braid, double braid, triple braid, or the like, and the knitting method is not particularly limited. That is, the stress relaxation material 22 only needs to have flexibility as compared with the case where the stress relaxation material 22 is formed of one metal plate.
また、応力緩和材２２は必ずしも金属線を編み込んだ金属繊維でなくともよく、線材を束ねた束線、または線材を撚って形成した撚線を用いてもよい。さらに、アルミニウム、銅、ニッケルまたはこれらの金属のうちのいずれかを主成分とする合金からなる発泡金属（ポーラス金属）または金属粉末を用いてもよい。応力緩和材２２の空隙率（単位体積あたりのすきまの割合を百分率で表したもの）は、２０％以上９０％以下程度の範囲である。空隙率は応力緩和材２２を切断した断面を撮像し、断面像の空隙率によって測定することができる。空隙率は２０％以上９０％以下の値をとることで、金属同士の接触により熱伝導を確保しつつ、空隙により応力を緩衝することができる。また、空隙率が５％以上２０％未満の場合は、熱伝導率をさらに向上させることができる。 Moreover, the stress relaxation material 22 does not necessarily need to be a metal fiber in which a metal wire is knitted, and may be a bundle of wires bundled or a twisted wire formed by twisting a wire. Further, foam metal (porous metal) or metal powder made of aluminum, copper, nickel, or an alloy mainly containing any of these metals may be used. The porosity of the stress relaxation material 22 (the percentage of the clearance per unit volume expressed as a percentage) is in the range of about 20% to about 90%. The porosity can be measured by imaging a cross section of the stress relaxation material 22 and measuring the porosity of the cross-sectional image. By taking a value of the porosity of 20% or more and 90% or less, the stress can be buffered by the void while ensuring heat conduction by contact between metals. Moreover, when the porosity is 5% or more and less than 20%, the thermal conductivity can be further improved.
第１金属材２１として、例えば厚さ３００μｍの銅箔を使用した。使用する第１金属材２１の形態としては箔形状が望ましく、その厚さは、１０μｍ〜１,０００μｍ程度の範囲であればよい。 As the first metal material 21, for example, a copper foil having a thickness of 300 μm was used. The form of the first metal material 21 to be used is desirably a foil shape, and the thickness thereof may be in the range of about 10 μm to 1,000 μm.
また、第２金属材２３として、例えば厚さ３５μｍの銅箔を使用した。使用する第２金属材２３の形態としては箔形状が望ましく、その厚さは、１０μｍ〜１,０００μｍ程度の範囲であればよい。第２金属材２３が厚すぎると、後述する加圧加熱工程において第２金属材２３が塑性変形し難くなり、金属封止部２４を得ることが難しくなる。逆に、第２金属材２３が薄すぎると、後述する加圧加熱工程において塑性変形により、第２金属材２３が破壊する恐れがある。そのため、使用する第２金属材２３の厚さのよりよい範囲は、２５μｍ〜３００μｍ程度である。また、本第１実施形態では、第１金属材２１および第２金属材２３に使用する銅箔の厚さが異なるが、後述する第２実施形態のように同じ厚さの金属箔または金属板としてもよい。 Further, as the second metal material 23, for example, a copper foil having a thickness of 35 μm was used. The form of the second metal material 23 to be used is preferably a foil shape, and the thickness may be in the range of about 10 μm to 1,000 μm. If the second metal material 23 is too thick, it becomes difficult for the second metal material 23 to be plastically deformed in a pressurizing and heating process described later, and it becomes difficult to obtain the metal sealing portion 24. On the other hand, if the second metal material 23 is too thin, the second metal material 23 may be destroyed due to plastic deformation in a pressurizing and heating process described later. Therefore, the better range of the thickness of the second metal material 23 to be used is about 25 μm to 300 μm. In the first embodiment, the thicknesses of the copper foils used for the first metal material 21 and the second metal material 23 are different, but a metal foil or metal plate having the same thickness as in the second embodiment to be described later. It is good.
また、第１金属材２１、応力緩和材２２および第２金属材２３の表面に、ニッケル、チタン、クロム、タングステンまたはモリブデンからなる金属薄膜、あるいはこれらの金属のうちのいずれかを主成分とする金属薄膜が形成されていてもよい。金属薄膜の形成方法としては、クラッド法、めっき法、エアロゾルデポジション法、溶射法、スパッタ法、蒸着法またはイオンプレーティング法などであればよい。金属薄膜の厚さは、１μｍ〜１００μｍ程度の範囲であればよい。例えば第２金属材２３の表面に金属薄膜を施すことにより、Ｐ型熱電変換素子１１またはＮ型熱電変換素子１２と第２金属材２３とを接合する際に接合性が向上する。ただし、金属薄膜が厚すぎると、後述する加圧加熱工程において第２金属材２３が塑性変形し難くなる。逆に、金属薄膜が薄すぎると、金属薄膜に割れが生じる。そのため、使用する金属薄膜の厚さのよりよい範囲は、３μｍ〜１０μｍ程度である。 Moreover, the surface of the first metal material 21, the stress relaxation material 22 and the second metal material 23 is mainly composed of a metal thin film made of nickel, titanium, chromium, tungsten or molybdenum, or one of these metals. A metal thin film may be formed. The metal thin film can be formed by any method such as a cladding method, a plating method, an aerosol deposition method, a thermal spraying method, a sputtering method, a vapor deposition method, or an ion plating method. The thickness of the metal thin film may be in the range of about 1 μm to 100 μm. For example, by applying a metal thin film to the surface of the second metal material 23, the bondability is improved when the P-type thermoelectric conversion element 11 or the N-type thermoelectric conversion element 12 and the second metal material 23 are bonded. However, if the metal thin film is too thick, it is difficult for the second metal material 23 to be plastically deformed in a pressurizing and heating process described later. Conversely, if the metal thin film is too thin, the metal thin film will crack. Therefore, the better range of the thickness of the metal thin film to be used is about 3 μm to 10 μm.
さらに、第１金属材２１の片面にはアルミナ、窒化アルミまたは窒化珪素などのセラミックスからなる絶縁膜が形成されていてもよい。絶縁膜の厚さは、０．５μｍ〜１００μｍ程度の範囲であればよい。絶縁膜を施すことにより、短絡することなく、熱源体に直接熱電変換モジュールを設置することが可能になる。ただし、絶縁膜が厚すぎると、熱抵抗が増加することで発電性能が低下する恐れがある。加えて絶縁膜の膜応力により、絶縁膜が破壊する恐れがある。逆に、絶縁膜が薄すぎると、絶縁性を確保できず、熱電変換モジュールが短絡する恐れがある。そのため、使用する絶縁膜の厚さのよりよい範囲は、１μｍ〜１０μｍ程度である。 Furthermore, an insulating film made of ceramics such as alumina, aluminum nitride, or silicon nitride may be formed on one surface of the first metal material 21. The thickness of the insulating film may be in the range of about 0.5 μm to 100 μm. By applying the insulating film, it is possible to install the thermoelectric conversion module directly on the heat source body without causing a short circuit. However, if the insulating film is too thick, power generation performance may be reduced due to an increase in thermal resistance. In addition, the insulating film may be destroyed by the film stress of the insulating film. Conversely, if the insulating film is too thin, insulation cannot be ensured, and the thermoelectric conversion module may be short-circuited. Therefore, a better range of the thickness of the insulating film to be used is about 1 μm to 10 μm.
≪熱電変換モジュールを構成する応力緩和電極の製造方法≫
次に、本第１実施形態による応力緩和電極の製造方法を、図２〜図５を用いて説明する。図２は、本第１実施形態による熱電変換モジュールを構成する下部応力緩和電極の製造工程を示す要部断面図である。図３は、図２に続く、下部応力緩和電極の製造工程を示す要部断面図である。図４は、図３に続く、下部応力緩和電極の製造工程を示す要部断面図である。なお、上部応力緩和電極の製造工程は、下部応力緩和電極の製造工程と同様である。図５は、本第１実施形態による応力緩和電極の断面写真である。
≪Manufacturing method of stress relaxation electrode constituting thermoelectric conversion module≫
Next, the manufacturing method of the stress relaxation electrode according to the first embodiment will be described with reference to FIGS. FIG. 2 is a cross-sectional view of a principal part showing a manufacturing process of a lower stress relaxation electrode constituting the thermoelectric conversion module according to the first embodiment. FIG. 3 is a cross-sectional view of a principal part illustrating the manufacturing process of the lower stress relaxation electrode continued from FIG. 2. 4 is a cross-sectional view of a principal part showing the manufacturing process of the lower stress relaxation electrode continued from FIG. The manufacturing process of the upper stress relaxation electrode is the same as the manufacturing process of the lower stress relaxation electrode. FIG. 5 is a cross-sectional photograph of the stress relaxation electrode according to the first embodiment.
まず、図２に示す支持治具３１および加圧治具３２を準備する。支持治具３１および加圧治具３２はカーボンからなる。本第１実施形態では、支持治具３１および加圧治具３２をカーボンにより形成したが、セラミックスまたは金属などであってもよい。すなわち、支持治具３１および加圧治具３２は、後述する加圧加熱工程において溶融しない材料で、かつ、第１金属材２１および第２金属材２３と反応しない材料から構成される。または、支持治具３１および加圧治具３２は、後述する加圧加熱工程において溶融しない材料で、かつ、表面に第１金属材２１および第２金属材２３との反応が抑制できる層が形成された構成であってもよい。 First, a support jig 31 and a pressure jig 32 shown in FIG. 2 are prepared. The support jig 31 and the pressure jig 32 are made of carbon. In the first embodiment, the support jig 31 and the pressure jig 32 are made of carbon, but may be ceramic or metal. That is, the support jig 31 and the pressurizing jig 32 are made of a material that does not melt in the pressurizing and heating process described later and that does not react with the first metal material 21 and the second metal material 23. Alternatively, the supporting jig 31 and the pressing jig 32 are made of a material that does not melt in the pressurizing and heating process described later, and a layer that can suppress the reaction with the first metal material 21 and the second metal material 23 is formed on the surface. It may be a configured.
また、加圧治具３２の加圧面３２ａは、凹凸形状になっている。これは、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２が搭載されない下部応力緩和電極２０１を薄く加工して、金属封止部２４を形成するためである。 Further, the pressing surface 32a of the pressing jig 32 has an uneven shape. This is to form the metal sealing portion 24 by thinly processing the lower stress relaxation electrode 201 on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are not mounted.
次に、支持治具３１の加圧面３１ａ側から、第１金属材２１、応力緩和材２２および第２金属材２３の順に配置し、第２金属材２３の上部に、加圧面３２ａを第２金属材２３側に向けて加圧治具３２を配置する。 Next, from the pressure surface 31 a side of the support jig 31, the first metal material 21, the stress relaxation material 22, and the second metal material 23 are arranged in this order, and the pressure surface 32 a is disposed on the second metal material 23 on the second side. A pressing jig 32 is arranged toward the metal material 23 side.
次に、図３に示すように、支持治具３１と加圧治具３２とで第１金属材２１、応力緩和材２２および第２金属材２３を挟持した状態で、これらを加熱および加圧する。加熱の条件は、例えば保持温度６５０℃、保持時間１０分、昇温速度６０℃／分である。また、接合雰囲気は窒素である。 Next, as shown in FIG. 3, in a state where the first metal material 21, the stress relaxation material 22 and the second metal material 23 are sandwiched between the support jig 31 and the pressure jig 32, these are heated and pressurized. . The heating conditions are, for example, a holding temperature of 650 ° C., a holding time of 10 minutes, and a heating rate of 60 ° C./min. The bonding atmosphere is nitrogen.
保持温度は、３００℃〜１,０００℃程度の範囲であればよい。保持温度が低すぎると、応力緩和材２２の塑性変形が不十分であり、金属封止部２４を形成し難い。逆に、保持温度が高すぎると、第１金属材２１、応力緩和材２２および第２金属材２３が溶融することで下部応力緩和電極２０１の成形ができない。上限温度については、第１金属材２１、応力緩和材２２および第２金属材２３が溶融しない温度であれば問題ないが、装置上の制限もあるため、保持温度のよりよい範囲は、３００℃〜７００℃程度である。 The holding temperature may be in the range of about 300 ° C to 1,000 ° C. If the holding temperature is too low, the plastic deformation of the stress relaxation material 22 is insufficient, and the metal sealing part 24 is difficult to form. On the other hand, if the holding temperature is too high, the first metal material 21, the stress relaxation material 22 and the second metal material 23 are melted, so that the lower stress relaxation electrode 201 cannot be formed. As for the upper limit temperature, there is no problem as long as the first metal material 21, the stress relaxation material 22 and the second metal material 23 are not melted. However, since there is a limitation on the apparatus, the better range of the holding temperature is 300 ° C. It is about -700 degreeC.
保持時間は、１分〜６０分程度の範囲であればよい。金属封止部２４は、第１金属材２１、応力緩和材２２および第２金属材２３が固体状態で原子が拡散することで形成される。そのため、保持時間が短いと、原子の拡散が十分に進行せず、金属封止部２４を形成し難い。保持時間が長い場合は特に問題はないが、製造上時間が短い方が効率的に製造できるため、保持時間のよりよい範囲は、５分〜２０分程度である。 The holding time may be in the range of about 1 minute to 60 minutes. The metal sealing portion 24 is formed by atoms diffusing in the solid state of the first metal material 21, the stress relaxation material 22, and the second metal material 23. Therefore, if the holding time is short, the diffusion of atoms does not proceed sufficiently and it is difficult to form the metal sealing portion 24. When the holding time is long, there is no particular problem, but the shorter the manufacturing time, the more efficiently the manufacturing can be performed. Therefore, a better range of the holding time is about 5 to 20 minutes.
昇温速度は保持温度と保持時間との関係で変化するが、１０℃／分〜６０℃／分程度の範囲であればよい。 The rate of temperature increase varies depending on the relationship between the holding temperature and the holding time, but may be in the range of about 10 ° C./min to 60 ° C./min.
接合加圧は３０ＭＰａとしたが、加圧は、１ＭＰａ〜１００ＭＰａ程度の範囲であればよい。加圧が低すぎると、応力緩和材２２の塑性変形が不十分で密接しないため、金属封止部２４を形成し難い。逆に、加圧が高すぎると、第２金属材２３および応力緩和材２２が破壊する恐れがある。そのため、加圧のよりよい範囲は、１０ＭＰａ〜５０ＭＰａ程度である。 Although the bonding pressure is 30 MPa, the pressure may be in the range of about 1 MPa to 100 MPa. If the pressurization is too low, the plastic deformation of the stress relaxation material 22 is insufficient and does not come into close contact with each other, so that it is difficult to form the metal sealing portion 24. Conversely, if the pressure is too high, the second metal material 23 and the stress relaxation material 22 may be destroyed. Therefore, the better range of pressurization is about 10 MPa to 50 MPa.
また、接合雰囲気を窒素としたが、真空雰囲気、水素雰囲気、窒素水素混合雰囲気またはアルゴン雰囲気などの非酸化雰囲気であればよい。 Further, although the bonding atmosphere is nitrogen, any non-oxidizing atmosphere such as a vacuum atmosphere, a hydrogen atmosphere, a nitrogen-hydrogen mixed atmosphere, or an argon atmosphere may be used.
上記製造工程によって接合した後、支持治具３１および加圧治具３２を取り外すことにより、図４に示す下部応力緩和電極２０１が製造される。また、同様の製造工程により、上部応力緩和電極２０２が製造される。 After joining by the said manufacturing process, the support jig | tool 31 and the pressurization jig | tool 32 are removed, and the lower stress relaxation electrode 201 shown in FIG. 4 is manufactured. Further, the upper stress relaxation electrode 202 is manufactured by the same manufacturing process.
図５に、本第１実施形態による応力緩和電極の断面写真を示す。 FIG. 5 shows a cross-sectional photograph of the stress relaxation electrode according to the first embodiment.
第１金属材２１と第２金属材２３との間に、空隙が含まれる応力緩和材２２が挟持されている。また、支持治具３２の凸部で加圧されることにより応力緩和材２２が塑性変形して、薄い金属封止部２４が形成され、第１金属材２１と第２金属材２３とが空隙の少ない状態で密接していることがわかる。 Between the first metal material 21 and the second metal material 23, a stress relaxation material 22 including a void is sandwiched. In addition, the stress relaxation material 22 is plastically deformed by being pressed by the convex portion of the support jig 32 to form a thin metal sealing portion 24, and the first metal material 21 and the second metal material 23 are voids. It can be seen that they are closely connected in a state with little.
一方、応力緩和材２２内に多くの空隙が含まれる応力緩和部２５では、第１金属材２１と第２金属材２３とが密接しておらず、応力緩和材２２が自由に変形することができる。従って、応力緩和部２５にＰ型熱電変換素子１１およびＮ型熱電変換素子１２を接合すると、熱電変換モジュールの稼動時に負荷される熱応力、および振動または衝撃を応力緩和材２２で吸収することが可能である。加えて、後述する熱電変換モジュールの製造時にＰ型熱電変換素子１１およびＮ型熱電変換素子１２のそれぞれの高さにバラツキがある場合でも、応力緩和材２２が変形することにより、その高さバラツキを吸収することができる。加えて、応力緩和材２２とＰ型熱電変換素子１１またはＮ型熱電変換素子１２との間には第１金属材２３が形成されており、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２を接合する際に、応力緩和材２２内への硬ろうまたは軟ろうなどの接合材の浸入を防ぐことができるので、応力緩和能を損なわない。 On the other hand, in the stress relaxation part 25 in which many voids are included in the stress relaxation material 22, the first metal material 21 and the second metal material 23 are not in close contact, and the stress relaxation material 22 can be freely deformed. it can. Therefore, when the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are joined to the stress relaxation portion 25, the stress relaxation material 22 can absorb thermal stress, vibration, or impact applied during operation of the thermoelectric conversion module. Is possible. In addition, even when there is a variation in the height of each of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 during the manufacture of a thermoelectric conversion module, which will be described later, the stress relaxation material 22 is deformed, thereby varying the height. Can be absorbed. In addition, a first metal material 23 is formed between the stress relaxation material 22 and the P-type thermoelectric conversion element 11 or the N-type thermoelectric conversion element 12, and the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are formed. In joining, it is possible to prevent the intrusion of a joining material such as a hard solder or a soft solder into the stress relieving material 22, so that the stress relieving ability is not impaired.
さらに、第１金属材２３によってＰ型熱電変換素子１１およびＮ型熱電変換素子１２を面で接合できるため、接合面積を確保して信頼性の高い接合部を形成することが可能である。 Further, since the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 can be joined by the first metal material 23, it is possible to secure a joining area and form a highly reliable joining portion.
さらに、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２を搭載しない金属封止部２４では、第１金属材２１と第２金属材２３とが空隙の少ない状態で密接しているため、熱伝導が向上する。加えて、加圧治具３２により金属封止部２４を薄くしているため、熱電変換モジュールの柔軟性が向上する。熱電変換モジュールの柔軟性が向上することにより、熱源体と接触しやすくなるため、熱電変換モジュールの温度差をとりやすくなり、発電性能が向上する。また、応力緩和材２２が金属封止部２４によって下部応力緩和電極２０１または上部応力緩和電極２０２の内部に封止されていることにより、熱電変換モジュールの組立時または設置環境による振動または衝撃、および熱電変換モジュールの稼動時の熱応力の影響による、応力緩和材２２の綻び、飛散または遊離を防止することが可能である。 Furthermore, in the metal sealing part 24 in which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are not mounted, the first metal material 21 and the second metal material 23 are in close contact with a small gap, Conduction is improved. In addition, since the metal sealing portion 24 is thinned by the pressurizing jig 32, the flexibility of the thermoelectric conversion module is improved. Since the flexibility of the thermoelectric conversion module is improved, the thermoelectric conversion module is easily brought into contact with the heat source body, so that the temperature difference of the thermoelectric conversion module is easily taken and the power generation performance is improved. Further, since the stress relaxation material 22 is sealed inside the lower stress relaxation electrode 201 or the upper stress relaxation electrode 202 by the metal sealing portion 24, vibration or impact due to the assembly or installation environment of the thermoelectric conversion module, and It is possible to prevent the stress relaxation material 22 from being broken, scattered or separated due to the influence of thermal stress during operation of the thermoelectric conversion module.
≪熱電変換モジュールの製造方法≫
次に、本第１実施形態による熱電変換モジュールの製造方法を、図６〜図９を用いて説明する。図６は、本第１実施形態による熱電変換モジュールの製造工程を示す概略図である。図７は、図６に続く、熱電変換モジュールの製造工程を示す概略図である。図８は、図７に続く、熱電変換モジュールの製造工程を示す概略図である。図９は、本第１実施形態による熱電変換モジュールの斜視図である。
≪Method of manufacturing thermoelectric conversion module≫
Next, the manufacturing method of the thermoelectric conversion module according to the first embodiment will be described with reference to FIGS. FIG. 6 is a schematic view showing a manufacturing process of the thermoelectric conversion module according to the first embodiment. FIG. 7 is a schematic diagram illustrating manufacturing steps of the thermoelectric conversion module following FIG. 6. FIG. 8 is a schematic diagram illustrating a manufacturing process of the thermoelectric conversion module following FIG. 7. FIG. 9 is a perspective view of the thermoelectric conversion module according to the first embodiment.
まず、図６に示すように、支持治具３３上に下部応力緩和電極２０１を載置する。次に、下部応力緩和電極２０１上であって、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２の接続箇所に接合材（図示は省略）を載置し、続いて、その接合材上にＰ型熱電変換素子１１およびＮ型熱電変換素子１２をそれぞれ位置合せして、載置する。次に、Ｐ型熱電変換素子１１上およびＮ型熱電変換素子１２上に接合材（図示は省略）を載置し、続いて、その接合材上に上部応力緩和電極２０２を載置する。 First, as shown in FIG. 6, the lower stress relaxation electrode 201 is placed on the support jig 33. Next, a bonding material (not shown) is placed on the lower stress relaxation electrode 201 at the connection point of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12, and then on the bonding material. The P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are aligned and placed. Next, a bonding material (not shown) is placed on the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12, and then the upper stress relaxation electrode 202 is placed on the bonding material.
接合材は、Ｐ型熱電変換素子１１の上面、下面（接合面）およびＮ型熱電変換素子１２の上面、下面（接合面）に接合層として予め形成していてもよい。または、接合材は、下部応力緩和電極２０１および上部応力緩和電極２０２に接合層として予め形成していてもよい。 The bonding material may be formed in advance as a bonding layer on the upper surface and lower surface (bonding surface) of the P-type thermoelectric conversion element 11 and on the upper surface and lower surface (bonding surface) of the N-type thermoelectric conversion element 12. Alternatively, the bonding material may be previously formed as a bonding layer on the lower stress relaxation electrode 201 and the upper stress relaxation electrode 202.
接合材は、アルミニウム、ニッケル、錫、銅、亜鉛、ゲルマニウム、シリコン、マグネシウム、金、銀、インジウム、鉛、ビスマス、アンチモン、テルル、チタン、マンガン、コバルト、リン、ボロンまたはこれらの金属のうちのいずれかを主成分とする合金であればよい。主成分の概念は上述した通りである。また、必ずしも接合材を使用しなくてもよく、例えばＰ型熱電変換素子１１の下面およびＮ型熱電変換素子１２の下面に形成した金属薄膜と下部応力緩和電極２０１、並びにＰ型熱電変換素子１１の上面およびＮ型熱電変換素子１２の上面に形成した金属薄膜と上部応力緩和電極２０２とを超音波接合または拡散接合などで固相接合してもよい。 Bonding materials are aluminum, nickel, tin, copper, zinc, germanium, silicon, magnesium, gold, silver, indium, lead, bismuth, antimony, tellurium, titanium, manganese, cobalt, phosphorus, boron or any of these metals Any alloy containing any one of them as a main component may be used. The concept of the main component is as described above. Further, it is not always necessary to use a bonding material. For example, the metal thin film and the lower stress relaxation electrode 201 formed on the lower surface of the P-type thermoelectric conversion element 11 and the lower surface of the N-type thermoelectric conversion element 12, and the P-type thermoelectric conversion element 11. Alternatively, the metal thin film formed on the upper surface of the N-type thermoelectric conversion element 12 and the upper stress relaxation electrode 202 may be solid-phase bonded by ultrasonic bonding or diffusion bonding.
また、下部応力緩和電極２０１、接合材、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２、接合材並びに上部応力緩和電極２０２の載置は、治具を用いて一括で行ってもよく、個別に行ってもよい。 Further, the placement of the lower stress relaxation electrode 201, the bonding material, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12, the bonding material, and the upper stress relaxation electrode 202 may be performed collectively using a jig, It may be done individually.
また、一括でなくとも、一方を予め接合したのち、他方を接合してもよく、方法は問わない。例えば支持治具３３上に下部応力緩和電極２０１、接合材並びにＰ型熱電変換素子１１およびＮ型熱電変換素子１２を載置し、加熱することにより、支持治具３３側の下部応力緩和電極２０１とＰ型熱電変換素子１１およびＮ型熱電変換素子１２とを仮に接合した後、Ｐ型熱電変換素子１１上およびＮ型熱電変換素子１２上に接合材および上部応力緩和電極２０２を載置してもよい。 Moreover, even if it is not lump, after joining one side previously, the other may be joined, and the method is not ask | required. For example, the lower stress relaxation electrode 201, the bonding material, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are placed on the support jig 33 and heated to heat the lower stress relaxation electrode 201 on the support jig 33 side. And the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are temporarily joined, and then the bonding material and the upper stress relaxation electrode 202 are placed on the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12. Also good.
次に、図７に示すように、上方から加圧治具３４により加圧を行うと共に、支持治具３３および加圧治具３４を介して、接合材が溶融する温度まで加熱する。ここでは接合材を溶融させて接合する工程を示しているが、接合材を用いない固相接合の場合は、Ｐ型熱電変換素子１１の上面、下面およびＮ型熱電変換素子１２の上面、下面に形成した金属薄膜、並びに下部応力緩和電極２０１および上部応力緩和電極２０２が溶融しない温度まで加熱して接合する。 Next, as shown in FIG. 7, pressurization is performed from above by the pressurizing jig 34, and heating is performed to a temperature at which the bonding material melts through the support jig 33 and the pressurizing jig 34. Here, the process of melting and bonding the bonding material is shown, but in the case of solid phase bonding without using the bonding material, the upper surface and lower surface of the P-type thermoelectric conversion element 11 and the upper surface and lower surface of the N-type thermoelectric conversion element 12. The metal thin film formed in the above, and the lower stress relaxation electrode 201 and the upper stress relaxation electrode 202 are heated and bonded to a temperature at which they do not melt.
接合後、支持治具３３および加圧治具３４を取り外すことにより、図８に示す熱電変換モジュール１００が製造される。 After joining, the thermoelectric conversion module 100 shown in FIG. 8 is manufactured by removing the support jig 33 and the pressure jig 34.
図９に、本第１実施形態による熱電変換モジュールの斜視図を示す。 FIG. 9 is a perspective view of the thermoelectric conversion module according to the first embodiment.
Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２は、下部応力緩和電極２０１および上部応力緩和電極２０２に接合された構造となる。熱電変換モジュール１００は、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２のそれぞれの上面に形成された上部応力緩和電極２０２とそれぞれの下面に形成された下部応力緩和電極２０１とから、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２へ温度差を与えることにより、温度差に応じた起電力が生じるモジュールである。Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２のそれぞれの上面およびそれぞれの下面に与えた温度差により、熱電変換モジュール１００には電流が生じる。 The P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 have a structure joined to the lower stress relaxation electrode 201 and the upper stress relaxation electrode 202. The thermoelectric conversion module 100 includes a P-type thermoelectric conversion element 11 and an N-type thermoelectric conversion element 12. The upper stress relaxation electrode 202 is formed on each upper surface and the lower stress relaxation electrode 201 is formed on each lower surface. This is a module in which an electromotive force corresponding to the temperature difference is generated by giving a temperature difference to the thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12. A current is generated in the thermoelectric conversion module 100 due to the temperature difference applied to the upper surface and the lower surface of each of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12.
電流は、Ｐ型熱電変換素子１１では高温側から低温側に、Ｎ型熱電変換素子１２では低温側から高温側に流れるので、これらを直列に接合することにより電気的な回路が形成される。このように直列に接続したＰ型熱電変換素子１１とＮ型熱電変換素子１２とを複数接合することでモジュール化する。熱電変換モジュール１００が有するＰ型熱電変換素子１１およびＮ型熱電変換素子１２の全てが電気的に直列で接続される関係が望ましい。この場合は、大きな起電力を得ることが可能となる。なお、取り出す電力によっては、一部並列と組み合わせてもよい。１回路あたりで得られる電力は低くなるが並列であるため冗長化させて、一部の系列が断線しても、他の系列が接続されていることにより、全体としての電流の切断を防ぐことができる。 Since the current flows from the high temperature side to the low temperature side in the P-type thermoelectric conversion element 11 and from the low temperature side to the high temperature side in the N-type thermoelectric conversion element 12, an electric circuit is formed by joining them in series. A module is formed by joining a plurality of P-type thermoelectric conversion elements 11 and N-type thermoelectric conversion elements 12 connected in series in this way. It is desirable that all of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 included in the thermoelectric conversion module 100 are electrically connected in series. In this case, a large electromotive force can be obtained. Depending on the power to be extracted, a part of the power may be combined in parallel. Although the power obtained per circuit is lower, it is redundant because it is parallel, and even if some series are disconnected, other series are connected to prevent current from being disconnected as a whole. Can do.
熱電変換モジュール１００は、ケースに封入して使用しても良いし、このまま使用しても良い。また、図９では、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２を四角柱として表したが、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２の形状は四角柱、三角柱、多角柱、円柱または楕円柱など、柱状であればよい。また、Ｐ型熱電変換素子１１とＮ型熱電変換素子１２とを下部応力緩和電極２０１および上部応力緩和電極２０２で接合したが、必ずしも、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２のそれぞれの上面、下面に下部応力緩和電極２０１または上部応力緩和電極２０２を接合しなくてもよい。例えばＰ型熱電変換素子１１およびＮ型熱電変換素子１２の下面のみに下部応力緩和電極２０１を接合し、上面は通常の金属板からなる電極を接合してもよい。このように、片側のみを下部応力緩和電極２０１としても、前述した効果を発揮することができる。 The thermoelectric conversion module 100 may be used by being enclosed in a case, or may be used as it is. In FIG. 9, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are represented as quadrangular columns. However, the shapes of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are square columns, triangular columns, and polygonal columns. Any columnar shape such as a cylinder or an elliptical column may be used. Further, although the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are joined by the lower stress relaxation electrode 201 and the upper stress relaxation electrode 202, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are not necessarily provided. The lower stress relaxation electrode 201 or the upper stress relaxation electrode 202 may not be bonded to the upper surface and the lower surface. For example, the lower stress relaxation electrode 201 may be bonded only to the lower surfaces of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12, and an electrode made of a normal metal plate may be bonded to the upper surface. Thus, even when only one side is used as the lower stress relaxation electrode 201, the above-described effects can be exhibited.
このように、本第１実施形態によれば、Ｐ型熱電変換素子１１とＮ型熱電変換素子１２とが、下部応力緩和電極２０１および上部応力緩和電極２０２によって互いに交互に接合された構造とすることにより、熱応力が発生する環境下、および振動または衝撃が負荷される環境下においても、高い信頼性および発電性能が確保できる熱電変換モジュール１００を提供することができる。また、熱電変換モジュール１００の組立時の接合性を向上させることができる。 As described above, according to the first embodiment, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are alternately joined by the lower stress relaxation electrode 201 and the upper stress relaxation electrode 202. Thus, it is possible to provide the thermoelectric conversion module 100 that can ensure high reliability and power generation performance even in an environment where thermal stress occurs and in an environment where vibration or impact is applied. Moreover, the joining property at the time of the assembly of the thermoelectric conversion module 100 can be improved.
［第２実施形態］
≪熱電変換モジュールの構造≫
本第２実施形態による熱電変換モジュールの構造を、図１０を用いて説明する。図１０は、本第２実施形態による熱電変換モジュールの一部を拡大して示す要部断面図である。
[Second Embodiment]
≪The structure of thermoelectric conversion module≫
The structure of the thermoelectric conversion module according to the second embodiment will be described with reference to FIG. FIG. 10 is an essential part cross-sectional view showing an enlarged part of the thermoelectric conversion module according to the second embodiment.
図１０に示すように、応力緩和材２２を挟持する金属材が上下とも第２金属材２３になっており、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２を搭載しない金属封止部２４が、前述の第１実施形態に示した金属封止部２４（例えば図１参照）よりもさらに薄くなっている。金属封止部２４がさらに薄くなることにより、熱電変換モジュール１０１の柔軟性がさらに向上し、熱電変換モジュール１０１の設置自由度が向上する。加えて、熱電変換モジュール１０１の組立時、稼動時において、熱電変換モジュール１０１が受ける外力によって、Ｐ型熱電変換素子１１と下部応力緩和電極２０３または上部応力緩和電極２０４との接合部、およびＮ型熱電変換素子１２と下部応力緩和電極２０３または上部応力緩和電極２０４との接合部に生じる応力集中を低減させることが可能になる。 As shown in FIG. 10, the metal material sandwiching the stress relieving material 22 is the second metal material 23 both above and below, and the metal sealing portion 24 on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are not mounted. However, it is thinner than the metal sealing portion 24 (see, for example, FIG. 1) shown in the first embodiment. When the metal sealing portion 24 is further thinned, the flexibility of the thermoelectric conversion module 101 is further improved, and the degree of freedom of installation of the thermoelectric conversion module 101 is improved. In addition, during the assembly and operation of the thermoelectric conversion module 101, the joint between the P-type thermoelectric conversion element 11 and the lower stress relaxation electrode 203 or the upper stress relaxation electrode 204, and the N type due to the external force received by the thermoelectric conversion module 101 It is possible to reduce the stress concentration generated at the joint between the thermoelectric conversion element 12 and the lower stress relaxation electrode 203 or the upper stress relaxation electrode 204.
≪熱電変換モジュールを構成する応力緩和電極の製造方法≫
次に、本第２実施形態による応力緩和電極の製造方法を、図１１〜図１３を用いて説明する。図１１は、本第２実施形態による熱電変換モジュールを構成する下部応力緩和電極の製造工程を示す要部断面図である。図１２は、図１１に続く、下部応力緩和電極の製造工程を示す要部断面図である。図１３は、図１２に続く、下部応力緩和電極の製造工程を示す要部断面図である。なお、上部応力緩和電極の製造工程は、下部応力緩和電極の製造工程と同様である。
≪Manufacturing method of stress relaxation electrode constituting thermoelectric conversion module≫
Next, a stress relaxation electrode manufacturing method according to the second embodiment will be described with reference to FIGS. FIG. 11 is a fragmentary cross-sectional view showing a manufacturing process of the lower stress relaxation electrode constituting the thermoelectric conversion module according to the second embodiment. FIG. 12 is a cross-sectional view of the principal part showing the manufacturing process of the lower stress relaxation electrode following FIG. 11. FIG. 13 is a cross-sectional view of the principal part showing the manufacturing process of the lower stress relaxation electrode continued from FIG. The manufacturing process of the upper stress relaxation electrode is the same as the manufacturing process of the lower stress relaxation electrode.
まず、図１１に示すように、２つの加圧治具３２を準備する。２つの加圧治具３２の加圧面３２ａは、凹凸形状になっている。１つの加圧治具３２の加圧面３２ａ側から、第２金属材２３、応力緩和材２２および第２金属材２３の順に配置し、第２金属材２３の上部に、加圧面３２ａを第２金属材２３側に向けて加圧治具３２を配置する。従って、応力緩和材２２および第２金属材２３を挟持する２つの加圧治具３２の加圧面３２ａが凹凸形状を有していることが、前述の第１実施形態における下部応力緩和電極２０１の製造方法と異なる。 First, as shown in FIG. 11, two pressure jigs 32 are prepared. The pressing surfaces 32a of the two pressing jigs 32 have an uneven shape. The second metal material 23, the stress relaxation material 22, and the second metal material 23 are arranged in this order from the pressure surface 32 a side of one pressure jig 32, and the pressure surface 32 a is disposed on the second metal material 23 on the second side. A pressing jig 32 is arranged toward the metal material 23 side. Therefore, the pressurizing surfaces 32a of the two pressurizing jigs 32 sandwiching the stress relieving material 22 and the second metal material 23 have an uneven shape, which indicates that the lower stress relieving electrode 201 in the first embodiment described above. Different from the manufacturing method.
次に、図１２に示すように、２つの加圧治具３２とで第２金属材２３、応力緩和材２２および第２金属材２３を挟持した状態で、これらを加熱および加圧する。 Next, as shown in FIG. 12, in a state where the second metal material 23, the stress relaxation material 22 and the second metal material 23 are sandwiched between the two pressing jigs 32, these are heated and pressed.
上記製造工程によって接合した後、２つの加圧治具３２を取り外すことにより、図１３に示す下部応力緩和電極２０３が製造される。また、同様の製造工程により、上部応力緩和電極２０４が製造される。 After joining by the said manufacturing process, the lower stress relaxation electrode 203 shown in FIG. 13 is manufactured by removing the two pressurization jigs 32. FIG. Further, the upper stress relaxation electrode 204 is manufactured by the same manufacturing process.
下部応力緩和電極２０３の上面および下面を凹凸形状に加工する加圧治具３２を用いることにより、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２が搭載される応力緩和部は、より厚く形成されて、下部応力緩和電極２０３は応力緩和能に優れる。さらに、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２が搭載されない金属封止部２４は、より薄く形成されて、下部応力緩和電極２０３は柔軟性に優れる。 By using the pressing jig 32 that processes the upper and lower surfaces of the lower stress relaxation electrode 203 into an uneven shape, the stress relaxation portion on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are mounted is formed to be thicker. Thus, the lower stress relaxation electrode 203 is excellent in stress relaxation capability. Furthermore, the metal sealing portion 24 on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are not mounted is formed thinner, and the lower stress relaxation electrode 203 is excellent in flexibility.
同様に、上部応力緩和電極２０４の上面および下面を凹凸形状に加工する加圧治具３２を用いることにより、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２が搭載される応力緩和部は、より厚く形成されて、上部応力緩和電極２０４は応力緩和能に優れる。さらに、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２が搭載されない金属封止部２４は、より薄く形成されて、上部応力緩和電極２０４は柔軟性に優れる。 Similarly, by using the pressing jig 32 that processes the upper and lower surfaces of the upper stress relaxation electrode 204 into a concavo-convex shape, the stress relaxation portion on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are mounted is The upper stress relaxation electrode 204 is formed thicker and has excellent stress relaxation capability. Furthermore, the metal sealing part 24 on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are not mounted is formed thinner, and the upper stress relaxation electrode 204 is excellent in flexibility.
熱電変換モジュール１０１の構成および製造方法については、上記に説明した以外は基本的に前述の第１実施形態において説明した内容と同様である。 The configuration and manufacturing method of the thermoelectric conversion module 101 are basically the same as those described in the first embodiment except for those described above.
このように、本第２実施形態によれば、前述の第１実施形態に記載した熱電変換モジュール１００よりも、さらに、応力緩和能および柔軟性に優れた下部応力緩和電極２０３および上部応力緩和電極２０４を備える熱電変換モジュール１０１を提供することができる。 Thus, according to the second embodiment, the lower stress relaxation electrode 203 and the upper stress relaxation electrode, which are more excellent in stress relaxation capability and flexibility than the thermoelectric conversion module 100 described in the first embodiment described above. A thermoelectric conversion module 101 including 204 can be provided.
［第３実施形態］
≪熱電変換モジュールの構造≫
本第３実施形態による熱電変換モジュールの構造を、図１４を用いて説明する。図１４は、本第３実施形態による熱電変換モジュールの一部を拡大して示す要部断面図である。
[Third Embodiment]
≪The structure of thermoelectric conversion module≫
The structure of the thermoelectric conversion module according to the third embodiment will be described with reference to FIG. FIG. 14 is an enlarged cross-sectional view showing a part of the thermoelectric conversion module according to the third embodiment.
図１４に示すように、本第３実施形態による熱電変換モジュールでは、下部応力緩和電極２０５の構造が、前述の第１実施形態に示した下部応力緩和電極２０１の構造と異なる。下部応力緩和電極２０５の基本的な構造は、前述の第１実施形態に示した下部応力緩和電極２０１の構造とほぼ同じであるが、下部応力緩和電極２０５を構成する応力緩和材２２の一部がＰ型熱電変換素子１１およびＮ型熱電変換素子１２の形状に合わせて陥没している点が、前述の第１実施形態に示した下部応力緩和電極２０１と異なる。下部応力緩和電極２０５の陥没部は、例えば前述の第１実施形態の図２で示した加圧治具３２の凹凸形状を調整することにより形成することが可能である。 As shown in FIG. 14, in the thermoelectric conversion module according to the third embodiment, the structure of the lower stress relaxation electrode 205 is different from the structure of the lower stress relaxation electrode 201 shown in the first embodiment. The basic structure of the lower stress relaxation electrode 205 is almost the same as the structure of the lower stress relaxation electrode 201 shown in the first embodiment, but a part of the stress relaxation material 22 constituting the lower stress relaxation electrode 205 is used. Is different from the lower stress relaxation electrode 201 shown in the first embodiment in that it is depressed in accordance with the shapes of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12. The depressed portion of the lower stress relaxation electrode 205 can be formed, for example, by adjusting the uneven shape of the pressing jig 32 shown in FIG. 2 of the first embodiment described above.
本第３実施形態による熱電変換モジュールの構造の変形例を、図１５〜図１９に示す。図１５〜図１９はそれぞれ、本第３実施形態による熱電変換モジュールの第１変形例〜第５変形例の一部を拡大して示す要部断面図である。 Modification examples of the structure of the thermoelectric conversion module according to the third embodiment are shown in FIGS. FIGS. 15 to 19 are enlarged cross-sectional views illustrating main parts of first to fifth modifications of the thermoelectric conversion module according to the third embodiment.
図１５に示す第１変形例では、上部応力緩和電極２０６の構造が、前述の第１実施形態に示した上部応力緩和電極２０２の構造と異なる。上部応力緩和電極２０６の基本的な構造は、前述の第１実施形態に示した上部応力緩和電極２０２の構造とほぼ同じであるが、上部応力緩和電極２０６を構成する応力緩和材２２の一部がＰ型熱電変換素子１１およびＮ型熱電変換素子１２の形状に合わせて陥没している点が、前述の第１実施形態に示した上部応力緩和電極２０２と異なる。 In the first modification shown in FIG. 15, the structure of the upper stress relaxation electrode 206 is different from the structure of the upper stress relaxation electrode 202 shown in the first embodiment. The basic structure of the upper stress relaxation electrode 206 is substantially the same as the structure of the upper stress relaxation electrode 202 shown in the first embodiment, but a part of the stress relaxation material 22 constituting the upper stress relaxation electrode 206. Is different from the upper stress relaxation electrode 202 shown in the first embodiment in that it is depressed according to the shapes of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12.
図１６に示す第２変形例では、下部応力緩和電極２０５および上部応力緩和電極２０６の構造がそれぞれ前述の第１実施形態に示した下部応力緩和電極２０１および上部応力緩和電極２０２の構造と異なる。すなわち、下部応力緩和電極２０５および上部応力緩和電極２０６をそれぞれ構成する応力緩和材２２の一部が陥没している。 In the second modification shown in FIG. 16, the structures of the lower stress relaxation electrode 205 and the upper stress relaxation electrode 206 are different from the structures of the lower stress relaxation electrode 201 and the upper stress relaxation electrode 202 shown in the first embodiment, respectively. That is, a part of the stress relaxation material 22 constituting the lower stress relaxation electrode 205 and the upper stress relaxation electrode 206 is depressed.
図１７に示す第３変形例では、下部応力緩和電極２０７の構造が、前述の第２実施形態に示した下部応力緩和電極２０３の構造と異なる。下部応力緩和電極２０７の基本的な構造は、前述の第２実施形態に示した下部応力緩和電極２０３の構造とほぼ同じであるが、下部応力緩和電極２０７を構成する応力緩和材２２の一部がＰ型熱電変換素子１１およびＮ型熱電変換素子１２の形状に合わせて陥没している点が、前述の第２実施形態に示した下部応力緩和電極２０３と異なる。 In the third modification shown in FIG. 17, the structure of the lower stress relaxation electrode 207 is different from the structure of the lower stress relaxation electrode 203 shown in the second embodiment. The basic structure of the lower stress relaxation electrode 207 is substantially the same as the structure of the lower stress relaxation electrode 203 shown in the second embodiment, but a part of the stress relaxation material 22 constituting the lower stress relaxation electrode 207. Is different from the lower stress relaxation electrode 203 shown in the second embodiment in that it is depressed in accordance with the shapes of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12.
図１８に示す第４変形例では、上部応力緩和電極２０８の構造が、前述の第２実施形態に示した上部応力緩和電極２０４の構造と異なる。上部応力緩和電極２０８の基本的な構造は、前述の第２実施形態に示した上部応力緩和電極２０４の構造とほぼ同じであるが、上部応力緩和電極２０８を構成する応力緩和材２２の一部がＰ型熱電変換素子１１およびＮ型熱電変換素子１２の形状に合わせて陥没している点が、前述の第２実施形態に示した上部応力緩和電極２０４と異なる。 In the fourth modified example shown in FIG. 18, the structure of the upper stress relaxation electrode 208 is different from the structure of the upper stress relaxation electrode 204 shown in the second embodiment. The basic structure of the upper stress relaxation electrode 208 is substantially the same as the structure of the upper stress relaxation electrode 204 shown in the second embodiment, but a part of the stress relaxation material 22 constituting the upper stress relaxation electrode 208 is used. Is different from the upper stress relaxation electrode 204 shown in the second embodiment in that it is depressed according to the shapes of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12.
図１９に示す第５変形例では、下部応力緩和電極２０７および上部応力緩和電極２０８の構造がそれぞれ前述の第２実施形態に示した下部応力緩和電極２０３および上部応力緩和電極２０４の構造と異なる。すなわち、下部応力緩和電極２０７および上部応力緩和電極２０８をそれぞれ構成する応力緩和材２２の一部が陥没している。 In the fifth modification shown in FIG. 19, the structures of the lower stress relaxation electrode 207 and the upper stress relaxation electrode 208 are different from the structures of the lower stress relaxation electrode 203 and the upper stress relaxation electrode 204 shown in the second embodiment, respectively. That is, a part of the stress relaxation material 22 constituting the lower stress relaxation electrode 207 and the upper stress relaxation electrode 208 is depressed.
≪熱電変換モジュールの製造方法≫
次に、本第３実施形態による熱電変換モジュールの製造方法を、図２０および図２１を用いて説明する。図２０は、本第３実施形態による熱電変換モジュールの製造工程を示す要部断面図である。図２１は、図２０に続く、熱電変換モジュールの製造工程を示す要部断面図である。
≪Method of manufacturing thermoelectric conversion module≫
Next, a method for manufacturing a thermoelectric conversion module according to the third embodiment will be described with reference to FIGS. FIG. 20 is a cross-sectional view of the main part showing the manufacturing process of the thermoelectric conversion module according to the third embodiment. FIG. 21 is a cross-sectional view of the principal part showing the manufacturing process of the thermoelectric conversion module following FIG. 20.
まず、図２０に示すように、下部応力緩和電極２０５のＰ型熱電変換素子１１およびＮ型熱電変換素子１２が搭載される応力緩和部であって、予め設けられた陥没している部分に、接合材（図示は省略）を載置し、続いて、その接合材上にＰ型熱電変換素子１１およびＮ型熱電変換素子１２を載置する。 First, as shown in FIG. 20, the stress relieving part on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 of the lower stress relaxation electrode 205 are mounted, and in a depressed portion provided in advance, A bonding material (not shown) is placed, and then the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are placed on the bonding material.
次に、図２１に示すように、Ｐ型熱電変換素子１１上およびＮ型熱電変換素子１２上に接合材（図示は省略）を載置し、続いて、その接合材上に上部応力緩和電極２０２を載置し、接合する。図２０および図２１では、組立時に使用する支持治具および加圧治具の記載は省略しているが、実際には前述の第１実施形態において説明した、例えば図６および図７に示した支持治具３３および加圧治具３４などを使用する。 Next, as shown in FIG. 21, a bonding material (not shown) is placed on the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12, and then the upper stress relaxation electrode is formed on the bonding material. 202 is mounted and joined. 20 and FIG. 21, the description of the supporting jig and the pressing jig used at the time of assembly is omitted, but actually, for example, as shown in FIG. 6 and FIG. 7 described in the first embodiment described above. A support jig 33 and a pressure jig 34 are used.
下部応力緩和電極２０５において、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２を搭載する応力緩和部の一部がＰ型熱電変換素子１１およびＮ型熱電変換素子１２の形状に合わせて陥没していることで、熱電変換モジュールの組立時に、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２を整列させる治具が不要となり、組立性が向上する。 In the lower stress relaxation electrode 205, a part of the stress relaxation portion on which the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 are mounted is depressed according to the shapes of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12. Therefore, when assembling the thermoelectric conversion module, a jig for aligning the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 becomes unnecessary, and the assemblability is improved.
また、図１５および図１８に示したように、上部応力緩和電極２０６，２０８の応力緩和部に陥没した部分を形成した熱電変換モジュールの場合は、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２の整列性が向上する。 As shown in FIGS. 15 and 18, in the case of the thermoelectric conversion module in which the recessed portion of the upper stress relaxation electrode 206, 208 is formed, the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element are used. 12 alignment is improved.
また、図１６および図１９に示したように、下部応力緩和電極２０５，２０７の応力緩和部および上部応力緩和電極２０６，２０８の応力緩和部に陥没した部分を形成した熱電変換モジュールの場合は、熱電変換モジュールの組立時に、組立性が向上し、Ｐ型熱電変換素子１１およびＮ型熱電変換素子１２の整列性が向上する。 Further, as shown in FIGS. 16 and 19, in the case of the thermoelectric conversion module in which the stress relief portions of the lower stress relaxation electrodes 205 and 207 and the portions depressed in the stress relaxation portions of the upper stress relaxation electrodes 206 and 208 are formed, When the thermoelectric conversion module is assembled, the assemblability is improved, and the alignment of the P-type thermoelectric conversion element 11 and the N-type thermoelectric conversion element 12 is improved.
熱電変換モジュールの構成および製造方法については、上記に説明した以外は基本的に前述の第１実施形態および第２実施形態において説明した内容と同様である。 The configuration and manufacturing method of the thermoelectric conversion module are basically the same as those described in the first embodiment and the second embodiment except for the above description.
このように、本第３実施形態によれば、前述の第１実施形態に記載した熱電変換モジュール１００および前述の第２実施形態に記載した熱電変換モジュール１０１よりも、さらに、組立時の組立性および整列性が向上した熱電変換モジュールを提供することができる。 As described above, according to the third embodiment, the assemblability at the time of assembly is further increased than the thermoelectric conversion module 100 described in the first embodiment and the thermoelectric conversion module 101 described in the second embodiment. A thermoelectric conversion module with improved alignment can be provided.
以上、本発明者によってなされた発明を実施の形態に基づき具体的に説明したが、本発明は前記実施の形態に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能であることはいうまでもない。 As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the embodiment, and various modifications can be made without departing from the scope of the invention. Needless to say.
１１ Ｐ型熱電変換素子
１２ Ｎ型熱電変換素子
２１ 第１金属材
２２ 応力緩和材
２３ 第２金属材
２４ 金属封止部
２５ 応力緩和部
３１ 支持治具
３１ａ 加圧面
３２ 加圧治具
３２ａ 加圧面
３３ 支持治具
３４ 加圧治具
１００ 熱電変換モジュール
１０１ 熱電変換モジュール
２０１ 下部応力緩和電極
２０２ 上部応力緩和電極
２０３ 下部応力緩和電極
２０４ 上部応力緩和電極
２０５ 下部応力緩和電極
２０６ 上部応力緩和電極
２０７ 下部応力緩和電極
２０８ 上部応力緩和電極
DESCRIPTION OF SYMBOLS 11 P type thermoelectric conversion element 12 N type thermoelectric conversion element 21 1st metal material 22 Stress relaxation material 23 2nd metal material 24 Metal sealing part 25 Stress relaxation part 31 Support jig 31a Pressure surface 32 Pressure jig 32a Pressure surface 33 support jig 34 pressure jig 100 thermoelectric conversion module 101 thermoelectric conversion module 201 lower stress relaxation electrode 202 upper stress relaxation electrode 203 lower stress relaxation electrode 204 upper stress relaxation electrode 205 lower stress relaxation electrode 206 upper stress relaxation electrode 207 lower stress Relaxation electrode 208 Upper stress relaxation electrode
Claims (15)
前記電極は、前記Ｐ型熱電変換素子を搭載する第１の部分と、前記Ｎ型熱電変換素子を搭載する第２の部分と、前記Ｐ型熱電変換素子および前記Ｎ型熱電変換素子を搭載しない第３の部分とを有し、
前記第１の部分および前記第２の部分の厚さが、前記第３の部分の厚さよりも厚い、熱電変換モジュール。 A thermoelectric conversion module comprising a P-type thermoelectric conversion element, an N-type thermoelectric conversion element, and electrode portions that alternately connect the P-type thermoelectric conversion element and the N-type thermoelectric conversion element in series,
The electrode is not mounted with a first portion on which the P-type thermoelectric conversion element is mounted, a second portion on which the N-type thermoelectric conversion element is mounted, and the P-type thermoelectric conversion element and the N-type thermoelectric conversion element. A third part,
The thermoelectric conversion module, wherein the first portion and the second portion are thicker than the third portion.
前記第１の部分および前記第２の部分は、金属繊維と、前記金属繊維を封止する金属箔とを有する、熱電変換モジュール。 The thermoelectric conversion module according to claim 1,
The first part and the second part are thermoelectric conversion modules each having a metal fiber and a metal foil that seals the metal fiber.
前記金属繊維は、金属線を編み込んだ編線、金属線を束ねた束線または金属線を撚った撚線である、熱電変換モジュール。 In the thermoelectric conversion module according to claim 2,
The said metal fiber is a thermoelectric conversion module which is the knitted wire which knitted the metal wire, the bundle wire which bundled the metal wire, or the twisted wire which twisted the metal wire.
前記金属繊維の線材の直径は、１μｍ〜５００μｍである、熱電変換モジュール。 In the thermoelectric conversion module according to claim 2,
The diameter of the said metal fiber wire is a thermoelectric conversion module which is 1 micrometer-500 micrometers.
前記金属繊維の線材は、銅、ニッケル、アルミニウム、チタン、モリブデン、タングステン、鉄、またはこれらの金属のうちのいずれかを主成分とする合金からなる、熱電変換モジュール。 In the thermoelectric conversion module according to claim 2,
The wire rod of the metal fiber is a thermoelectric conversion module made of copper, nickel, aluminum, titanium, molybdenum, tungsten, iron, or an alloy mainly containing any one of these metals.
前記金属箔の厚さは、１０μｍ〜１,０００μｍである、熱電変換モジュール。 In the thermoelectric conversion module according to claim 2,
The thermoelectric conversion module, wherein the metal foil has a thickness of 10 μm to 1,000 μm.
前記金属箔は、銅からなる、熱電変換モジュール。 In the thermoelectric conversion module according to claim 2,
The metal foil is a thermoelectric conversion module made of copper.
前記第１の部分および前記第２の部分は、発泡金属と、前記発泡金属を封止する金属箔とを有する、熱電変換モジュール。 The thermoelectric conversion module according to claim 1,
The first part and the second part are thermoelectric conversion modules having a foam metal and a metal foil that seals the foam metal.
前記発泡金属は、アルミニウム、銅、ニッケル、またはこれらの金属のうちのいずれかを主成分とする合金からなる、熱電変換モジュール。 The thermoelectric conversion module according to claim 8, wherein
The said foam metal is a thermoelectric conversion module which consists of an alloy which has aluminum, copper, nickel, or any one of these metals as a main component.
前記第１の部分および前記第２の部分は、金属粉末と、前記金属粉末を封止する金属箔とを有する、熱電変換モジュール。 The thermoelectric conversion module according to claim 1,
The first part and the second part include a metal powder and a metal foil that seals the metal powder.
前記金属粉末は、アルミニウム、銅、ニッケル、またはこれらの金属のうちのいずれかを主成分とする合金からなる、熱電変換モジュール。 The thermoelectric conversion module according to claim 10, wherein
The said metal powder is a thermoelectric conversion module which consists of aluminum, copper, nickel, or the alloy which has either of these metals as a main component.
前記第１の部分および前記第２の部分の空隙率が、前記第３の部分の空隙率よりも高い、熱電変換モジュール。 The thermoelectric conversion module according to claim 1,
The thermoelectric conversion module, wherein the porosity of the first part and the second part is higher than the porosity of the third part.
前記第１の部分および前記第２の部分は、第１金属繊維と、前記第１金属繊維を封止する第１金属箔とを有し、
前記第３の部分は、第２金属繊維と、前記第２金属繊維を封止する第２金属箔とを有し、
前記第１金属繊維と前記第２金属繊維とは、一体的に形成された同一の材料からなり、
前記第２金属繊維の塑性変形が前記第１金属繊維の塑性変形よりも大きい、熱電変換モジュール。 The thermoelectric conversion module according to claim 1,
The first part and the second part have a first metal fiber and a first metal foil that seals the first metal fiber,
The third portion includes a second metal fiber and a second metal foil that seals the second metal fiber,
The first metal fiber and the second metal fiber are made of the same material formed integrally,
The thermoelectric conversion module, wherein the plastic deformation of the second metal fiber is larger than the plastic deformation of the first metal fiber.
（ａ）第１支持治具上に、複数の第１応力緩和電極を互いに離間して配置する工程；
（ｂ）Ｐ型熱電変換素子およびＮ型熱電変換素子を、前記複数の第１応力緩和電極のそれぞれ上に配置する工程；
（ｃ）複数の第２応力緩和電極のそれぞれを、互いに隣り合う前記第１応力緩和電極の一方に配置された前記Ｐ型熱電変換素子上と、互いに隣り合う前記第１応力緩和電極の他方に配置された前記Ｎ型熱電変換素子上とにわたるように配置する工程；
（ｄ）前記複数の第２応力緩和電極上に、第１加圧治具を載置する工程；
（ｅ）前記第１支持治具および前記第１加圧治具をそれぞれ前記複数の第１応力緩和電極および前記複数の第２応力緩和電極に押し付けて加熱する工程、
さらに、前記第１応力緩和電極および前記第２応力緩和電極の製造工程は、以下の工程を含む：
（i）第２支持治具上に、第１金属箔、金属繊維、第２金属箔および第２加圧治具を順に配置する工程；
（ii）前記第２支持治具および前記第２加圧治具をそれぞれ前記第１金属箔および前記第２金属箔に押し付けて加熱する工程、
ここで、前記第２支持治具の前記第１金属箔側の第１面に、凹凸形状が形成されており、前記Ｐ型熱電変換素子および前記Ｎ型熱電変換素子が搭載される部分に対応する位置の前記第１面が凹部、前記Ｐ型熱電変換素子および前記Ｎ型熱電変換素子が搭載されない部分に対応する位置の前記第１面が凸部となっている。 A method for producing a thermoelectric conversion module including the following steps:
(A) a step of arranging a plurality of first stress relaxation electrodes spaced apart from each other on the first support jig;
(B) disposing a P-type thermoelectric conversion element and an N-type thermoelectric conversion element on each of the plurality of first stress relaxation electrodes;
(C) Each of the plurality of second stress relaxation electrodes is placed on the P-type thermoelectric conversion element disposed on one of the first stress relaxation electrodes adjacent to each other and on the other of the first stress relaxation electrodes adjacent to each other. Disposing over the N-type thermoelectric conversion element disposed;
(D) placing a first pressing jig on the plurality of second stress relaxation electrodes;
(E) a step of pressing and heating the first support jig and the first pressure jig against the plurality of first stress relaxation electrodes and the plurality of second stress relaxation electrodes, respectively;
Furthermore, the manufacturing process of the first stress relaxation electrode and the second stress relaxation electrode includes the following steps:
(I) a step of sequentially arranging a first metal foil, a metal fiber, a second metal foil, and a second pressure jig on the second support jig;
(Ii) a step of pressing and heating the second support jig and the second pressure jig against the first metal foil and the second metal foil, respectively.
Here, an uneven shape is formed on the first surface of the second supporting jig on the first metal foil side, and corresponds to a portion on which the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are mounted. The first surface at a position corresponding to a concave portion, and the first surface at a position corresponding to a portion where the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are not mounted is a convex portion.
前記第２加圧治具の前記第２金属箔側の第２面に、凹凸形状が形成されており、前記Ｐ型熱電変換素子および前記Ｎ型熱電変換素子が搭載される部分に対応する位置の前記第２面が凹部、前記Ｐ型熱電変換素子および前記Ｎ型熱電変換素子が搭載されない部分に対応する位置の前記第２面が凸部となっている、熱電変換モジュールの製造方法。 In the manufacturing method of the thermoelectric conversion module according to claim 14,
An uneven shape is formed on the second surface of the second pressure jig on the second metal foil side, and a position corresponding to a portion on which the P-type thermoelectric conversion element and the N-type thermoelectric conversion element are mounted. The manufacturing method of the thermoelectric conversion module in which the said 2nd surface of the said 2nd surface of the position corresponding to the recessed part and the part in which the said P type thermoelectric conversion element and the said N type thermoelectric conversion element are not mounted is a convex part.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016015339A JP2017135309A (en) | 2016-01-29 | 2016-01-29 | Thermoelectric conversion module and method of manufacturing the same |
| PCT/JP2016/078701 WO2017130461A1 (en) | 2016-01-29 | 2016-09-28 | Thermoelectric conversion module and method for manufacturing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016015339A JP2017135309A (en) | 2016-01-29 | 2016-01-29 | Thermoelectric conversion module and method of manufacturing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2017135309A true JP2017135309A (en) | 2017-08-03 |
Family
ID=59397751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016015339A Pending JP2017135309A (en) | 2016-01-29 | 2016-01-29 | Thermoelectric conversion module and method of manufacturing the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2017135309A (en) |
| WO (1) | WO2017130461A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019062118A (en) * | 2017-09-27 | 2019-04-18 | 株式会社日立製作所 | Connection material, thermoelectric conversion module and electronic device |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10303470A (en) * | 1997-04-25 | 1998-11-13 | Aisin Seiki Co Ltd | Thermoelectric cooler |
| JP2007103580A (en) * | 2005-10-03 | 2007-04-19 | Toyota Motor Corp | Thermoelectric transducer and method of manufacturing same |
| JP2008277394A (en) * | 2007-04-26 | 2008-11-13 | Kyocera Corp | Thermoelectric module |
| JP2010212339A (en) * | 2009-03-09 | 2010-09-24 | Sumitomo Chemical Co Ltd | Thermoelectric conversion module |
| JP2014112587A (en) * | 2012-12-05 | 2014-06-19 | Kelk Ltd | Thermoelectric module |
| JP2014204093A (en) * | 2013-04-10 | 2014-10-27 | 日立化成株式会社 | Thermoelectric conversion module and manufacturing method therefor |
| JP2015177047A (en) * | 2014-03-14 | 2015-10-05 | 日立化成株式会社 | thermoelectric conversion module |
-
2016
- 2016-01-29 JP JP2016015339A patent/JP2017135309A/en active Pending
- 2016-09-28 WO PCT/JP2016/078701 patent/WO2017130461A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10303470A (en) * | 1997-04-25 | 1998-11-13 | Aisin Seiki Co Ltd | Thermoelectric cooler |
| JP2007103580A (en) * | 2005-10-03 | 2007-04-19 | Toyota Motor Corp | Thermoelectric transducer and method of manufacturing same |
| JP2008277394A (en) * | 2007-04-26 | 2008-11-13 | Kyocera Corp | Thermoelectric module |
| JP2010212339A (en) * | 2009-03-09 | 2010-09-24 | Sumitomo Chemical Co Ltd | Thermoelectric conversion module |
| JP2014112587A (en) * | 2012-12-05 | 2014-06-19 | Kelk Ltd | Thermoelectric module |
| JP2014204093A (en) * | 2013-04-10 | 2014-10-27 | 日立化成株式会社 | Thermoelectric conversion module and manufacturing method therefor |
| JP2015177047A (en) * | 2014-03-14 | 2015-10-05 | 日立化成株式会社 | thermoelectric conversion module |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019062118A (en) * | 2017-09-27 | 2019-04-18 | 株式会社日立製作所 | Connection material, thermoelectric conversion module and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017130461A1 (en) | 2017-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9601679B2 (en) | Thermoelectric module and method of manufacturing the same | |
| JP4901350B2 (en) | Thermoelectric conversion device and manufacturing method thereof | |
| JP3927784B2 (en) | Method for manufacturing thermoelectric conversion member | |
| US8222724B2 (en) | Semiconductor element module and method for manufacturing the same | |
| US20170250334A1 (en) | Thermo-compression bonding of thermoelectric materials | |
| WO2016013366A1 (en) | Thermoelectric conversion module and method for making same | |
| JP5829403B2 (en) | Insulating substrate for heat dissipation and manufacturing method thereof | |
| JP2007109942A (en) | Thermoelectric module and manufacturing method thereof | |
| US20140102500A1 (en) | Thermoelectric Device Assembly, Thermoelectric Module and its Manufacturing Method | |
| JP2013070044A (en) | Thermoelectric conversion module and method for manufacturing the same | |
| WO2010103949A1 (en) | Method of producing thermoelectric conversion device | |
| WO2017098863A1 (en) | Thermoelectric conversion module and method for manufacturing same | |
| JP2011029295A (en) | Thermoelectric conversion module and method of manufacturing the same | |
| TW201448294A (en) | Thermoelectric device fabrication using direct bonding | |
| JP2007035974A (en) | Thermoelectric converter | |
| WO2006043402A1 (en) | Thermoelectric conversion module | |
| JP6390546B2 (en) | Thermoelectric conversion module and manufacturing method thereof | |
| JP2017130596A (en) | Thermoelectric conversion module and method of manufacturing the same | |
| JP6115047B2 (en) | Thermoelectric conversion module and manufacturing method thereof | |
| WO2017130461A1 (en) | Thermoelectric conversion module and method for manufacturing same | |
| JP6225756B2 (en) | Thermoelectric conversion module | |
| JP2017143111A (en) | Thermoelectric conversion module and method for manufacturing the same | |
| JP2018160560A (en) | Thermoelectric conversion module and manufacturing method thereof | |
| JP2008109054A (en) | Thermoelectric conversion module and method for manufacturing the same | |
| JP6010941B2 (en) | Thermoelectric conversion module with airtight case |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180409 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181218 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20190702 |