JP2017204550A - Thermoelectric conversion material, thermoelectric conversion element and method of manufacturing thermoelectric conversion element - Google Patents
Thermoelectric conversion material, thermoelectric conversion element and method of manufacturing thermoelectric conversion element Download PDFInfo
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本発明は、熱電変換材料に関する。また、本発明は、上記熱電変換材料を用いた熱電変換素子に関する。さらに、本発明は、上記熱電変換材料を用いた熱電変換素子の製造方法に関する。 The present invention relates to a thermoelectric conversion material. Moreover, this invention relates to the thermoelectric conversion element using the said thermoelectric conversion material. Furthermore, this invention relates to the manufacturing method of the thermoelectric conversion element using the said thermoelectric conversion material.
近年、エネルギー問題への取り組みが活発化しており、熱エネルギーの回収技術への期待が高まっている。熱は、体温、太陽熱、エンジン及び工業排熱など様々な場面から回収することができ、最も一般的なエネルギー源である。また、エネルギー効率の高い低炭素社会を実現するために、熱エネルギーの回収技術の必要性は増大している。 In recent years, efforts for energy problems have become active, and expectations for thermal energy recovery technology are increasing. Heat can be recovered from various scenes such as body temperature, solar heat, engine and industrial waste heat, and is the most common energy source. In addition, in order to realize a low-carbon society with high energy efficiency, the need for thermal energy recovery technology is increasing.
熱エネルギーの回収技術としては、ゼーベック効果（又はペルチェ効果）に基づく熱電変換デバイスが、温度差発電、熱センサ及び冷却などの様々な場面で既に活用されている。熱電変換デバイスは、例えば、ｐ型半導体とｎ型半導体との組み合わせである熱電対が多数直列に接続されたモジュール構造を有する。このような熱電変換デバイスは、可動部がないことから騒音及び振動が無く、スケール効果が無く、小さな温度差でも発電でき、様々な機器及び環境に組み込めるという多くの利点を有する。 As a thermal energy recovery technique, a thermoelectric conversion device based on the Seebeck effect (or Peltier effect) has already been used in various scenes such as temperature difference power generation, a thermal sensor, and cooling. The thermoelectric conversion device has, for example, a module structure in which many thermocouples that are combinations of a p-type semiconductor and an n-type semiconductor are connected in series. Such a thermoelectric conversion device has many advantages in that it has no moving parts, has no noise and vibration, has no scale effect, can generate power even with a small temperature difference, and can be incorporated into various devices and environments.
上記のような熱電変換デバイスの一例が、下記の特許文献１に開示されている。特許文献１に記載の熱電変換デバイスは、複数の熱電変換材料を有する。熱電変換材料は、カーボンナノチューブ及びドーパントを含む。ドーパントをカーボンナノチューブの凝集体の内部にも吸着させることにより、ドーパントとカーボンナノチューブとの接触抵抗が小さくなる。複数の熱電変換材料は、電極を介して電気的に接続されている。 An example of the thermoelectric conversion device as described above is disclosed in Patent Document 1 below. The thermoelectric conversion device described in Patent Document 1 has a plurality of thermoelectric conversion materials. The thermoelectric conversion material includes carbon nanotubes and a dopant. By adsorbing the dopant also inside the aggregate of carbon nanotubes, the contact resistance between the dopant and the carbon nanotubes is reduced. The plurality of thermoelectric conversion materials are electrically connected via electrodes.
熱電変換材料と電極とは、例えば、銀ペーストなどの導電性接合部を用いて接合され得る。しかしながら、上記のような熱電変換材料に対する銀ペーストなどの濡れ性が低いことなどから、十分な導電接続を得ることは困難である。この場合には、熱電変換材料と電極との間の電気抵抗を十分に低くすること及び接合力を高めることは困難である。 The thermoelectric conversion material and the electrode can be bonded using, for example, a conductive bonding portion such as a silver paste. However, it is difficult to obtain a sufficient conductive connection due to the low wettability of silver paste or the like with respect to the thermoelectric conversion material as described above. In this case, it is difficult to sufficiently reduce the electrical resistance between the thermoelectric conversion material and the electrode and to increase the bonding force.
本発明の目的は、電極との間の電気抵抗を十分に低くすることができ、かつ接合力を高めることができる、熱電変換材料を提供することである。本発明は、上記熱電変換材料を用いた熱電変換素子を提供することも目的とする。また、本発明は、上記熱電変換材料を用いた熱電変換素子の製造方法を提供することも目的とする。 The objective of this invention is providing the thermoelectric conversion material which can fully make the electrical resistance between electrodes low, and can raise joining force. Another object of the present invention is to provide a thermoelectric conversion element using the thermoelectric conversion material. Another object of the present invention is to provide a method for producing a thermoelectric conversion element using the thermoelectric conversion material.
本発明の広い局面によれば、第１の導電性接合部に接合され、かつ前記第１の導電性接合部を介して、第１の電極に導電接続されて用いられる熱電変換材料であって、かつ前記第１の電極と離れた位置において第２の電極に導電接続されて用いられる熱電変換材料であって、前記熱電変換材料は、前記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する、熱電変換材料が提供される。 According to a wide aspect of the present invention, there is provided a thermoelectric conversion material that is used by being joined to a first conductive joint and being conductively connected to the first electrode via the first conductive joint. And a thermoelectric conversion material used by being conductively connected to the second electrode at a position away from the first electrode, the thermoelectric conversion material being applied to a portion joined to the first conductive joint portion A thermoelectric conversion material having a surface with an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less is provided.
本発明に係る熱電変換材料のある特定の局面では、第２の導電性接合部に接合され、かつ前記第２の導電性接合部を介して、前記第２の電極に導電接続されて用いられる熱電変換材料であって、前記熱電変換材料は、前記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する。 In a specific aspect of the thermoelectric conversion material according to the present invention, the thermoelectric conversion material is used by being joined to the second conductive joint and conductively connected to the second electrode via the second conductive joint. It is a thermoelectric conversion material, Comprising: The said thermoelectric conversion material has the surface whose arithmetic mean roughness Ra is 7.5 micrometers or more and 50 micrometers or less in the part joined to a said 2nd electroconductive junction part.
本発明の広い局面によれば、第１の電極と、第１の導電性接合部と、熱電変換材料と、第２の電極とを備え、前記熱電変換材料は、前記第１の導電性接合部に接合されている部分を有し、かつ前記第１の導電性接合部を介して、前記第１の電極に導電接続されており、前記熱電変換材料は、前記第１の電極と離れた位置において前記第２の電極に導電接続されており、前記熱電変換材料は、前記第１の導電性接合部に接合されている部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する、熱電変換素子が提供される。 According to a wide aspect of the present invention, the thermoelectric conversion material includes a first electrode, a first conductive junction, a thermoelectric conversion material, and a second electrode, and the thermoelectric conversion material is the first conductive junction. A portion joined to the first portion and electrically conductively connected to the first electrode via the first conductive joint, and the thermoelectric conversion material is separated from the first electrode. The thermoelectric conversion material has an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint at a position. A thermoelectric conversion element having a surface is provided.
本発明に係る熱電変換素子のある特定の局面では、第２の導電性接合部を備え、前記熱電変換材料は、前記第２の導電性接合部に接合されている部分を有し、かつ前記第２の導電性接合部を介して、前記第１の電極と離れた位置において前記第２の電極に導電接続されており、前記熱電変換材料は、前記第２の導電性接合部に接合されている部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する。 In a specific aspect of the thermoelectric conversion element according to the present invention, the thermoelectric conversion material includes a second conductive joint portion, and the thermoelectric conversion material has a portion joined to the second conductive joint portion, and The second electrode is conductively connected to the second electrode at a position away from the first electrode via a second conductive joint, and the thermoelectric conversion material is joined to the second conductive joint. The surface has an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less.
本発明に係る熱電変換素子のある特定の局面では、前記熱電変換材料は、対向し合う第１の表面と第２の表面とを有し、前記熱電変換材料は、前記第１の表面側において、前記第１の導電性接合部を介して、前記第１の電極に導電接続されており、かつ、前記第２の表面側において、前記第２の電極に導電接続されている。 In a specific aspect of the thermoelectric conversion element according to the present invention, the thermoelectric conversion material has a first surface and a second surface facing each other, and the thermoelectric conversion material is on the first surface side. The first electrode is conductively connected to the first electrode through the first conductive joint, and is conductively connected to the second electrode on the second surface side.
本発明に係る熱電変換素子のある特定の局面では、前記熱電変換材料が、カーボンナノチューブを含む。 On the specific situation with the thermoelectric conversion element which concerns on this invention, the said thermoelectric conversion material contains a carbon nanotube.
本発明に係る熱電変換素子のある特定の局面では、前記熱電変換材料が、シート状である。 On the specific situation with the thermoelectric conversion element which concerns on this invention, the said thermoelectric conversion material is a sheet form.
本発明に係る熱電変換素子のある特定の局面では、前記熱電変換材料の厚みが、０．７５μｍ以上、１５０μｍ以下である。 On the specific situation with the thermoelectric conversion element which concerns on this invention, the thickness of the said thermoelectric conversion material is 0.75 micrometer or more and 150 micrometers or less.
本発明に係る熱電変換素子のある特定の局面では、前記第１の導電性接合部が、導電性フィラーを含み、前記第１の導電性接合部に含まれる前記導電性フィラーが、銀又は銅を含む。 In a specific aspect of the thermoelectric conversion element according to the present invention, the first conductive joint includes a conductive filler, and the conductive filler included in the first conductive joint includes silver or copper. including.
本発明に係る熱電変換素子のある特定の局面では、前記第１の導電性接合部が、導電性フィラーを含み、前記第１の導電性接合部に含まれる前記導電性フィラーの平均粒子径が、０．０１μｍ以上、５０μｍ以下である。 In a specific aspect of the thermoelectric conversion element according to the present invention, the first conductive joint includes a conductive filler, and an average particle diameter of the conductive filler included in the first conductive joint is , 0.01 μm or more and 50 μm or less.
本発明に係る熱電変換素子のある特定の局面では、断熱材を備え、前記断熱材が、前記第１の電極と前記２の電極との間に配置されている。 In a specific aspect of the thermoelectric conversion element according to the present invention, a heat insulating material is provided, and the heat insulating material is disposed between the first electrode and the second electrode.
本発明のある広い局面によれば、熱電変換材料を、第１の導電性接合部に接合し、かつ前記第１の導電性接合部を介して、第１の電極に導電接続する第１の導電接続工程と、前記熱電変換材料を、第２の電極に導電接続する第２の導電接続工程とを備え、前記第１の導電接続工程において、前記熱電変換材料として、前記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する熱電変換材料を用いる、熱電変換素子の製造方法が提供される。 According to a broad aspect of the present invention, a first thermoelectric conversion material is joined to a first conductive joint and is electrically connected to the first electrode via the first conductive joint. A conductive connection step; and a second conductive connection step for conductively connecting the thermoelectric conversion material to a second electrode. In the first conductive connection step, the first conductive property is used as the thermoelectric conversion material. A method for manufacturing a thermoelectric conversion element is provided in which a thermoelectric conversion material having a surface with an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less is used for a portion to be joined to the joint.
本発明に係る熱電変換素子の製造方法のある特定の局面では、前記第１の導電接続工程の前に、前記熱電変換材料の前記第１の導電性接合部に接合される部分の表面の算術平均粗さＲａを大きくし、該熱電変換材料の前記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を形成する表面処理工程を備える。 In a specific aspect of the method for manufacturing a thermoelectric conversion element according to the present invention, the arithmetic operation of the surface of the portion of the thermoelectric conversion material to be joined to the first conductive joint portion before the first conductive connection step. A surface treatment step of increasing the average roughness Ra and forming a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion to be joined to the first conductive joint portion of the thermoelectric conversion material Is provided.
本発明に係る熱電変換素子の製造方法のある特定の局面では、前記表面処理工程が、前記第１の導電性接合部に接合される部分に表面算術平均粗さＲａが７．５μｍ未満である表面を有する熱電変換材料を用いて、該熱電変換材料の前記第１の導電性接合部に接合される部分の表面の算術平均粗さＲａを大きくし、該熱電変換材料の前記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を形成する表面処理工程である。 In a specific aspect of the method for manufacturing a thermoelectric conversion element according to the present invention, the surface treatment process has a surface arithmetic average roughness Ra of less than 7.5 μm at a portion joined to the first conductive joint. Using a thermoelectric conversion material having a surface, the arithmetic mean roughness Ra of the surface of the thermoelectric conversion material to be joined to the first conductive joint is increased, and the first electrical conductivity of the thermoelectric conversion material is increased. This is a surface treatment step of forming a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion to be joined to the adhesive joint.
本発明に係る熱電変換素子の製造方法のある特定の局面では、前記第２の導電接続工程が、前記熱電変換材料を、第２の導電性接合部に接合し、かつ前記第２の導電性接合部を介して、前記第２の電極に導電接続する第２の導電接続工程であり、前記第２の導電接続工程において、前記熱電変換材料として、前記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する熱電変換材料を用いる。 On the specific situation with the manufacturing method of the thermoelectric conversion element which concerns on this invention, a said 2nd electroconductive connection process joins the said thermoelectric conversion material to a 2nd electroconductive junction part, and said 2nd electroconductivity. A second conductive connection step for conductively connecting to the second electrode via a bonding portion; in the second conductive connection step, the thermoelectric conversion material is bonded to the second conductive bonding portion; A thermoelectric conversion material having a surface with an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less is used for the portion.
本発明に係る熱電変換素子の製造方法のある特定の局面では、前記第１の導電接続工程において、前記第１の導電性接合部を、導電性フィラーを含む導電ペーストにより形成する。 On the specific situation with the manufacturing method of the thermoelectric conversion element which concerns on this invention, in the said 1st conductive connection process, the said 1st conductive junction part is formed with the electrically conductive paste containing a conductive filler.
本発明に係る熱電変換材料は、第１の導電性接合部に接合され、かつ第１の導電性接合部を介して、第１の電極に導電接続されて用いられる熱電変換材料であって、該熱電変換材料は、第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有するので、電極との間の電気抵抗を十分に低くすることができ、かつ接合力を高めることができる。 The thermoelectric conversion material according to the present invention is a thermoelectric conversion material that is joined to the first conductive joint and is conductively connected to the first electrode through the first conductive joint, Since the thermoelectric conversion material has a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint portion, the electric resistance between the electrodes is sufficiently high It can be lowered and the bonding force can be increased.
本発明に係る熱電変換素子は、第１の電極と、第１の導電性接合部と、熱電変換材料と、第２の電極とを備え、熱電変換材料は、第１の導電性接合部に接合されている部分を有し、かつ第１の導電性接合部を介して、第１の電極に導電接続されており、熱電変換材料は、第１の電極と離れた位置において第２の電極に導電接続されており、熱電変換材料は、第１の導電性接合部に接合されている部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有するので、電気抵抗を十分に低くすることができ、かつ接合力を高めることができる。 The thermoelectric conversion element according to the present invention includes a first electrode, a first conductive joint, a thermoelectric conversion material, and a second electrode, and the thermoelectric conversion material is provided at the first conductive joint. The thermoelectric conversion material has a second electrode at a position apart from the first electrode. The thermoelectric conversion material is electrically connected to the first electrode via the first conductive junction. Since the thermoelectric conversion material has a surface with an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint, the thermoelectric conversion material has an electric resistance. It can be made sufficiently low and the bonding force can be increased.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に係る熱電変換材料は、第１の導電性接合部に接合され、上記第１の導電性接合部を介して、第１の電極に導電接続されて用いられる。さらに、上記熱電変換材料は、上記第１の電極と離れた位置において第２の電極に導電接続されて用いられる。上記熱電変換材料は、上記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する。 The thermoelectric conversion material according to the present invention is used by being joined to the first conductive joint and conductively connected to the first electrode through the first conductive joint. Further, the thermoelectric conversion material is used by being conductively connected to the second electrode at a position away from the first electrode. The thermoelectric conversion material has a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint.
本明細書における算術平均粗さＲａは、ＪＩＳ Ｂ０６０１：２００１に準拠して測定される。 The arithmetic average roughness Ra in the present specification is measured according to JIS B0601: 2001.
上記熱電変換材料の表面は、上記第１の導電性接合部に接合される部分の少なくとも一部において、算術平均粗さＲａが上記範囲内となる凹凸部を有する。上記第１の導電性接合部は、上記熱電変換材料の表面の上記凹凸部において、上記熱電変換材料に接合された部分を有するので、上記第１の導電性接合部と上記熱電変換材料との接合力を高めることができる。上記第１の導電性接合部を介して、上記熱電変換材料と上記第１の電極との接合力を高めることができる。加えて、上記熱電変換材料と上記第１の導電性接合部との接触面積を大きくすることができるので、電気抵抗を低くすることができる。 The surface of the thermoelectric conversion material has a concavo-convex portion having an arithmetic average roughness Ra within the above range in at least a part of a portion joined to the first conductive joint portion. Since the first conductive joint has a portion joined to the thermoelectric conversion material in the concavo-convex portion on the surface of the thermoelectric conversion material, the first conductive joint and the thermoelectric conversion material Bonding force can be increased. The bonding force between the thermoelectric conversion material and the first electrode can be increased via the first conductive bonding portion. In addition, since the contact area between the thermoelectric conversion material and the first conductive joint can be increased, the electrical resistance can be reduced.
上記第１の導電性接合部の形成には、例えば、導電ペーストなどが用いられる。上記熱電変換材料の、上記第１の導電性接合部に接合される部分の算術平均粗さＲａが５０μｍよりも大きい場合、上記導電ペーストが好適に濡れ拡がらないおそれがある。この場合には、上記熱電変換材料と上記第１の電極とを好適に導電接続することができないおそれがある。 For example, a conductive paste or the like is used to form the first conductive joint. When the arithmetic average roughness Ra of the portion to be joined to the first conductive joint portion of the thermoelectric conversion material is larger than 50 μm, the conductive paste may not be suitably spread. In this case, there is a possibility that the thermoelectric conversion material and the first electrode cannot be suitably conductively connected.
上記第１の導電性接合部に接合される部分の算術平均粗さＲａが７．５μｍよりも小さい場合、上記熱電変換材料と上記第１の導電性接合部との接触面積を十分に大きくすることができないおそれがある。 When the arithmetic average roughness Ra of the portion joined to the first conductive joint is less than 7.5 μm, the contact area between the thermoelectric conversion material and the first conductive joint is sufficiently increased. There is a risk that it will not be possible.
上記熱電変換材料は、上記第１の導電性接合部に接合される部分の全体に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有していなくてもよい。上記熱電変換材料は、上記第１の導電性接合部に接合される部分の表面積の全体１００％中の好ましくは５０％以上、より好ましくは８０％以上に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する。 The thermoelectric conversion material may not have a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less over the entire portion joined to the first conductive joint. The thermoelectric conversion material is preferably 50% or more, more preferably 80% or more of the entire surface area of the portion to be joined to the first conductive joint, and the arithmetic average roughness Ra is 7.5 μm. The surface has a thickness of 50 μm or less.
上記第２の電極と上記熱電変換材料との電気抵抗を十分に低くし、かつ接合力を高める観点からは、上記熱電変換材料が第２の導電性接合部に接合され、上記第２の導電性接合部を介して、上記第２の電極に導電接続されて用いられることが好ましい。上記熱電変換材料は、上記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有することが好ましい。 From the viewpoint of sufficiently reducing the electrical resistance between the second electrode and the thermoelectric conversion material and increasing the bonding force, the thermoelectric conversion material is bonded to the second conductive joint, and the second conductive It is preferable that the second electrode is conductively connected through a conductive junction. The thermoelectric conversion material preferably has a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the second conductive joint.
上記熱電変換材料は、上記第２の導電性接合部に接合される部分の全体に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有していなくてもよい。上記熱電変換材料は、上記第２の導電性接合部に接合される部分の表面積の全体１００％中の好ましくは５０％以上、より好ましくは８０％以上に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する。 The thermoelectric conversion material may not have a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less over the entire portion joined to the second conductive joint. The thermoelectric conversion material is preferably 50% or more, more preferably 80% or more of the entire surface area of the portion to be joined to the second conductive joint, and the arithmetic average roughness Ra is 7.5 μm. The surface has a thickness of 50 μm or less.
なお、上記熱電変換材料は、上記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有していなくてもよい。この場合にも、上記熱電変換材料と上記第１の電極との導電接続部分においては、本発明の効果が発揮される。 In addition, the thermoelectric conversion material does not need to have the surface whose arithmetic mean roughness Ra is 7.5 micrometers or more and 50 micrometers or less in the part joined to the said 2nd electroconductive junction part. Also in this case, the effect of the present invention is exhibited in the conductive connection portion between the thermoelectric conversion material and the first electrode.
上記熱電変換材料は、上記第２の導電性接合部を介して上記第２の電極に導電接続されていなくてもよい。上記熱電変換材料は、上記第２の電極と直接接合されていてもよい。この場合においても、上記熱電変換材料と上記第１の電極との導電接続部分において、本発明の効果が発揮される。 The thermoelectric conversion material may not be conductively connected to the second electrode through the second conductive joint. The thermoelectric conversion material may be directly joined to the second electrode. Even in this case, the effect of the present invention is exhibited in the conductive connection portion between the thermoelectric conversion material and the first electrode.
本発明に係る熱電変換素子は、第１の電極と、第１の導電性接合部と、上記熱電変換材料と、第２の電極とを備える。上記熱電変換材料は、上記第１の電極と離れた位置において上記第２の電極に導電接続されている。上記熱電変換材料は、上記第１の導電性接合部に接合されている部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する。上記熱電変換素子は上記熱電変換材料を有するため、上記熱電変換材料と上記第１の電極との接合力を高めることができ、かつ電気抵抗を低くすることができる。 The thermoelectric conversion element according to the present invention includes a first electrode, a first conductive joint, the thermoelectric conversion material, and a second electrode. The thermoelectric conversion material is conductively connected to the second electrode at a position away from the first electrode. The thermoelectric conversion material has a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint. Since the thermoelectric conversion element includes the thermoelectric conversion material, the bonding force between the thermoelectric conversion material and the first electrode can be increased, and the electrical resistance can be reduced.
上記第２の電極と上記熱電変換材料との電気抵抗を十分に低くし、かつ接合力を高める観点からは、上記熱電変換素子は第２の導電性接合部を介して上記第２の電極に導電接続されていることが好ましい。上記熱電変換材料は、上記第２の導電性接合部に接合されている部分を有し、当該部分において、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有することが好ましい。 From the viewpoint of sufficiently reducing the electrical resistance between the second electrode and the thermoelectric conversion material and increasing the bonding force, the thermoelectric conversion element is connected to the second electrode via the second conductive joint. Conductive connection is preferred. It is preferable that the thermoelectric conversion material has a portion bonded to the second conductive bonding portion, and the surface has an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less in the portion.
上記熱電変換材料は、対向し合う第１の表面と第２の表面とを有していてもよい。上記熱電変換材料は、上記第１の表面側において、上記第１の導電性接合部を介して、上記第１の電極に導電接続されており、かつ、上記第２の表面側において、上記第２の電極に導電接続されていてもよい。 The thermoelectric conversion material may have a first surface and a second surface facing each other. The thermoelectric conversion material is conductively connected to the first electrode on the first surface side through the first conductive joint, and on the second surface side, the thermoelectric conversion material is electrically connected to the first surface. The two electrodes may be conductively connected.
上記熱電変換材料は、上記第１の電極に導電接続された表面と同じ表面上における離れた位置において、上記第２の電極に導電接続されていてもよい。 The thermoelectric conversion material may be conductively connected to the second electrode at a position on the same surface as the surface conductively connected to the first electrode.
上記熱電変換材料は、カーボンナノチューブを含むことが好ましい。上記熱電変換材料の上記第１の導電性接合部に接合される部分における、算術平均粗さＲａが上記範囲内となる凹凸部において、カーボンナノチューブの軸の配向方向は、凹凸表面の面方向に沿うことが好ましい。この場合には、上記第１の導電性接合部と上記熱電変換材料との接触抵抗を効果的に低くすることができる。 The thermoelectric conversion material preferably contains carbon nanotubes. In the concavo-convex portion where the arithmetic average roughness Ra is within the above range in the portion joined to the first conductive joint portion of the thermoelectric conversion material, the orientation direction of the carbon nanotube axis is in the plane direction of the concavo-convex surface. It is preferable to follow. In this case, the contact resistance between the first conductive joint and the thermoelectric conversion material can be effectively reduced.
上記熱電変換材料は、カーボンナノチューブのみから構成されていてもよく、上記熱電変換材料に、カーボンナノチューブ以外に吸着物質や残留溶媒等が含まれていてもよい。カーボンナノチューブを含む熱電変換材料は、例えば、カーボンナノチューブを好ましくは９０重量％以上、好ましくは１００重量％以下で含む。 The thermoelectric conversion material may be composed only of carbon nanotubes, and the thermoelectric conversion material may contain an adsorbent, a residual solvent, and the like in addition to the carbon nanotubes. The thermoelectric conversion material containing carbon nanotubes contains, for example, carbon nanotubes preferably at 90% by weight or more, preferably 100% by weight or less.
上記熱電変換材料はシート状であってもよい。上記熱電変換材料は不織布状であってもよい。シート状又は不織布状の熱電変換材料は、屈曲されて用いられてもよい。シート状又は不織布状の熱電変換材料は、屈曲された形状を有していてもよく、折り曲げられた形状又は湾曲された形状を有していてもよい。 The thermoelectric conversion material may be in the form of a sheet. The thermoelectric conversion material may be a nonwoven fabric. The sheet-shaped or nonwoven fabric-shaped thermoelectric conversion material may be bent and used. The sheet-like or nonwoven fabric-like thermoelectric conversion material may have a bent shape, or may have a bent shape or a curved shape.
断熱性を効果的に高める観点からは、上記熱電変換材料の平均厚みは、好ましくは０．７５μｍ以上、より好ましくは１μｍ以上、更に好ましくは１．５μｍ以上である。 From the viewpoint of effectively improving the heat insulation, the average thickness of the thermoelectric conversion material is preferably 0.75 μm or more, more preferably 1 μm or more, and further preferably 1.5 μm or more.
上記熱電変換材料の平均厚みは、好ましくは１５０μｍ以下、より好ましくは１００μｍ以下、更に好ましくは７５μｍ以下である。 The average thickness of the thermoelectric conversion material is preferably 150 μm or less, more preferably 100 μm or less, and still more preferably 75 μm or less.
上記第１の導電性接合部は、導電性フィラーを含んでいてもよい。上記第１の導電性接合部に含まれる上記導電性フィラーが、銀又は銅を含むことが好ましい。電気抵抗を効果的に低くすることができる。 The first conductive joint may include a conductive filler. It is preferable that the conductive filler included in the first conductive joint includes silver or copper. The electric resistance can be effectively reduced.
上記導電性フィラーの平均粒子径は、好ましくは０．０１μｍ以上、より好ましくは０．０５μｍ以上である。上記導電性フィラーの平均粒子径は、好ましくは５０μｍ以下、より好ましくは１５μｍ以下である。 The average particle diameter of the conductive filler is preferably 0.01 μm or more, more preferably 0.05 μm or more. The average particle diameter of the conductive filler is preferably 50 μm or less, more preferably 15 μm or less.
上記第１の電極と上記第２の電極との温度差を大きくする観点からは、上記熱電変換素子は、断熱材を備えることが好ましい。上記断熱材は、上記第１の電極と上記第２の電極との間に配置されていることが好ましい。例えば、上記熱電変換材料は、上記断熱材を挟むように屈曲されていてもよい。この場合には、上記熱電変換材料の上記断熱材を介して対向し合う部分のうち一方の部分の、上記断熱材側とは反対側の表面が、上記第１の電極に導電接続されていることが好ましい。他方の部分の、上記断熱材側とは反対側の表面が、上記第２の電極に導電接続されていることが好ましい。上記熱電変換材料間に上記断熱材を介在させることによって、上記熱電変換材料がシート状であっても、上記第１の電極と上記第２の電極との距離を長くすることができる。 From the viewpoint of increasing the temperature difference between the first electrode and the second electrode, the thermoelectric conversion element preferably includes a heat insulating material. It is preferable that the heat insulating material is disposed between the first electrode and the second electrode. For example, the thermoelectric conversion material may be bent so as to sandwich the heat insulating material. In this case, the surface of one part of the thermoelectric conversion material that faces each other through the heat insulating material on the side opposite to the heat insulating material side is conductively connected to the first electrode. It is preferable. It is preferable that the surface of the other part opposite to the heat insulating material is conductively connected to the second electrode. By interposing the heat insulating material between the thermoelectric conversion materials, the distance between the first electrode and the second electrode can be increased even if the thermoelectric conversion material is in a sheet form.
上記熱電変換素子を複数有する熱電変換デバイスが構成されていてもよい。上記熱電変換素子の電気抵抗は低いので、上記熱電変換デバイスの出力を効果的に高めることができ、熱電性能を効果的に高めることができる。さらに、上記熱電変換材料と上記第１の電極との接合力が高いため、耐久性、信頼性を高めることができる。 A thermoelectric conversion device having a plurality of the thermoelectric conversion elements may be configured. Since the electric resistance of the thermoelectric conversion element is low, the output of the thermoelectric conversion device can be effectively increased, and the thermoelectric performance can be effectively increased. Furthermore, since the joining force between the thermoelectric conversion material and the first electrode is high, durability and reliability can be improved.
本発明に係る熱電変換素子の製造方法は、熱電変換材料を、第１の導電性接合部に接合し、かつ上記第１の導電性接合部を介して、第１の電極に導電接続する第１の導電接続工程と、上記熱電変換材料を、第２の電極に導電接続する第２の導電接続工程とを備える。上記第１の導電接続工程において、上記熱電変換材料として、上記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する熱電変換材料を用いる。 In the method for manufacturing a thermoelectric conversion element according to the present invention, the thermoelectric conversion material is bonded to the first conductive joint, and the first electrode is conductively connected to the first electrode via the first conductive joint. And a second conductive connection step of conductively connecting the thermoelectric conversion material to the second electrode. In the first conductive connection step, as the thermoelectric conversion material, a thermoelectric conversion having a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint. Use materials.
上記第１の導電接続工程の前に、上記熱電変換材料の上記第１の導電性接合部に接合される部分の表面の算術平均粗さＲａを大きくする表面処理工程を備えていてもよい。上記表面処理工程において、上記熱電変換材料の上記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を形成する。上記表面処理工程は、熱電変換材料の作製時に行われてもよく、熱電変換材料を作製した後に行われてもよい。 Before the first conductive connection step, a surface treatment step of increasing the arithmetic average roughness Ra of the surface of the portion of the thermoelectric conversion material joined to the first conductive joint portion may be provided. In the surface treatment step, a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less is formed on a portion of the thermoelectric conversion material to be joined to the first conductive joint. The said surface treatment process may be performed at the time of preparation of the thermoelectric conversion material, and may be performed after producing the thermoelectric conversion material.
上記表面処理工程において、上記第１の導電性接合部に接合される部分に算術平均粗さＲａが７．５μｍ未満である表面を有する熱電変換材料を用いてもよい。該熱電変換材料の上記第１の導電性接合部に接合される部分の表面の算術平均粗さＲａを大きくする。また、上記熱電変換材料の上記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を形成する。 In the surface treatment step, a thermoelectric conversion material having a surface with an arithmetic average roughness Ra of less than 7.5 μm may be used at a portion joined to the first conductive joint. The arithmetic average roughness Ra of the surface of the portion to be joined to the first conductive joint portion of the thermoelectric conversion material is increased. Moreover, the surface whose arithmetic mean roughness Ra is 7.5 micrometers or more and 50 micrometers or less is formed in the part joined to the said 1st electroconductive junction part of the said thermoelectric conversion material.
電気抵抗を効果的に低くする観点からは、上記第２の導電接続工程は、上記熱電変換材料を、第２の導電性接合部に接合し、かつ上記第２の導電性接合部を介して、上記第２の電極に導電接続する第２の導電接続工程であることが好ましい。上記第２の導電接続工程において、上記熱電変換材料として、上記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する熱電変換材料を用いることが好ましい。 From the viewpoint of effectively reducing the electrical resistance, the second conductive connection step is to join the thermoelectric conversion material to the second conductive joint, and through the second conductive joint. It is preferable that the second conductive connection step be conductively connected to the second electrode. In the second conductive connection step, as the thermoelectric conversion material, a thermoelectric conversion having a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion to be joined to the second conductive joint. It is preferable to use a material.
なお、上記第２の導電性接合部に接合される部分に算術平均粗さＲａが７．５μｍ未満である表面を有する熱電変換材料を用いてもよい。この場合には、該熱電変換材料の上記第２の導電性接合部に接合される部分の表面の算術平均粗さＲａを大きくする表面処理工程を有することが好ましい。上記熱電変換材料の上記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を形成することが好ましい。上記表面処理工程は、熱電変換材料の作製時に行われてもよく、熱電変換材料を作製した後に行われてもよい。 In addition, you may use the thermoelectric conversion material which has the surface whose arithmetic mean roughness Ra is less than 7.5 micrometers in the part joined to the said 2nd electroconductive junction part. In this case, it is preferable to have a surface treatment step for increasing the arithmetic average roughness Ra of the surface of the portion of the thermoelectric conversion material to be joined to the second conductive joint. It is preferable to form a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion of the thermoelectric conversion material to be joined to the second conductive joint. The said surface treatment process may be performed at the time of preparation of the thermoelectric conversion material, and may be performed after producing the thermoelectric conversion material.
上記第１の導電接続工程において、上記第１の導電性接合部を、導電性フィラーを含む導電ペーストにより形成してもよい。上記第２の導電接続工程において、導電性フィラーを含む導電ペーストにより、上記第２の導電性接合部を形成してもよい。 In the first conductive connection step, the first conductive joint portion may be formed of a conductive paste containing a conductive filler. In the second conductive connection step, the second conductive joint portion may be formed of a conductive paste containing a conductive filler.
以下、図面を参照しつつ、本発明の具体的な実施形態を説明する。 Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.
図１は、本発明の第１の実施形態に係る熱電変換素子の模式的断面図である。 FIG. 1 is a schematic cross-sectional view of a thermoelectric conversion element according to the first embodiment of the present invention.
なお、実施形態において参照する図面は、模式的に記載されており、図面に描画された物体の寸法の比率などは、現実の物体の寸法の比率などとは異なる場合がある。具体的な物体の寸法の比率などは、以下の説明を参酌して判断されるべきである。 Note that the drawings referred to in the embodiments are schematically described, and the ratio of the dimensions of an object drawn in the drawings may be different from the ratio of the dimensions of an actual object. The specific ratio of the dimensions of the object should be determined in consideration of the following explanation.
図１に示す熱電変換素子１は、シート状の熱電変換材料２を備える。熱電変換材料２はカーボンナノチューブを含む。熱電変換材料２は、対向し合う第１，第２の表面２ａ１，２ｂ１を有する。 A thermoelectric conversion element 1 shown in FIG. 1 includes a sheet-like thermoelectric conversion material 2. The thermoelectric conversion material 2 includes carbon nanotubes. The thermoelectric conversion material 2 has first and second surfaces 2a1 and 2b1 that face each other.
熱電変換素子１は、熱電変換材料２の第１の表面２ａ１に接合されている第１の導電性接合部３Ａと、第２の表面２ｂ１に接合されている第２の導電性接合部３Ｂとを備える。第１，第２の導電性接合部３Ａ，３Ｂは、導電性フィラーを含み、該導電性フィラーは銀を含む。 The thermoelectric conversion element 1 includes a first conductive bonding portion 3A bonded to the first surface 2a1 of the thermoelectric conversion material 2, and a second conductive bonding portion 3B bonded to the second surface 2b1. Is provided. The first and second conductive joint portions 3A and 3B include a conductive filler, and the conductive filler includes silver.
第１，第２の表面２ａ１，２ｂ１は、それぞれ全面が、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である。第１，第２の導電性接合部３Ａ，３Ｂは、熱電変換材料２における、算術平均粗さＲａが上記範囲である部分に接合されている。 The entire surfaces of the first and second surfaces 2a1 and 2b1 are arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less. The 1st, 2nd electroconductive junction part 3A, 3B is joined to the part in the thermoelectric conversion material 2 whose arithmetic mean roughness Ra is the said range.
熱電変換素子１は、第１の導電性接合部３Ａに接合されている第１の電極４Ａ及び第２の導電性接合部３Ｂに接合されている第２の電極４Ｂを備える。熱電変換素子２は、第１の導電性接合部３Ａを介して第１の電極４Ａに導電接続されている。熱電変換素子２は、第２の導電性接合部３Ｂを介して第２の電極４Ｂに導電接続されている。 The thermoelectric conversion element 1 includes a first electrode 4A joined to the first conductive joint 3A and a second electrode 4B joined to the second conductive joint 3B. The thermoelectric conversion element 2 is conductively connected to the first electrode 4A via the first conductive joint 3A. The thermoelectric conversion element 2 is conductively connected to the second electrode 4B through the second conductive joint 3B.
第１の電極４Ａの熱電変換材料２側とは反対側には、第１の基板５Ａが設けられている。第２の電極４Ｂの熱電変換材料２側とは反対側には、第２の基板５Ｂが設けられている。第１，第２の基板５Ａ，５Ｂの材料は、ポリイミドなどの樹脂材料や、適宜のセラミック材料などである。 On the opposite side of the first electrode 4A from the thermoelectric conversion material 2 side, a first substrate 5A is provided. A second substrate 5B is provided on the opposite side of the second electrode 4B to the thermoelectric conversion material 2 side. The material of the first and second substrates 5A and 5B is a resin material such as polyimide or an appropriate ceramic material.
図２は、本発明の第２の実施形態に係る熱電変換素子の模式的断面図である。 FIG. 2 is a schematic cross-sectional view of a thermoelectric conversion element according to the second embodiment of the present invention.
図２に示す熱電変換素子１１は、シート状の熱電変換材料１２と、断熱材１６とを備える。断熱材１６の材料は、例えば、シリコンスポンジなどの絶縁材料である。 The thermoelectric conversion element 11 shown in FIG. 2 includes a sheet-like thermoelectric conversion material 12 and a heat insulating material 16. The material of the heat insulating material 16 is an insulating material such as silicon sponge, for example.
熱電変換材料１２は、断熱材１６を挟むように屈曲されている。熱電変換材料１２は、断熱材１６を介して対向し合う第１，第２の部分１２ａ，１２ｂを有する。第１の部分１２ａは、断熱材１６側とは反対側の第１の表面１２ａ１を有する。第２の部分１２ｂは、断熱材１６側とは反対側の第２の表面１２ｂ１を有する。第１，第２の表面１２ａ１，１２ｂ１は、それぞれ全面が、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である。 The thermoelectric conversion material 12 is bent so as to sandwich the heat insulating material 16. The thermoelectric conversion material 12 has first and second portions 12 a and 12 b that face each other with a heat insulating material 16 interposed therebetween. The first portion 12a has a first surface 12a1 opposite to the heat insulating material 16 side. The second portion 12b has a second surface 12b1 opposite to the heat insulating material 16 side. The entire surface of the first and second surfaces 12a1 and 12b1 has an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less.
第１の表面１２ａ１は、第１の導電性接合部３Ａを介して第１の電極４Ａに導電接続されている。第２の表面１２ｂ１は、第２の導電性接合部３Ｂを介して第２の電極４Ｂに導電接続されている。 The first surface 12a1 is conductively connected to the first electrode 4A via the first conductive joint 3A. The second surface 12b1 is conductively connected to the second electrode 4B through the second conductive joint 3B.
次に、熱電変換素子の製造方法の一例を説明する。 Next, an example of a method for manufacturing a thermoelectric conversion element will be described.
図３（ａ）〜（ｃ）は、本発明の第１の実施形態に係る熱電変換素子の製造方法を説明するための断面図である。 3A to 3C are cross-sectional views for explaining a method for manufacturing a thermoelectric conversion element according to the first embodiment of the present invention.
図３（ａ）に示すように、対向し合う第１，第２の表面２Ｘａ，２Ｘｂを有する熱電変換材料２Ｘを用意する。第１，第２の表面２Ｘａ，２Ｘｂは、算術平均粗さＲａが７．５μｍより小さい。 As shown in FIG. 3A, a thermoelectric conversion material 2X having first and second surfaces 2Xa and 2Xb facing each other is prepared. The first and second surfaces 2Xa and 2Xb have an arithmetic average roughness Ra of less than 7.5 μm.
次に、熱電変換材料２Ｘの対向し合う第１，第２の表面２Ｘａ，２Ｘｂの算術平均粗さＲａを大きくし、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面とする表面処理工程を行う。表面処理工程は、例えば、研磨などにより行うことができる。これにより、図３（ｂ）に示す熱電変換材料２を得る。なお、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である第１，第２の表面２ａ１，２ｂ１を有する熱電変換材料２を予め用意してもよい。 Next, the arithmetic average roughness Ra of the first and second surfaces 2Xa and 2Xb facing each other of the thermoelectric conversion material 2X is increased, and the surface having the arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less. Perform processing steps. The surface treatment step can be performed by, for example, polishing. Thereby, the thermoelectric conversion material 2 shown in FIG.3 (b) is obtained. In addition, you may prepare the thermoelectric conversion material 2 which has the 1st, 2nd surface 2a1, 2b1 whose arithmetic mean roughness Ra is 7.5 micrometers or more and 50 micrometers or less previously.
他方、図３（ｂ）に示す、第１の電極４Ａを表面に有する第１の基板５Ａと、図３（ｃ）に示す、第２の電極４Ｂを表面に有する第２の基板５Ｂとを用意する。次に、図３（ｂ）に示すように、熱電変換材料２の第１の表面２ａ１に第１の導電性接合部３Ａを接合し、かつ第１の導電性接合部３Ａを介して第１の電極４Ａに導電接続する第１の導電接続工程を行う。第１の導電接続工程においては、例えば、第１の導電性接続部３Ａを、導電性フィラーを含む導電ペーストにより形成することができる。 On the other hand, a first substrate 5A having the first electrode 4A on the surface shown in FIG. 3B and a second substrate 5B having the second electrode 4B on the surface shown in FIG. prepare. Next, as shown in FIG. 3B, the first conductive joint 3A is joined to the first surface 2a1 of the thermoelectric conversion material 2, and the first conductive joint 3A is used for the first. A first conductive connection step for conductively connecting to the electrode 4A is performed. In the first conductive connection step, for example, the first conductive connection portion 3A can be formed of a conductive paste containing a conductive filler.
次に、図３（ｃ）に示すように、熱電変換材料２の第２の表面２ｂ１に第２の導電性接合部３Ｂを接合し、かつ第２の導電性接合部３Ｂを介して第２の電極４Ｂに導電接続する第２の導電接続工程を行う。第２の導電接続工程においては、例えば、第２の導電性接続部３Ｂを、導電性フィラーを含む導電ペーストにより形成することができる。 Next, as shown in FIG. 3 (c), the second conductive joint 3B is joined to the second surface 2b1 of the thermoelectric conversion material 2, and the second conductive joint 3B is connected to the second surface 2b1. A second conductive connection step for conductively connecting to the electrode 4B is performed. In the second conductive connection step, for example, the second conductive connection portion 3B can be formed of a conductive paste containing a conductive filler.
以下、本発明について、具体的な実施例に基づいて、さらに詳細に説明する。 Hereinafter, the present invention will be described in more detail based on specific examples.
（実施例１）
熱電変換材料の作製：
Ｎ−メチルピロリドン１００ｍＬ中に、平均直径２ｎｍ、Ｇ／Ｄ比５０のシングルウォールカーボンナノチューブ（ＳＷＣＮＴ）２５ｍｇを入れ、マグネチックスターラーを用いて撹拌した。その後、湿式高圧衝突式ホモジナイザーを用いて、圧力１００ＭＰａにて、分散処理を３回（繰り返し処理回数）、繰り返して行い、ＳＷＣＮＴ分散液を得た。得られたＳＷＣＮＴ分散液を、孔径０．２μｍのメンブレンフィルタを用いて減圧ろ過し、ＳＷＣＮＴ堆積物を得た。得られたＳＷＣＮＴ堆積物を乾燥させることにより、厚み１００μｍの熱電変換材料を得た。その後、得られた熱電変換材料の対向し合う両側の表面を、直径３０μｍの金属ワイヤーを束ねたワイヤーブラシにより５回擦ることによって、表面に凹凸を形成した。
Example 1
Production of thermoelectric conversion materials:
In 100 mL of N-methylpyrrolidone, 25 mg of single-walled carbon nanotubes (SWCNT) having an average diameter of 2 nm and a G / D ratio of 50 were placed and stirred using a magnetic stirrer. Thereafter, using a wet high-pressure collision type homogenizer, the dispersion treatment was repeated three times (the number of repetition treatments) at a pressure of 100 MPa to obtain a SWCNT dispersion. The obtained SWCNT dispersion was filtered under reduced pressure using a membrane filter having a pore size of 0.2 μm to obtain a SWCNT deposit. The obtained SWCNT deposit was dried to obtain a thermoelectric conversion material having a thickness of 100 μm. Then, the surface of the both sides which the obtained thermoelectric conversion material opposes was rubbed 5 times with the wire brush which bundled the metal wire of diameter 30 micrometers, and the unevenness | corrugation was formed in the surface.
熱電変換デバイスの作製：
短辺５ｃｍ及び長辺１０ｃｍの矩形の平面形状を有し、電極を表面に有するポリイミド基板を２枚用意した。一方のポリイミド基板上の電極部分に銀ペーストを塗布した。銀ペースト上に１００枚の熱電変換材料を、ポリイミド基板の主面方向に並べて載置した。各熱電変換材料上に銀ペーストを更に塗布した。熱電変換材料上の銀ペースト上に、ポリイミド基板の電極部分が重なるように積層した。２枚のポリイミド基板及び２枚の電極に熱電変換材料が挟まれた熱電変換素子を連続的に１００対有する積層体を得た。得られた積層体周辺を熱硬化性樹脂によってシーリングし、加熱しながらプレスすることにより、短辺５ｃｍ及び長辺１０ｃｍの矩形の平面形状を有する熱電変換デバイスを得た。
Production of thermoelectric conversion device:
Two polyimide substrates having a rectangular planar shape with a short side of 5 cm and a long side of 10 cm and having electrodes on the surface were prepared. A silver paste was applied to the electrode portion on one polyimide substrate. On the silver paste, 100 thermoelectric conversion materials were placed side by side in the main surface direction of the polyimide substrate. A silver paste was further applied on each thermoelectric conversion material. It laminated | stacked so that the electrode part of a polyimide substrate might overlap on the silver paste on a thermoelectric conversion material. A laminate having 100 pairs of thermoelectric conversion elements in which a thermoelectric conversion material was sandwiched between two polyimide substrates and two electrodes was obtained. The periphery of the obtained laminate was sealed with a thermosetting resin, and pressed while heating to obtain a thermoelectric conversion device having a rectangular planar shape with a short side of 5 cm and a long side of 10 cm.
（実施例２）
熱電変換材料の作製において、熱電変換材料の対向し合う両側の表面をワイヤーブラシにより擦る回数を１０回に変更したこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Example 2)
In the production of the thermoelectric conversion material, a thermoelectric conversion device was produced in the same manner as in Example 1 except that the number of times of rubbing the opposite surfaces of the thermoelectric conversion material with a wire brush was changed to 10.
（実施例３）
熱電変換材料の作製において、熱電変換材料の対向し合う両側の表面をワイヤーブラシにより擦る回数を２０回に変更したこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Example 3)
In the production of the thermoelectric conversion material, a thermoelectric conversion device was produced in the same manner as in Example 1 except that the number of times of rubbing the opposite surfaces of the thermoelectric conversion material with a wire brush was changed to 20 times.
（比較例１）
熱電変換材料の作製において、熱電変換材料の対向し合う両側の表面をワイヤーブラシにより擦らなかったこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Comparative Example 1)
In producing the thermoelectric conversion material, a thermoelectric conversion device was produced in the same manner as in Example 1 except that the opposite surfaces of the thermoelectric conversion material were not rubbed with a wire brush.
（比較例２）
熱電変換素子を連続的に１００対有する積層体を得る工程において、銀ペーストを用いず、各熱電変換素子における対向する両電極と熱電変換材料の対向し合う両側の表面とが直接接触した積層体を得たこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Comparative Example 2)
In the step of obtaining a laminated body having 100 pairs of thermoelectric conversion elements continuously, a laminated body in which both electrodes facing each other and the opposite surfaces of each thermoelectric conversion material are in direct contact without using silver paste. A thermoelectric conversion device was produced in the same manner as in Example 1 except that.
（比較例３）
熱電変換材料の作製において、熱電変換材料の対向し合う両側の表面をワイヤーブラシにより擦る回数を２回に変更したこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Comparative Example 3)
In the production of the thermoelectric conversion material, a thermoelectric conversion device was produced in the same manner as in Example 1 except that the number of times of rubbing the opposite surfaces of the thermoelectric conversion material with a wire brush was changed to 2.
（比較例４）
熱電変換材料の作製において、熱電変換材料の対向し合う両側の表面をワイヤーブラシにより擦る回数を５０回に変更したこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Comparative Example 4)
In the production of the thermoelectric conversion material, a thermoelectric conversion device was produced in the same manner as in Example 1 except that the number of times of rubbing the opposite surfaces of the thermoelectric conversion material with a wire brush was changed to 50 times.
（比較例５）
熱電変換材料の作製において、熱電変換材料の対向し合う両側の表面をワイヤーブラシにより擦る回数を１００回に変更したこと以外は、実施例１と同様にして熱電変換デバイスを作製した。
(Comparative Example 5)
In the production of the thermoelectric conversion material, a thermoelectric conversion device was produced in the same manner as in Example 1 except that the number of times of rubbing the opposite surfaces of the thermoelectric conversion material with a wire brush was changed to 100 times.
（評価）
算術平均粗さＲａの算出：
熱電変換材料表面を、レーザー顕微鏡（オリンパス社製「ＯＬＳ４１００」）を用いて表面観察し、２．５ｍｍ四方の観察像を得た。また観察場所をそれぞれ変更して合計２０枚の観察像を得た。それぞれの観察像の中心部において、水平方向に沿う幅２ｍｍにおける線粗さを解析し、２０枚の観察像における平均値を更に算出した。
(Evaluation)
Calculation of arithmetic average roughness Ra:
The surface of the thermoelectric conversion material was observed using a laser microscope (“OLS4100” manufactured by Olympus) to obtain a 2.5 mm square observation image. In addition, a total of 20 observation images were obtained by changing the observation location. At the center of each observation image, the line roughness at a width of 2 mm along the horizontal direction was analyzed, and the average value of 20 observation images was further calculated.
図４は、比較例１における熱電変換材料の表面の顕微鏡写真である。図５は、比較例１における熱電変換材料の等高線変換図である。図６は、実施例１における熱電変換材料の表面の顕微鏡写真である。図７は、実施例１における熱電変換材料の等高線変換図である。 4 is a photomicrograph of the surface of the thermoelectric conversion material in Comparative Example 1. FIG. FIG. 5 is a contour conversion diagram of the thermoelectric conversion material in Comparative Example 1. 6 is a photomicrograph of the surface of the thermoelectric conversion material in Example 1. FIG. FIG. 7 is a contour line conversion diagram of the thermoelectric conversion material in Example 1.
図４及び図５に示すように、比較例１においては、熱電変換材料の表面に凹凸がほぼ形成されていないことがわかる。図６及び図７に示すように、実施例１においては、熱電変換材料の表面に凹凸が好適に形成されていることがわかる。 As shown in FIGS. 4 and 5, it can be seen that in Comparative Example 1, almost no irregularities are formed on the surface of the thermoelectric conversion material. As shown in FIGS. 6 and 7, in Example 1, it can be seen that irregularities are suitably formed on the surface of the thermoelectric conversion material.
抵抗値測定：
熱電変換デバイスをデジタルマルチメータ（ヒューレットパッカード社製「３６８０Ａ」）に接続し、熱電変換デバイスの抵抗値を測定した。
Resistance measurement:
The thermoelectric conversion device was connected to a digital multimeter ("3680A" manufactured by Hewlett-Packard Company), and the resistance value of the thermoelectric conversion device was measured.
曲げ試験後劣化率：
上記方法により熱電変換デバイスの抵抗値を測定した後に、熱電変換デバイスを直径７．５μｍの金属棒に巻き付ける操作を２５回繰り返し、曲げ試験を行った。その後、再度上記方法により熱電変換デバイスの抵抗値を測定した。曲げ試験前の抵抗値の曲げ試験後劣化率を求めた。
Deterioration rate after bending test:
After measuring the resistance value of the thermoelectric conversion device by the above method, an operation of winding the thermoelectric conversion device around a metal rod having a diameter of 7.5 μm was repeated 25 times to perform a bending test. Thereafter, the resistance value of the thermoelectric conversion device was measured again by the above method. The deterioration rate after the bending test of the resistance value before the bending test was determined.
熱電性能：
室温（２５℃）の熱電変換デバイスを一方のポリイミド基板側から、１００℃のホットプレート上に載置した。熱電変換デバイスをホットプレートにより１００℃に加熱し、かつ熱電変換デバイスの上面の温度をペルチェ素子により冷却して２５℃とし、上面と下面との間に７５℃の温度差を付与した。温度差を付与してから１０秒後に、デジタルマルチメータ（ヒューレットパッカード社製「３６８０Ａ」）を用いて、熱電変換デバイスの熱起電力を測定した。比較例１において得られた熱電変換デバイスの熱起電力を熱電性能「１（ＳＴＤ）」として、実施例及び他の比較例の熱電性能を相対評価した。
Thermoelectric performance:
A thermoelectric conversion device at room temperature (25 ° C.) was placed on a hot plate at 100 ° C. from one polyimide substrate side. The thermoelectric conversion device was heated to 100 ° C. by a hot plate, and the temperature of the upper surface of the thermoelectric conversion device was cooled by a Peltier element to 25 ° C., and a temperature difference of 75 ° C. was given between the upper surface and the lower surface. Ten seconds after applying the temperature difference, the thermoelectromotive force of the thermoelectric conversion device was measured using a digital multimeter ("3680A" manufactured by Hewlett-Packard Company). The thermoelectric power of the thermoelectric conversion device obtained in Comparative Example 1 was regarded as the thermoelectric performance “1 (STD)”, and the thermoelectric performances of the examples and other comparative examples were relatively evaluated.
評価の結果を下記の表１に示す。 The evaluation results are shown in Table 1 below.
表１に示すように、比較例１〜５ではいずれも抵抗値が高く、１００Ωを超えていることがわかる。さらに、比較例１〜５では曲げ試験後劣化率も高く、１２％より大きい。 As shown in Table 1, it can be seen that in Comparative Examples 1 to 5, the resistance value is high and exceeds 100Ω. Furthermore, in Comparative Examples 1-5, the deterioration rate after a bending test is also high, and is larger than 12%.
実施例１〜３では、いずれも抵抗値は９０Ω未満となっており、電気抵抗が低いことがわかる。熱電性能は、いずれも比較例１の１．５倍以上である。さらに、曲げ試験後劣化率はいずれも１０％未満となっており、曲げ試験後劣化率が低いことがわかる。 In each of Examples 1 to 3, the resistance value is less than 90Ω, indicating that the electrical resistance is low. The thermoelectric performance is 1.5 times or more that of Comparative Example 1. Furthermore, the deterioration rate after the bending test is less than 10%, and it can be seen that the deterioration rate after the bending test is low.
１…熱電変換素子
２，２Ｘ…熱電変換材料
２ａ１，２ｂ１…第１，第２の表面
２Ｘａ，２Ｘｂ…第１，第２の表面
３Ａ，３Ｂ…第１，第２の導電性接合部
４Ａ，４Ｂ…第１，第２の電極
５Ａ，５Ｂ…第１，第２の基板
１１…熱電変換素子
１２…熱電変換材料
１２ａ，１２ｂ…第１，第２の部分
１２ａ１，１２ｂ１…第１，第２の表面
１６…断熱材
DESCRIPTION OF SYMBOLS 1 ... Thermoelectric conversion element 2, 2X ... Thermoelectric conversion material 2a1, 2b1 ... 1st, 2nd surface 2Xa, 2Xb ... 1st, 2nd surface 3A, 3B ... 1st, 2nd electroconductive junction part 4A, 4B ... 1st, 2nd electrode 5A, 5B ... 1st, 2nd board | substrate 11 ... Thermoelectric conversion element 12 ... Thermoelectric conversion material 12a, 12b ... 1st, 2nd part 12a1, 12b1 ... 1st, 2nd Surface 16 ... heat insulation
Claims (16)
前記熱電変換材料は、前記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する、熱電変換材料。 A thermoelectric conversion material that is joined to a first conductive joint and is conductively connected to the first electrode via the first conductive joint, and is separated from the first electrode. A thermoelectric conversion material used by being electrically connected to the second electrode at a certain position,
The thermoelectric conversion material is a thermoelectric conversion material having a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint.
前記熱電変換材料は、前記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する、請求項１に記載の熱電変換材料。 A thermoelectric conversion material that is joined to a second conductive joint and is electrically connected to the second electrode through the second conductive joint;
2. The thermoelectric conversion material according to claim 1, wherein the thermoelectric conversion material has a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the second conductive joint portion.
第１の導電性接合部と、
熱電変換材料と、
第２の電極とを備え、
前記熱電変換材料は、前記第１の導電性接合部に接合されている部分を有し、かつ前記第１の導電性接合部を介して、前記第１の電極に導電接続されており、
前記熱電変換材料は、前記第１の電極と離れた位置において前記第２の電極に導電接続されており、
前記熱電変換材料は、前記第１の導電性接合部に接合されている部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する、熱電変換素子。 A first electrode;
A first conductive joint;
A thermoelectric conversion material;
A second electrode,
The thermoelectric conversion material has a portion joined to the first conductive joint, and is conductively connected to the first electrode via the first conductive joint,
The thermoelectric conversion material is conductively connected to the second electrode at a position away from the first electrode,
The thermoelectric conversion material is a thermoelectric conversion element having a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint.
前記熱電変換材料は、前記第２の導電性接合部に接合されている部分を有し、かつ前記第２の導電性接合部を介して、前記第１の電極と離れた位置において前記第２の電極に導電接続されており、
前記熱電変換材料は、前記第２の導電性接合部に接合されている部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する、請求項３に記載の熱電変換素子。 A second conductive joint,
The thermoelectric conversion material has a portion joined to the second conductive joint, and the second electroconductive material is separated from the first electrode via the second conductive joint. Conductively connected to the electrodes of
The thermoelectric conversion element according to claim 3, wherein the thermoelectric conversion material has a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the second conductive joint. .
前記熱電変換材料は、前記第１の表面側において、前記第１の導電性接合部を介して、前記第１の電極に導電接続されており、かつ、前記第２の表面側において、前記第２の電極に導電接続されている、請求項３又は４に記載の熱電変換素子。 The thermoelectric conversion material has a first surface and a second surface facing each other,
The thermoelectric conversion material is conductively connected to the first electrode on the first surface side via the first conductive joint, and on the second surface side, the thermoelectric conversion material is electrically connected to the first electrode. The thermoelectric conversion element according to claim 3, wherein the thermoelectric conversion element is conductively connected to the two electrodes.
前記第１の導電性接合部に含まれる前記導電性フィラーが、銀又は銅を含む、請求項３〜８のいずれか１項に記載の熱電変換素子。 The first conductive joint includes a conductive filler;
The thermoelectric conversion element according to claim 3, wherein the conductive filler contained in the first conductive joint includes silver or copper.
前記第１の導電性接合部に含まれる前記導電性フィラーの平均粒子径が、０．０１μｍ以上、５０μｍ以下である、請求項３〜９のいずれか１項に記載の熱電変換素子。 The first conductive joint includes a conductive filler;
The thermoelectric conversion element of any one of Claims 3-9 whose average particle diameter of the said electroconductive filler contained in a said 1st electroconductive junction part is 0.01 micrometer or more and 50 micrometers or less.
前記断熱材が、前記第１の電極と前記２の電極との間に配置されている、請求項３〜１０のいずれか１項に記載の熱電変換素子。 With thermal insulation,
The thermoelectric conversion element according to any one of claims 3 to 10, wherein the heat insulating material is disposed between the first electrode and the second electrode.
前記熱電変換材料を、第２の電極に導電接続する第２の導電接続工程とを備え、
前記第１の導電接続工程において、前記熱電変換材料として、前記第１の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する熱電変換材料を用いる、熱電変換素子の製造方法。 A first conductive connection step of joining the thermoelectric conversion material to the first conductive joint and conductively connecting to the first electrode via the first conductive joint;
A second conductive connection step of conductively connecting the thermoelectric conversion material to a second electrode;
In the first conductive connection step, as the thermoelectric conversion material, a thermoelectric conversion having a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion joined to the first conductive joint. A method for manufacturing a thermoelectric conversion element using a material.
前記第２の導電接続工程において、前記熱電変換材料として、前記第２の導電性接合部に接合される部分に、算術平均粗さＲａが７．５μｍ以上、５０μｍ以下である表面を有する熱電変換材料を用いる、請求項１２〜１４のいずれか１項に記載の熱電変換素子の製造方法。 In the second conductive connection step, the thermoelectric conversion material is bonded to the second conductive joint, and the second conductive joint is conductively connected to the second electrode via the second conductive joint. The conductive connection process of
In the second conductive connection step, as the thermoelectric conversion material, a thermoelectric conversion having a surface having an arithmetic average roughness Ra of 7.5 μm or more and 50 μm or less at a portion to be joined to the second conductive joint. The manufacturing method of the thermoelectric conversion element of any one of Claims 12-14 using a material.
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