[go: up one dir, main page]

WO2010058526A1 - Dispositif générateur de puissance thermique et procédé de génération de puissance l’utilisant - Google Patents

Dispositif générateur de puissance thermique et procédé de génération de puissance l’utilisant Download PDF

Info

Publication number
WO2010058526A1
WO2010058526A1 PCT/JP2009/005641 JP2009005641W WO2010058526A1 WO 2010058526 A1 WO2010058526 A1 WO 2010058526A1 JP 2009005641 W JP2009005641 W JP 2009005641W WO 2010058526 A1 WO2010058526 A1 WO 2010058526A1
Authority
WO
WIPO (PCT)
Prior art keywords
thermoelectric
generation device
layer
power generation
stacking
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.)
Ceased
Application number
PCT/JP2009/005641
Other languages
English (en)
Japanese (ja)
Inventor
菅野勉
酒井章裕
高橋宏平
四橋聡史
足立秀明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Corp
Original Assignee
Panasonic Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Panasonic Corp filed Critical Panasonic Corp
Priority to CN2009801203138A priority Critical patent/CN102047458B/zh
Priority to US12/811,182 priority patent/US7994415B2/en
Priority to JP2010510018A priority patent/JP4584355B2/ja
Publication of WO2010058526A1 publication Critical patent/WO2010058526A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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

Definitions

  • the present invention relates to a thermoelectric power generation device that converts thermal energy into electric energy and a power generation method using the thermoelectric power generation device.
  • Thermoelectric power generation technology is a technology that directly converts thermal energy into electrical energy using the Seebeck effect, in which an electromotive force is generated in proportion to the temperature difference that occurs at both ends of a substance. This technology is used and practically used for power supplies for remote areas, space power supplies, military power supplies, and the like.
  • thermoelectric power generation device has a ⁇ -type structure in which p-type semiconductor and n-type semiconductor thermoelectric materials having different carrier signs are combined and connected so that they are thermally parallel and electrically in series. It has a configuration called.
  • thermoelectric material used for a thermoelectric power generation device is often evaluated by a figure of merit ZT or a figure of merit ZT made dimensionless by multiplying Z by an absolute temperature.
  • S 2 / ⁇ indicated by the Seebeck coefficient S and the electrical resistivity ⁇ is a value called a power factor, and determines whether the power generation performance of the thermoelectric material and the thermoelectric conversion device is constant when the temperature difference is constant.
  • the standard The standard.
  • Bi 2 Te 3 materials such as Bi 2-a Sb a Te 3 (0 ⁇ a ⁇ 2), which are currently in practical use as thermoelectric materials, have a ZT of about 1 and a power factor of 40 to 50 ⁇ W / It is cmK 2 and currently has relatively high thermoelectric properties.
  • a ⁇ -type thermoelectric power generation device using this Bi 2 Te 3 material cannot be said to have sufficient power generation performance for practical use in more applications.
  • thermoelectric power generation device other than the ⁇ -type structure
  • a thermoelectric power generation device using anisotropy of thermoelectric characteristics in a natural or artificial laminated structure has been proposed for a long time (for example, non-patent literature).
  • Patent Document 1 describes a thermoelectric power generation device using anisotropy of thermoelectric characteristics in a laminated structure composed of a metal and Bi as a thermoelectric material.
  • the thermoelectric power generation device described in Patent Document 1 has a ⁇ -type structure using Bi or Bi 2 Te 3 based material by appropriately selecting the thickness ratio of metal and Bi or the inclination angle in the stacking direction. It has a power factor that greatly exceeds that of thermoelectric power generation devices.
  • thermoelectric power generation device described in Non-Patent Document 1 does not have a high ZT and no improvement is observed, there is a technical development that is not intended for thermoelectric power generation but mainly for measurement applications such as infrared sensors. Has been done.
  • a thermoelectric power generation device having a ⁇ -type structure cannot be said to have sufficient power generation performance for practical use in more applications.
  • the thermoelectric generator described in Patent Document 1 has a larger power factor than the thermoelectric generator having a ⁇ -type structure, but a thermoelectric generator having a larger power factor is desired.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a thermoelectric power generation device having high power generation performance and a power generation method using the same.
  • thermoelectric power generation device includes a first electrode and a second electrode that are disposed to face each other, and the first electrode and the second electrode sandwiched between the first electrode and the second electrode.
  • thermoelectric material layer has a thermoelectric material layer, and a first sandwiching layer and a second sandwiching layer arranged so as to sandwich the thermoelectric material layer, and the first sandwiching layer and the second sandwiching layer are made of a metal and an insulator, respectively.
  • the stacking direction of the stacked structure is parallel to the stacking surface of the stacked body and is inclined with respect to the electromotive force extraction direction, and the first sandwiching An insulator of the layer, and an insulator of the second sandwich layer
  • the stacking direction is arranged so as to appear alternately, and a temperature difference is generated in a direction orthogonal to the stacking direction of the stacked body and orthogonal to the electromotive force extraction direction, whereby the first electrode and the first electrode Electric power is output through two electrodes.
  • a power generation method is a power generation method using a thermoelectric power generation device that generates a temperature difference in a thermoelectric power generation device and obtains electric power from the thermoelectric power generation device, the thermoelectric power generation The device is electrically connected to both the first electrode and the second electrode, sandwiched between the first electrode and the second electrode disposed opposite to each other, and the first electrode and the second electrode.
  • thermoelectric material layer and the thermoelectric material layer A first sandwiching layer and a second sandwiching layer disposed so as to sandwich the first sandwiching layer, and the first sandwiching layer and the second sandwiching layer each have a stacked structure in which metals and insulators are alternately stacked.
  • the stacking direction of the stacked structure is the product Parallel to the laminate surface of the body and inclined with respect to the electromotive force extraction direction, and the insulator of the first sandwiching layer and the insulator of the second sandwich layer are about the stacking direction, Electric power is arranged via the first electrode and the second electrode by arranging them so as to appear alternately and generating a temperature difference in a direction perpendicular to the lamination direction of the laminate and perpendicular to the electromotive force extraction direction. Get.
  • thermoelectric power generation device having high power generation performance and a power generation method using the same can be provided.
  • thermoelectric power generation device 1 is a perspective view of a thermoelectric power generation device according to Embodiment 1 of the present invention.
  • Front view of thermoelectric power generation device according to Embodiment 1 of the present invention The top view of the thermoelectric power generation device which concerns on Embodiment 1 of this invention
  • the top view which shows the 1st modification of the thermoelectric power generation element which concerns on Embodiment 1 of this invention The top view which shows the 2nd modification of the thermoelectric power generation element which concerns on Embodiment 1 of this invention
  • the front view which showed the structure at the time of driving the thermoelectric power generation device which concerns on Embodiment 1 of this invention
  • the flowchart which showed the manufacturing process of the thermoelectric power generation device which concerns on Embodiment 1 of this invention 1st process drawing in the manufacturing method of the thermoelectric power generation device concerning Embodiment 1 of the present invention 2nd process drawing in the manufacturing method of the thermoelectric power generation device concerning Embodiment 1 of the present invention 3rd process drawing in the manufacturing method of the thermoelectric
  • FIG. 1 is a perspective view of the thermoelectric generator device according to Embodiment 1 of the present invention. As shown in FIG. 1, the thermoelectric generator according to the first embodiment is installed by being sandwiched between a first electrode 11 and a second electrode 12 that are arranged to face each other, and a first electrode 11 and a second electrode 12. The laminate 20 is electrically connected to both the first electrode 11 and the second electrode 12.
  • the first electrode 11 and the second electrode 12 are preferably made of a material having high electrical conductivity, and metals such as Cu, Ag, Mo, W, Al, Ti, Cr, Au, Pt, and In, or addition of TiN or tin Nitride or oxide such as indium oxide (ITO) and SnO 2 is preferable.
  • the first electrode 11 and the second electrode 12 may be formed using solder or conductive paste.
  • the laminate 20 includes a first sandwiching layer 13, a thermoelectric material layer 15, and a second sandwiching layer 14, which are sequentially stacked. That is, the thermoelectric material layer 15 is sandwiched between the first sandwiching layer 13 and the second sandwiching layer 14.
  • the electromotive force extraction direction is the X direction in FIG.
  • the lamination direction of the laminated body 20 is a direction orthogonal to an electromotive force taking-out direction, and is a Z direction of FIG.
  • the Y direction in FIG. 1 is orthogonal to the X direction and the Z direction.
  • thermoelectric material layer 15 includes the metal 16 and the insulator. 17 is in contact. Further, the stacking direction of the metal 16 and the insulator 17 in the first sandwiching layer 13 and the second sandwiching layer 14 is parallel to the stacking surface (XY plane) of the stack 20 and in the electromotive force extraction direction (X direction). It is the direction which inclines with respect.
  • FIG. 2 is a front view of the thermoelectric generator according to Embodiment 1 of the present invention.
  • the laminated surface 18 of the first sandwiching layer 13 and the second sandwiching layer 14 is inclined with respect to the electromotive force extraction direction (X direction).
  • the direction 21 of the laminated surface 18 is inclined by an angle ⁇ with respect to the X direction (electromotive force extraction direction). Note that the direction 21 is specifically a direction of intersection between the stacked surface (XY plane) of the stacked body 20 and the stacked surface 18.
  • thermoelectric material constituting the thermoelectric material layer 15 of the first embodiment for example, Bi 2-a Sb a Te 3 , Bi, PbTe, Si 0.8 Ge 0.2 , CoSi, SrTiO 3 , Na b CoO 2 and the like are preferable.
  • a and b are 0 ⁇ a ⁇ 2 and 0.3 ⁇ b ⁇ 0.8.
  • These heat conversion materials have properties suitable for the configuration of the thermoelectric generation device 100, and can provide the thermoelectric generation device 100 having high power generation performance.
  • thermoelectric material layer 15 when Si 0.8 Ge 0.2 is used as the material of the thermoelectric material layer 15, impurities such as B (boron), P (phosphorus), and Al may be included. Further, when SrTiO 3 is used as the material of the thermoelectric material layer 15, impurities such as La and Nb may be contained. Further, when Na b CoO 2 (0.3 ⁇ b ⁇ 0.8) is used as the material of the thermoelectric material layer 15, impurities such as Sr and Ca may be contained. The thermoelectric material layer 15 may cause a compositional deviation depending on the manufacturing method. However, if the deviation is within 20% of the composition ratio, the performance is not significantly impaired, which is acceptable.
  • the insulator 17 and the metal 16 are periodically arranged.
  • the insulators 17 of the first sandwiching layer 13 and the second sandwiching layer 14 both have the same stacking cycle and stacking direction. Therefore, the insulators 17 adjacent to each other are arranged at the same interval.
  • the stacking period of the insulator 17 in each of the first sandwiching layer 13 and the second sandwiching layer 14 is the period x (see FIG. 2).
  • the insulators 17 of the first sandwiching layer 13 and the insulators 17 of the second sandwiching layer 14 are arranged so as to appear alternately in the stacking direction. It is preferable that the insulator 17 of the first sandwiching layer 13 and the insulator 17 of the second sandwiching layer 14 are arranged so as to be shifted by a half cycle of the cycle x in the stacking direction.
  • the insulators 17 of the first sandwiching layer 13 and the second sandwiching layer 14 are preferably disposed periodically, but are not periodically disposed. Even if it exists, the thermoelectric generation device 100 can generate electric power. However, the thermoelectric device 100 exhibits better characteristics in the configuration in which the insulators 17 are periodically arranged.
  • the displacement of the insulator 17 of the first sandwiching layer 13 and the insulator 17 of the second sandwiching layer 14 in the stacking direction is most preferably a half cycle (0.5 cycle) of the cycle x.
  • the thermoelectric device 100 exhibits the most favorable characteristics.
  • the thermoelectric power generation device 100 can generate power even when the misalignment is other than this, and it is preferable that the misalignment is 0.3 to 0.7 of the cycle x, and 0.4 to 0.00 of the cycle x. 6 is more preferable.
  • this displacement is referred to as a substantially half-cycle displacement.
  • FIG. 3 is a plan view of the thermoelectric generator according to Embodiment 1 of the present invention.
  • the thickness of the insulator 17 in the Z direction is preferably equal to the sum of the thicknesses of the metal 16 and the thermoelectric material layer 15 in the Z direction, but the other thicknesses. But you can.
  • FIG. 4 is a plan view showing a first modification of the thermoelectric generator according to the first embodiment of the present invention
  • FIG. 5 shows a second modification of the thermoelectric generator according to the first embodiment of the present invention. It is a top view which shows an example. As shown in FIG.
  • the insulator 17 may enter a part of the thermoelectric material layer 15. Further, as shown in FIG. 5, the insulator 17 of the first sandwiching layer 13 divides the thermoelectric material layer 15 to reach the second sandwiching layer 14, and the insulator 17 of the second sandwiching layer 14 is joined to the thermoelectric material. The layer 15 may be divided to reach the first sandwiching layer 13. However, the stacked body 20 is not completely divided by the insulator 17.
  • the metal 16 of the first sandwiching layer 13 and the second sandwiching layer 14 preferably has a high thermal conductivity and a low electrical resistivity. Thereby, the power generation performance of the thermoelectric generation device 100 is enhanced.
  • the metal 16 it is preferable to use Cu, Ag, Au, Al, or an alloy made of these materials. In consideration of conductivity, thermal conductivity, difficulty in production, and the like, the metal 16 is more preferably Cu, Ag, or Au than Al, and more preferably Cu and Ag.
  • the insulator 17 is not particularly limited as long as it is an electrically insulating material. Specifically, oxides such as SiO 2 , Al 2 O 3 , ZrO 2 , and Ta 2 O 5 , nitrides such as Si 3 N 4, and resins such as epoxy are preferable.
  • the insulator 17 may be a gas such as air or nitrogen, or a vacuum.
  • the insulator 17 can be made into air by forming a groove at a place where the insulator 17 is disposed and operating the thermoelectric device 100 in the air. Further, the thermoelectric power generation device 100 in which a groove is formed at the place where the insulator 17 is disposed is installed and operated in a container filled with a gas other than air and sealed so that the gas does not leak.
  • the insulator 17 becomes the filled gas. Moreover, the insulator 17 becomes a vacuum by making this container into a vacuum state.
  • the thermoelectric power generation device 100 can be reduced in weight as compared with the case where the insulator 17 is made solid, but attention should be paid to a decrease in strength.
  • FIG. 6 is a front view showing a configuration when driving the thermoelectric generator according to the first embodiment of the present invention.
  • a temperature difference may be generated in the Y direction.
  • the high temperature portion 62 and the low temperature portion 63 are arranged to face each other along the Y direction, and these are brought into close contact with the thermoelectric generation device 100.
  • the high temperature part 62 and the low temperature part 63 are a heater, a radiator, etc., for example.
  • thermoelectric generation device 100 An electromotive force is generated in the stacked body 20 due to a temperature difference in the Y direction of the thermoelectric generation device 100 caused by the high temperature portion 62 and the low temperature portion 63, and the thermoelectric generation device 100 includes the first electrode 11 and the second electrode 12. To output power.
  • thermoelectric power generation device having a ⁇ -type structure generates an electromotive force in a direction parallel to a direction in which a temperature difference occurs, and does not generate an electromotive force in the vertical direction.
  • the direction in which the temperature gradient is generated (Y direction) is different from the electromotive force extraction direction (X direction). That is, the thermoelectric generation device 100 generates electric power by utilizing the anisotropy of thermoelectric characteristics in the laminated structure of different materials.
  • the stacked body 20 has a structure in which a first sandwiching layer 13 and a second sandwiching layer 14, which are a stacked structure of a metal 16 and an insulator 17, and a thermoelectric material layer 15 are stacked. Since the laminated body 20 has such a structure, the electromotive force is generated in the thermoelectric power generation device along the electromotive force extraction direction (X direction) that is different from the direction in which the temperature difference is generated (Y direction). Arise.
  • thermoelectric power generation device 100 As shown in the examples described later. As a result, it has been found that unexpectedly large thermoelectric power generation performance can be obtained in the process of examining in detail the relationship between the predetermined conditions in the thermoelectric power generation device 100 and the thermoelectric power generation performance. Specifically, the thermoelectric generation performance with respect to an angle (angle ⁇ ) formed by the direction 21 of the laminated surface 18 and the electromotive force extraction direction (X direction) was examined. Further, the thermoelectric generation performance with respect to the ratio between the stacking period (period x) of the insulator 17 in the first sandwiching layer 13 and the second sandwiching layer 14 and the thickness of the metal 16 was examined.
  • thermoelectric generation performance with respect to the ratio between the period x and the thickness of the thermoelectric material layer 15 was examined. These examination results will be described later.
  • the thickness of the metal 16 or the thickness of the thermoelectric material layer 15 is a thickness in the stacking direction (Z direction) of the stacked body 20 (see FIG. 1).
  • thermoelectric generation device 100 when the material of the thermoelectric material layer 15 is Bi 2-a Sb a Te 3 (0 ⁇ a ⁇ 2), the ratio of the period x to the thickness of the metal 16 is from 100: 1. It is preferably in the range of 0.4: 1, more preferably in the range of 40: 1 to 1: 1 (see Example 2 described later). As can be seen from the examples, the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the metal 16 is within this range is an extremely practical value.
  • the ratio of the period x to the thickness of the thermoelectric material layer (Bi2 -a Sb a Te 3 layer) 15 is preferably in the range of 1000: 1 to 20: 1. More preferably, it is in the range of 400: 1 to 100: 1 (see Example 3 below).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in the range of 10 ° to 70 °, and more preferably in the range of 20 ° to 50 ° (described later). See Example 1). As can be seen from the examples, the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • the ratio of the period x to the thickness of the metal 16 is preferably in the range of 20: 1 to 1: 1. It is more preferable that it is in the range of: 1 to 2.5: 1 (see Example 6 described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio of the period x to the thickness of the metal 16 is within this range is a very practical value.
  • the ratio of the period x to the thickness of the thermoelectric material layer (Bi layer) 15 is preferably in the range of 100: 1 to 5: 1, and is preferably 50: 1 to 10: 1. It is more preferable that it is in the range (see Example 7 described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in the range of 20 ° to 60 °, and more preferably in the range of 20 ° to 50 ° (described later). See Example 5).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • the ratio of the period x to the thickness of the metal 16 is preferably in the range of 100: 1 to 0.4: 1. More preferably, it is in the range of 40: 1 to 1: 1 (see Example 10 described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the ratio of the period x to the thickness of the metal 16 is within this range is a very practical value.
  • the ratio of the period x and the thickness of the thermoelectric material layer (PbTe layer) 15 is preferably in the range of 1000: 1 to 10: 1, and 400: 1 to 40 :. A range of 1 is more preferable (see Example 11 described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in the range of 10 ° to 60 °, and more preferably in the range of 20 ° to 50 ° (described later, See Example 9).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • thermoelectric generation device 100 when the material of the thermoelectric material layer 15 is Si 0.8 Ge 0.2 , the ratio between the period x and the thickness of the metal 16 is in the range of 20: 1 to 1.67: 1. It is preferable that it is in the range of 10: 1 to 2: 1 (see Example 14 described later). As can be seen from the examples, the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio of the period x to the thickness of the metal 16 is within this range is a very practical value.
  • the ratio between the period x and the thickness of the thermoelectric material layer (Si 0.8 Ge 0.2 layer) 15 is preferably in the range of 250: 1 to 10: 1, More preferably, it is in the range of 25: 1 (see Example 15 below).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in the range of 10 ° to 50 °, and more preferably in the range of 20 ° to 40 ° (described later). See Example 13).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • the ratio between the period x and the thickness of the metal 16 is preferably in the range of 20: 1 to 1.25: 1. More preferably, it is in the range of 10: 1 to 2.5: 1 (see Example 18 below).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the ratio of the period x to the thickness of the metal 16 is within this range is a very practical value.
  • the ratio of the period x to the thickness of the thermoelectric material layer (CoSi layer) 15 is preferably in the range of 100: 1 to 6.25: 1, and 50: More preferably, it is in the range of 1 to 12.5: 1 (see Example 19 below).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in a range of 20 ° or more and 50 ° or less, and more preferably in a range of 20 ° or more and 40 ° or less (described later, See Example 17).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • the ratio of the period x to the thickness of the metal 16 may be in the range of 20: 1 to 1.25: 1. Preferably, it is in the range of 10: 1 to 2.5: 1 (see Example 22 described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the ratio of the period x to the thickness of the metal 16 is within this range is a very practical value.
  • the ratio between the period x and the thickness of the thermoelectric material layer (SrTiO 3 layer) 15 is preferably in the range of 250: 1 to 8: 1, and 100: 1 to 10 :. It is more preferable that it is in the range of 1 (see Example 23 described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in the range of 10 ° to 50 °, and more preferably in the range of 20 ° to 40 ° (described later). See Example 21).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • the ratio of the period x to the thickness of the metal 16 is 50: It is preferably in the range of 1 to 2: 1, more preferably in the range of 10: 1 to 5: 1 (see Example 26, described below).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the ratio of the period x to the thickness of the metal 16 is within this range is a very practical value.
  • the ratio of the period x to the thickness of the thermoelectric material layer (Na b CoO 2 layer) 15 is preferably in the range of 250: 1 to 12.5: 1. 1 to 25: 1 is more preferable (see Example 27, which will be described later).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generation device 100 when the ratio between the period x and the thickness of the thermoelectric material layer 15 is within this range is an extremely practical value. Become.
  • the angle ⁇ is preferably manufactured so as to be in a range of 20 ° to 50 °, and more preferably in a range of 20 ° to 40 ° ( See Example 25 below).
  • the power factor (S 2 / ⁇ ) of the thermoelectric generator 100 when the angle ⁇ is within this range is a very practical value.
  • the power factor of the thermoelectric generator 100 is particularly preferably 70 ( ⁇ W / (cm ⁇ K 2 )) or more. Thereby, the thermoelectric generator device 100 can be used for many applications.
  • thermoelectric generation device 100 has an effect of having high power generation performance.
  • the ratio of the period x to the thickness of the metal, the ratio of the period x to the thickness of the thermoelectric generation material layer, and the angle ⁇ are set according to the material of the thermoelectric generation material layer 15. This greatly exceeds the thermoelectric performance when the material of the power generation material layer 15 is used alone. Therefore, a more practical thermoelectric power generation device 100 can be provided.
  • FIG. 7A is a flowchart showing manufacturing steps of the thermoelectric generator device according to Embodiment 1 of the present invention.
  • 7B to 7E are first to fourth process diagrams in the method for manufacturing a thermoelectric power generation device according to Embodiment 1 of the present invention.
  • step S1 two metal flat plates 16a made of the same material as the metal 16 and a flat thermoelectric material layer 15 are prepared, and the thermoelectric material layer 15 is sandwiched between the two metal flat plates 16a. By heating and pressure bonding, these are integrated to produce a laminated structure 20a having a three-layer structure (step S1).
  • step S2 groove processing is performed on the three-layer laminated structure 20a using a blade or the like (step S2).
  • the groove portion 17a formed by this groove processing is a place where the insulator 17 is formed. Therefore, it is necessary to perform groove processing in consideration of the period of the groove portion 17a, the angle with respect to the laminated structure 20a, and the like.
  • the groove processing is performed from both surfaces of the laminated structure 20a on the metal flat plate 16a side.
  • the period of the position of the groove portion 17a on both surfaces is the same period (period x).
  • the groove portions 17a formed in the two metal flat plates 16a are arranged so as to be shifted from each other by a half cycle.
  • the depth of the groove portion 17a needs to be equal to or greater than the thickness of the metal flat plate 16a so that at least the metal flat plate 16a on the side to be grooved is completely divided.
  • an insulator 17 is formed in the groove 17a (step S3).
  • the insulator 17 may be formed in the groove portion 17a by filling the groove portion 17a with the paste containing the electric insulator powder and then solidifying the paste by heat treatment or the like.
  • the insulator 17 may be formed by filling the groove portion 17a with a liquid resin and drying it. Thereby, the laminated body 20 is produced.
  • the first electrode 11 and the second electrode 12 are produced (step S4). Specifically, in the stacked body 20, the first electrode 11 and the second electrode 12 are installed on two surfaces that are perpendicular to the longitudinal direction and face each other. Thereby, the thermoelectric generation device 100 is produced.
  • various methods such as application of conductive paste, plating, thermal spraying, and joining by soldering are used in addition to vapor phase growth such as vapor deposition and sputtering. be able to.
  • thermoelectric material layer 15 and the metal flat plate 16a prepared in step S1 may not have the same size as the stacked body 20, but may have a size enough to form a plurality of stacked bodies 20. In that case, each laminated body 20 may be cut out from the laminated structure 20a after step S3. In this case, since the stacking direction of the insulator 17 and the metal 16 differs depending on the cutting position, direction, and the like, it is necessary to cut out the desired stacking direction.
  • the manufacturing method of the thermoelectric generation device 100 is not limited to the above method, and any other method may be used as long as the manufacturing method can realize the structure of the thermoelectric generation device 100.
  • the laminated structure 20a is manufactured by periodically bonding the parallelogram-shaped metal flat plates to be the respective metals 16 to both surfaces of the rectangular thermoelectric material flat plate while maintaining a constant interval, and then the step S3 and Step S4 may be performed. In this case, a constant interval between the metal flat plates corresponds to the groove portion 17a.
  • FIG. 8 is a perspective view of the thermoelectric generator according to Embodiment 2 of the present invention.
  • the thermoelectric generator 200 according to Embodiment 2 has a configuration in which a plurality of stacked bodies 20 are electrically connected in series. Since the configuration, function, and the like of the stacked body 20 have been described in the first embodiment, a description thereof will be omitted.
  • the thermoelectric generation device 200 includes a plurality (four) of stacked bodies 20 arranged in parallel on the same surface, and a plurality (three) of connecting them.
  • a connection electrode 81 and two extraction electrodes 82 for extracting electric power from the thermoelectric generator 200 to the outside are provided.
  • connection electrodes 81 so as to be electrically in series.
  • extraction electrode 82 is installed in the edge part of the side which is not connected with the other laminated body 20 among the edge parts of the laminated body 20 located in the both ends of this connection body.
  • connection electrode 81 and the extraction electrode 82 are not particularly limited as long as they are materials having electrical conductivity. Specifically, a metal such as Cu, Ag, Mo, W, Al, Ti, Cr, Au, Pt, or In, or a nitride or oxide such as TiN, tin-added indium oxide (ITO), or SnO 2 may be used. Good.
  • a metal such as Cu, Ag, Mo, W, Al, Ti, Cr, Au, Pt, or In, or a nitride or oxide such as TiN, tin-added indium oxide (ITO), or SnO 2 may be used. Good.
  • solder or conductive paste As the connection electrode 81 and the extraction electrode 82, it is possible to use solder or conductive paste.
  • the connection electrode 81 and the extraction electrode 82 can be produced by using various methods such as plating and thermal spraying in addition to vapor phase growth such as vapor deposition and sputtering.
  • thermoelectric generation device 200 has a configuration in which the four laminated bodies 20 that are electrically connected are arranged side by side on the same surface, but, for example, by filling a resin between adjacent laminated bodies 20,
  • the thermoelectric generator device 200 may have a flat plate shape.
  • thermoelectric generation device 200 When driving the thermoelectric generation device 200, a high temperature portion is brought into close contact with the upper surface of the thermoelectric generation device 200, and a low temperature portion is brought into close contact with the lower surface, thereby generating a temperature difference in the device and generating a heat flow.
  • the thermoelectric generation device 200 converts the heat flow into electric power and outputs the electric power to the outside via the extraction electrode 82.
  • a larger power generation amount can be obtained by increasing the mounting area for generating the heat flow in the thermoelectric generation device 200.
  • the mounting area is an area of a region for allowing heat to enter and exit from the outside in order to generate a temperature gradient necessary for power generation.
  • thermoelectric generation device 200 uses a larger number of the stacked bodies 20 than the thermoelectric generation device 100, the mounting area is large and a larger amount of power generation can be obtained.
  • thermoelectric power generation device 200 may be configured by electrically connecting a plurality of stacked bodies 20 in parallel via the connection electrode 81.
  • the thermoelectric power generation device 200 configured by connecting the stacked bodies 20 in series has an effect that the voltage at the time of taking out electric power is large.
  • thermoelectric power generating device configured by connecting the stacked bodies 20 in parallel is There is an effect that the internal resistance of the entire power generation device is small.
  • thermoelectric power generation device configured by connecting the stacked bodies 20 in parallel has an advantage that the electrical connection of the entire device can be maintained even if the electrical connection is partially broken.
  • thermoelectric power generation device of the present invention has excellent power generation performance, promotes application of energy conversion between heat and electricity, and has high industrial value.
  • the thermoelectric generator of the present invention can be used as a generator using heat such as exhaust gas discharged from an automobile or a factory, for example. It can also be applied to small portable generators.
  • thermoelectric power generation device 100 shown in FIG. 1 was manufactured and its performance was measured.
  • the material of the thermoelectric material layer 15 was Bi 0.5 Sb 1.5 Te 3 .
  • Au, Ag, Cu, and Al were used as the metal 16.
  • Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is obtained by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 2 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.2 mm. (See FIG. 7B).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes.
  • the thermoelectric power generation device 100 using the metal 16 as copper had an electromotive force of 18.4 mV and a resistance of 0.44 m ⁇ . From this, the power factor was estimated to be 457 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 1 were obtained.
  • thermoelectric power generation device 100 exhibits excellent thermoelectric power generation device characteristics exceeding 200 ⁇ W / cmK 2 when the angle ⁇ is 20 ° or more and 50 ° or less. understood.
  • the thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. Further, in the thermoelectric generator 100, even when the metal 16 is Al, if the angle ⁇ is 10 ° or more and 70 ° or less, the same or better performance as that of the ⁇ -type device using Bi 2 Te 3 is obtained.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 1, the thickness of the metal 16 was changed and the performance was measured.
  • the thermoelectric material layer 15 Bi 1.0 Sb 1.0 Te 3 was used. The angle ⁇ was 30 ° and the period x was 20 mm. Further, the thickness of the thermoelectric material layer 15 was fixed to 0.2 mm, and the outer shape of the thermoelectric device 100 was 200 mm long and 5 mm high.
  • the metal 16 was made of Cu, and the thickness was changed to 0.1 mm, 0.2 mm, 0.5 mm, 1 mm, 2 mm, 5 mm, 20 mm, and 50 mm. Table 2 shows the measurement results of the power factor of the thermoelectric generator device 100. It can be seen that the performance of the thermoelectric generation device 100 depends on the ratio between the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance around 10: 1.
  • Table 3 shows the measurement results of the power factor of the thermoelectric generator device 100 when the metal 16 is Ag. As shown in Table 3, even when the metal 16 was made of Ag, the power factor showed the same tendency as when the metal 16 was Cu.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 1, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was Bi 1.5 Sb 0.5 Te 3 .
  • the angle ⁇ was 30 ° and the period x was 20 mm.
  • the metal 16 is Cu
  • the thickness is fixed to 10 mm
  • the thermoelectric device 100 has an outer shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.01 mm, 0.02 mm, 0.05 mm, 0.2 mm, 0.5 mm, 1 mm, 2 mm, and 5 mm.
  • Table 4 shows the measurement results of the power factor of the thermoelectric generation device 100. It can be seen that the performance of the thermoelectric generator 100 depends on the ratio of the groove period (period x) to the thickness of the Bi 1.5 Sb 0.5 Te 3 layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance
  • Table 5 shows the measurement results of the power factor of the thermoelectric generator device 100 when the metal 16 is Ag. As shown in Table 5, even when the metal 16 is Ag, the power factor tends to be close to that when the metal 16 is Cu.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured.
  • the thermoelectric power generation device 200 shown in FIG. 8 is configured by four stacked bodies 20, but the thermoelectric power generation device 200 of Example 4 electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG.
  • thermoelectric generator 200 of Example 4 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu
  • the material of the thermoelectric material layer 15 was Bi 0.5 Sb 1.5 Te 3 .
  • Each laminate 20 was manufactured by the same manufacturing method as in Example 1.
  • a 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both sides of a 200 mm ⁇ 5 mm ⁇ 0.2 mm Bi 0.5 Sb 1.5 Te 3 plate to obtain a laminated structure 20a (see FIG. 7B).
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made. Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured by filling the gaps between the adjacent stacked bodies 20 and the grooves (insulators 17) of the stacked bodies 20 with resin. When the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 9 m ⁇ .
  • thermoelectric power generation device 200 of Example 4 The power generation characteristics of the thermoelectric power generation device 200 of Example 4 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.35 V, and a high value of 240 ⁇ W / cmK 2 was obtained when the power factor was estimated. A maximum of 4.4 W of electric power could be extracted from the thermoelectric power generation device 200.
  • Example 5 the thermoelectric device 100 shown in FIG. 1 was manufactured using Bi as the material of the thermoelectric material layer 15 and Au, Ag, Cu, and Al as the metal 16. Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is obtained by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 2 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.4 mm. (See FIG. 7B).
  • groove processing with a width of 0.5 mm, a depth of 2.4 mm, and an inclination angle of 30 ° with respect to the long side of the laminated structure 20a is performed on the metal flat plate 16a portion of the laminated structure 20a by an end mill.
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • the groove portions 17a formed in the two metal flat plates 16a were arranged so as to be shifted from each other by a half cycle. Thereafter, electrodes made of Au were formed by sputtering on both ends of the long side of the laminated structure 20a, and the thermoelectric generator 100 was manufactured (see FIG. 7E).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes. In the case of the thermoelectric power generation device 100 using the metal 16 as copper, the electromotive force was 8.7 mV and the resistance was 0.4 m ⁇ . From this, the power factor was estimated to be 106 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 6 were obtained.
  • thermoelectric power generation device 100 when the metal 16 is other than Al, the thermoelectric power generation device 100 is currently in practical use when the angle ⁇ is 20 ° or more and 60 ° or less, and is a ⁇ -type using Bi 2 Te 3. It has been found that the device has excellent thermoelectric device characteristics of about 40 ⁇ W / cmK 2 or more, which is a power factor of the device. The thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. Further, in the thermoelectric power generation device 100, even when the metal 16 is made of Al, if the angle ⁇ is 20 ° or more and 50 ° or less, performance equivalent to or higher than that of a ⁇ -type device using Bi 2 Te 3 is obtained. It was.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 5, the thickness of the metal 16 was changed and the performance was measured. Bi was used as the thermoelectric material layer 15. The angle ⁇ was 30 ° and the period x was 10 mm. The thickness of the thermoelectric material layer 15 was fixed to 0.4 mm, and the outer shape of the thermoelectric generation device 100 was 200 mm long and 5 mm high. The metal 16 was made of Cu, and the thickness was changed to 0.2 mm, 0.5 mm, 1 mm, 2 mm, 4 mm, 6 mm, 10 mm, and 15 mm. Table 7 shows the measurement results of the power factor of the thermoelectric generation device 100. It can be seen that the performance of the thermoelectric generation device 100 depends on the ratio between the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance around 5: 1.
  • Table 8 shows the measurement results of the power factor of the thermoelectric generator device 100 when the metal 16 is Ag. As shown in Table 8, the power factor showed the same tendency as when the metal 16 was Cu even when the metal 16 was Ag.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 5, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was Bi.
  • the angle ⁇ was 30 ° and the period x was 10 mm.
  • the metal 16 was Cu
  • the thickness was fixed to 2 mm
  • the thermoelectric device 100 had an external shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.04 mm, 0.1 mm, 0.2 mm, 0.4 mm, 0.8 mm, 1 mm, 2 mm, and 3 mm.
  • Table 9 shows the measurement results of the power factor of the thermoelectric generation device 100. It can be seen that the performance of the thermoelectric power generation device 100 is influenced by the ratio between the groove period (period x) and the thickness of the Bi layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance around 25: 1.
  • Table 10 shows the measurement results of the power factor of the thermoelectric generator device 100 when the metal 16 is Ag. As shown in Table 10, the power factor showed the same tendency as when the metal 16 was Cu even when the metal 16 was Ag.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured. Note that the thermoelectric generation device 200 illustrated in FIG. 8 includes the four stacked bodies 20, but the thermoelectric generation device 200 according to the eighth embodiment electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG. 8 will be referred to hereinafter.
  • thermoelectric generator 200 of Example 8 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu and the material of the thermoelectric material layer 15 was Bi.
  • Each laminate 20 was manufactured by the same manufacturing method as in Example 5.
  • a 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both sides of a 200 mm ⁇ 5 mm ⁇ 0.4 mm Bi plate material to obtain a laminated structure 20a (see FIG. 7B).
  • groove processing with a width of 0.5 mm, a depth of 2.4 mm, and an inclination angle of 30 ° with respect to the long side of the laminated structure 20a is performed on the metal flat plate 16a portion of the laminated structure 20a by an end mill. (See FIG. 7C). Therefore, the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made.
  • Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured.
  • the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 7 m ⁇ .
  • thermoelectric power generation device 200 of Example 8 The power generation characteristics of the thermoelectric power generation device 200 of Example 8 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.2 V, and a high value of 96 ⁇ W / cmK 2 was obtained when the power factor was estimated. From this thermoelectric power generation device 200, a maximum of 1.4 W of power could be taken out.
  • Example 9 In Example 9, the thermoelectric device 100 shown in FIG. 1 was manufactured using PbTe as the material of the thermoelectric material layer 15 and Au, Ag, Cu, and Al as the metal 16. Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is obtained by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 2 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.2 mm. (See FIG. 7B).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes. In the case of the thermoelectric power generation device 100 using the metal 16 as copper, the electromotive force was 23.5 mV and the resistance was 1.1 m ⁇ . From this, the power factor was estimated to be 306 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 11 were obtained.
  • thermoelectric power generation device 100 when the metal 16 is other than Al, the thermoelectric power generation device 100 is currently in practical use when the angle ⁇ is 20 ° or more and 50 ° or less, and the ⁇ -type using Bi 2 Te 3. It has been found that the device exhibits excellent thermoelectric device characteristics that are about 4 times or more than the power factor of about 40 ⁇ W / cmK 2 . The thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. Further, in the thermoelectric generator 100, even when the metal 16 is made of Al, if the angle ⁇ is 10 ° or more and 60 ° or less, the same or better performance as that of the ⁇ -type device using Bi 2 Te 3 is obtained.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 5, the thickness of the metal 16 was changed and the performance was measured. PbTe was used as the thermoelectric material layer 15. The angle ⁇ was 30 ° and the period x was 20 mm. Further, the thickness of the thermoelectric material layer 15 was fixed to 0.2 mm, and the outer shape of the thermoelectric device 100 was 200 mm long and 5 mm high. The metal 16 was made of Cu and its thickness was changed to 0.1 mm, 0.2 mm, 0.5 mm, 1 mm, 2 mm, 5 mm, 20 mm, and 50 mm. Table 12 shows the measurement results of the power factor of the thermoelectric generation device 100. It can be seen that the performance of the thermoelectric generation device 100 depends on the ratio between the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance around 10: 1.
  • Table 13 shows the measurement results of the power factor of the thermoelectric generation device 100 when the metal 16 is Ag. As shown in Table 13, even when the metal 16 was Ag, the power factor showed the same tendency as when the metal 16 was Cu.
  • thermoelectric generation device 100 In the thermoelectric generation device 100 manufactured in the same manner as in Example 9, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was PbTe.
  • the angle ⁇ was 30 ° and the period x was 20 mm.
  • the metal 16 is Cu
  • the thickness is fixed to 5 mm
  • the thermoelectric device 100 has an outer shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.01 mm, 0.02 mm, 0.05 mm, 0.2 mm, 0.5 mm, 1 mm, 2 mm, and 5 mm.
  • Table 14 shows the measurement results of the power factor of the thermoelectric generator 100. It can be seen that the performance of the thermoelectric power generation device 100 depends on the ratio between the groove period (period x) and the thickness of the PbTe layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance around 100: 1.
  • Table 15 shows the measurement results of the power factor of the thermoelectric generation device 100 when the metal 16 is Ag. As shown in Table 15, the power factor showed the same tendency as when the metal 16 was Cu even when the metal 16 was Ag.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured.
  • the thermoelectric power generation device 200 shown in FIG. 8 is configured by four stacked bodies 20, but the thermoelectric power generation device 200 of Example 4 electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG.
  • thermoelectric generation device 200 of Example 12 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu
  • the material of the thermoelectric material layer 15 was PbTe.
  • Each laminate 20 was produced by the same production method as in Example 9. A 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both surfaces of a 200 mm ⁇ 5 mm ⁇ 0.2 mm PbTe plate to obtain a laminated structure 20a (see FIG. 7B).
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made.
  • Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured.
  • the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 18 m ⁇ .
  • thermoelectric power generation device 200 of Example 12 The power generation characteristics of the thermoelectric power generation device 200 of Example 12 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.48 V, and a high value of 230 ⁇ W / cmK 2 was obtained when the power factor was estimated. A maximum of 3.3 W of electric power could be extracted from the thermoelectric power generation device 200.
  • Example 13 In Example 13, the thermoelectric device 100 shown in FIG. 1 was manufactured using Si 0.8 Ge 0.2 as the material of the thermoelectric material layer 15 and Au, Ag, Cu, and Al as the metal 16. Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is obtained by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 2 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.2 mm. (See FIG. 7B).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes. In the case of the thermoelectric power generation device 100 using the metal 16 as copper, the electromotive force was 17.7 mV and the resistance was 1.5 m ⁇ . From this, the power factor was estimated to be 124 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric power generation device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 16 were obtained.
  • thermoelectric power generation device 100 when the metal 16 is other than Al, the thermoelectric power generation device 100 is currently in practical use when the angle ⁇ is not less than 20 ° and not more than 40 °, and is a ⁇ -type using Bi 2 Te 3. It has been found that the device exhibits excellent thermoelectric device characteristics that are about three times or more than the power factor of about 40 ⁇ W / cmK 2 . The thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. Further, in the thermoelectric power generation device 100, even when the metal 16 was made of Al, if the angle ⁇ was 10 ° or more and 50 ° or less, the same or better performance as that of the ⁇ -type device using Bi 2 Te 3 was obtained.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 13, the thickness of the metal 16 was changed and the performance was measured. As the thermoelectric material layer 15, Si 0.8 Ge 0.2 was used. The angle ⁇ was 30 ° and the period x was 10 mm. Moreover, the thickness of the thermoelectric material layer 15 was fixed to 0.2 mm, and the outer shape of the thermoelectric generation device 100 was 200 mm long and 5 mm high. Table 17 shows the measurement results of the power factor of the thermoelectric device 100 in which the metal 16 is Cu and the thickness is changed to 0.2 mm, 0.5 mm, 1 mm, 2 mm, 4 mm, 5 mm, 6 mm, and 10 mm. .
  • thermoelectric generation device 100 depends on the ratio between the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance at 10: 1 or around 5: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 13, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was Si 0.8 Ge 0.2 .
  • the angle ⁇ was 30 ° and the period x was 10 mm.
  • the metal 16 was Cu
  • the thickness was fixed to 2 mm
  • the thermoelectric power generation device 100 had an external shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.02 mm, 0.04 mm, 0.1 mm, 0.2 mm, 0.4 mm, 0.8 mm, 1 mm, and 2 mm.
  • Table 18 shows the measurement result of the power factor of the thermoelectric generator 100.
  • thermoelectric generator 100 depends on the ratio between the groove period (period x) and the thickness of the Si 0.8 Ge 0.2 layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance around 50: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured.
  • the thermoelectric power generation device 200 shown in FIG. 8 is configured by four stacked bodies 20, but the thermoelectric power generation device 200 of Example 4 electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG.
  • thermoelectric generator 200 of Example 16 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu
  • the material of the thermoelectric material layer 15 was Si 0.8 Ge 0.2 .
  • Each laminate 20 was manufactured by the same manufacturing method as in Example 13. A 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both sides of a 200 mm ⁇ 5 mm ⁇ 0.2 mm Si 0.8 Ge 0.2 plate to obtain a laminated structure 20a (see FIG. 7B).
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made.
  • Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured.
  • the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 24 m ⁇ .
  • thermoelectric power generation device 200 of Example 16 The power generation characteristics of the thermoelectric power generation device 200 of Example 16 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.39 V, and a high value of 112 ⁇ W / cmK 2 was obtained when the power factor was estimated. A maximum of 1.6 W of electric power could be extracted from the thermoelectric power generation device 200.
  • Example 17 the thermoelectric device 100 shown in FIG. 1 was manufactured using CoSi as the material of the thermoelectric material layer 15 and Au, Ag, Cu, and Al as the metal 16. Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is obtained by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 2 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.4 mm. (See FIG. 7B).
  • groove processing with a width of 0.5 mm, a depth of 2.4 mm, and an inclination angle of 30 ° with respect to the long side of the laminated structure 20a is performed on the metal flat plate 16a portion of the laminated structure 20a by an end mill.
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • the groove portions 17a formed in the two metal flat plates 16a were arranged so as to be shifted from each other by a half cycle. Thereafter, electrodes made of Au were formed by sputtering on both ends of the long side of the laminated structure 20a, and the thermoelectric generator 100 was manufactured (see FIG. 7E).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes. In the case of the thermoelectric power generation device 100 using the metal 16 as copper, the electromotive force was 8.6 mV and the resistance was 0.49 m ⁇ . From this, the power factor was estimated to be 87 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 19 were obtained.
  • thermoelectric power generation device 100 when the metal 16 is other than Al, the thermoelectric power generation device 100 is currently in practical use when the angle ⁇ is 20 ° or more and 50 ° or less, and the ⁇ -type using Bi 2 Te 3. It has been found that it exhibits excellent thermoelectric device characteristics that are about twice or more than the power factor of about 40 ⁇ W / cmK 2 . The thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. Further, in the thermoelectric generator 100, even when the metal 16 is made of Al, if the angle ⁇ is 20 ° or more and 40 ° or less, the same or better performance as the ⁇ -type device using Bi 2 Te 3 is obtained.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 17, the thickness of the metal 16 was changed and the performance was measured. CoSi was used as the thermoelectric material layer 15. The angle ⁇ was 30 ° and the period x was 10 mm. Moreover, the thickness of the thermoelectric material layer 15 was fixed to 0.4 mm, and the outer shape of the thermoelectric generation device 100 was 200 mm in length and 5 mm in height. Table 20 shows the measurement results of the power factor of the thermoelectric power generation device 100 in which the metal 16 is Cu and the thickness is changed to 0.2 mm, 0.5 mm, 1 mm, 2 mm, 4 mm, 5 mm, 8 mm, and 10 mm. .
  • thermoelectric generation device 100 depends on the ratio between the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance around 5: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 17, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was CoSi.
  • the angle ⁇ was 30 ° and the period x was 10 mm.
  • the metal 16 was Cu
  • the thickness was fixed to 2 mm
  • the thermoelectric device 100 had an external shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.04 mm, 0.1 mm, 0.2 mm, 0.4 mm, 0.8 mm, 1.2 mm, 1.6 mm, and 2 mm.
  • Table 21 shows the measurement result of the power factor of the thermoelectric generator 100.
  • thermoelectric generator 100 is influenced by the ratio of the groove period (period x) and the thickness of the CoSi layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance around 25: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured.
  • the thermoelectric power generation device 200 shown in FIG. 8 is configured by four stacked bodies 20, but the thermoelectric power generation device 200 of Example 4 electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG.
  • thermoelectric power generation device 200 of Example 20 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu
  • the material of the thermoelectric material layer 15 was CoSi.
  • Each laminate 20 was produced by the same production method as in Example 20.
  • a 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both sides of a 200 mm ⁇ 5 mm ⁇ 0.4 mm CoSi plate to obtain a laminated structure 20a (see FIG. 7B).
  • the groove part 17a was arrange
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made.
  • Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured.
  • the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 7.3 m ⁇ .
  • thermoelectric power generation device 200 of Example 20 The power generation characteristics of the thermoelectric power generation device 200 of Example 20 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.20 V, and a high value of 87 ⁇ W / cmK 2 was obtained when the power factor was estimated. From this thermoelectric power generation device 200, a maximum of 1.4 W of power could be taken out.
  • Example 21 In Example 21, the thermoelectric device 100 shown in FIG. 1 was manufactured using SrTiO 3 as the material of the thermoelectric material layer 15 and Au, Ag, Cu, and Al as the metal 16. Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is obtained by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 2 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.2 mm. (See FIG. 7B).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes. In the case of the thermoelectric power generation device 100 using the metal 16 as copper, the electromotive force was 20.0 mV and the resistance was 1.8 m ⁇ . From this, the power factor was estimated to be 104 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric power generation device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 22 were obtained.
  • thermoelectric power generation device 100 when the metal 16 is other than Al, the thermoelectric power generation device 100 is currently in practical use when the angle ⁇ is 10 ° or more and 50 ° or less, and is a ⁇ -type using Bi 2 Te 3. It has been found that the device exhibits excellent thermoelectric device characteristics equal to or higher than the device power factor of about 40 ⁇ W / cmK 2 . The thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. In addition, even when Al is used for the metal 16 in the thermoelectric power generation device 100, if the angle ⁇ is 20 ° or more and 40 ° or less, performance equivalent to or higher than that of a ⁇ -type device using Bi 2 Te 3 is obtained. Obtained.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 21, the thickness of the metal 16 was changed and the performance was measured. As the thermoelectric material layer 15, SrTiO 3 was used. The angle ⁇ was 30 ° and the period x was 10 mm. The thickness of the thermoelectric material layer 15 was fixed to 0.2 mm, and the outer shape of the thermoelectric generator device 100 was 200 mm and the width was 5 mm. Table 23 shows the measurement results of the power factor of the thermoelectric power generation device 100 in which the metal 16 is Cu and the thickness is changed to 0.2 mm, 0.5 mm, 1 mm, 2 mm, 4 mm, 6 mm, 8 mm, and 10 mm. .
  • thermoelectric generator 100 is influenced by the ratio of the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance around 5: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 21, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was SrTiO 3 .
  • the angle ⁇ was 30 ° and the period x was 10 mm.
  • the metal 16 was Cu
  • the thickness was fixed to 2 mm
  • the thermoelectric device 100 had an external shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.02 mm, 0.04 mm, 0.1 mm, 0.2 mm, 0.8 mm, 1.2 mm, 1.6 mm, and 2 mm.
  • Table 24 shows the measurement results of the power factor of the thermoelectric generator 100.
  • thermoelectric generator 100 is influenced by the ratio between the groove period (period x) and the thickness of the SrTiO 3 layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance around 50: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured.
  • the thermoelectric power generation device 200 shown in FIG. 8 is configured by four stacked bodies 20, but the thermoelectric power generation device 200 of Example 4 electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG.
  • thermoelectric generator 200 of Example 24 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu
  • the material of the thermoelectric material layer 15 was SrTiO 3 .
  • Each laminate 20 was produced by the same production method as in Example 21.
  • a 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both surfaces of a 200 mm ⁇ 5 mm ⁇ 0.2 mm SrTiO 3 plate to obtain a laminated structure 20a (see FIG. 7B).
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • the groove portions 17a formed in the two metal flat plates 16a are arranged so as to be shifted from each other by a half cycle.
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made.
  • Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured.
  • the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 27.5 m ⁇ .
  • thermoelectric power generation device 200 of Example 24 The power generation characteristics of the thermoelectric power generation device 200 of Example 24 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.40 V, and a high value of 105 ⁇ W / cm K 2 was obtained when the power factor was estimated. From this thermoelectric power generation device 200, a maximum of 1.5 W of electric power could be taken out.
  • Example 25 the thermoelectric device 100 shown in FIG. 1 was manufactured using Na 0.5 CoO 2 as the material of the thermoelectric material layer 15 and Au, Ag, Cu, and Al as the metal 16. Au was used for the first electrode 11 and the second electrode 12.
  • the laminated structure 20a composed of the thermoelectric material layer 15 and the two metal flat plates 16a is formed by thermocompression bonding a metal plate of 200 mm ⁇ 5 mm ⁇ 1 mm on both sides of a plate made of a thermoelectric material of 200 mm ⁇ 5 mm ⁇ 0.2 mm. (See FIG. 7B).
  • groove processing is performed on the metal flat plate 16a portion of the laminated structure 20a from both sides by an end mill with a width of 0.5 mm, a depth of 1.2 mm, and an inclination angle of 30 ° with respect to the long side of the laminated structure 20a. (See FIG. 7C). Therefore, the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • the groove portions 17a formed in the two metal flat plates 16a were arranged so as to be shifted from each other by a half cycle. Thereafter, electrodes made of Au were formed by sputtering on both ends of the long side of the laminated structure 20a, and the thermoelectric generator 100 was manufactured (see FIG. 7E).
  • thermoelectric power generation device The power generation performance was evaluated for the produced sample (thermoelectric power generation device). As shown in FIG. 6, one of the surfaces perpendicular to the Y direction of the thermoelectric generator 100 is heated to 40 ° C. by a ceramic heater (high temperature portion 62), and the other is heated to 30 ° C. by a water cooling device (low temperature portion 63). It cooled and measured the electromotive force and electrical resistance between both electrodes. In the case of the thermoelectric power generation device 100 using the metal 16 as copper, the electromotive force was 10.7 mV and the resistance was 1.3 m ⁇ . From this, the power factor was estimated to be 99 ⁇ W / cmK 2 . Similarly, when the performance of the thermoelectric device 100 was measured while changing the metal 16 and the angle ⁇ , the results shown in Table 25 were obtained.
  • thermoelectric power generation device 100 when the metal 16 is other than Al, the thermoelectric power generation device 100 is currently in practical use when the angle ⁇ is not less than 20 ° and not more than 40 °, and is a ⁇ -type using Bi 2 Te 3. It has been found that it exhibits excellent thermoelectric device characteristics that are about twice or more than the power factor of about 40 ⁇ W / cmK 2 . The thermoelectric power generation device 100 was confirmed to have higher performance when Ag or Cu was used as the metal 16 than when other metals were used. Further, in the thermoelectric generator 100, even when the metal 16 is made of Al, if the angle ⁇ is 20 ° or more and 50 ° or less, the same or better performance as that of the ⁇ -type device using Bi 2 Te 3 is obtained.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 25, the thickness of the metal 16 was changed and the performance was measured. As the thermoelectric material layer 15, Na 0.8 CoO 2 was used. The angle ⁇ was 30 ° and the period x was 10 mm. Further, the thickness of the thermoelectric material layer 15 was fixed to 0.2 mm, and the outer shape of the thermoelectric device 100 was 200 mm long and 5 mm high. Table 26 shows the measurement result of the power factor of the thermoelectric power generation device 100 in which the metal 16 is Cu and the thickness thereof is changed to 0.1 mm, 0.2 mm, 0.5 mm, 1 mm, 2 mm, 5 mm, 8 mm, and 10 mm.
  • thermoelectric generation device 100 depends on the ratio between the groove period (period x) and the thickness of Cu (metal 16). This ratio was confirmed to be the best performance around 10: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 100 In the thermoelectric power generation device 100 manufactured in the same manner as in Example 25, the thickness of the thermoelectric material layer 15 was changed and the performance was measured.
  • the material of the thermoelectric material layer 15 was Na 0.3 CoO 2 .
  • the angle ⁇ was 30 ° and the period x was 10 mm.
  • the metal 16 was Cu, the thickness was fixed to 1 mm, and the thermoelectric device 100 had an outer shape of 200 mm in length and 5 mm in height.
  • the thickness of the thermoelectric material layer 15 was changed to 0.02 mm, 0.04 mm, 0.1 mm, 0.2 mm, 0.4 mm, 0.8 mm, 1 mm, and 1.6 mm.
  • Table 27 shows the measurement result of the power factor of the thermoelectric generator 100.
  • thermoelectric generator 100 depends on the ratio of the groove period (period x) and the thickness of the Na 0.3 CoO 2 layer (thermoelectric material layer 15). This ratio was confirmed to be the best performance around 50: 1. Moreover, although the measurement result is not shown, the same tendency was obtained when the metal 16 was Ag.
  • thermoelectric power generation device 200 shown in FIG. 8 was manufactured and its performance was measured.
  • the thermoelectric power generation device 200 shown in FIG. 8 is configured by four stacked bodies 20, but the thermoelectric power generation device 200 of Example 4 electrically connects the 15 stacked bodies 20 in series. It is constituted by. Except for this point, the configuration is the same as that of FIG. 8, and therefore, FIG.
  • thermoelectric generator 200 of Example 28 In was used for the connection electrode 81 and the extraction electrode 82.
  • the metal 16 was Cu
  • the material of the thermoelectric material layer 15 was Na 0.4 CoO 2 .
  • Each laminate 20 was produced by the same production method as in Example 25.
  • a 200 mm ⁇ 5 mm ⁇ 2 mm Cu plate was thermocompression bonded to both surfaces of a 200 mm ⁇ 5 mm ⁇ 0.2 mm Na 0.4 CoO 2 plate to obtain a laminated structure 20a (see FIG. 7B).
  • the angle ⁇ illustrated in FIG. 2 is 30 °.
  • the groove part 17a was arrange
  • the groove portions 17a formed in the two metal flat plates 16a are arranged so as to be shifted from each other by a half cycle.
  • a total of 15 laminates 20 were produced by the above process.
  • the 15 laminated bodies 20 produced were arranged side by side on the same surface at intervals of 1 mm, and were formed by heating and pressurizing 50 ⁇ m-thick In foil as connection electrodes 81 and extraction electrodes 82. Electrical connection was made.
  • Fifteen laminates 20 were connected in series with the direction of the electromotive force aligned.
  • a plate-shaped thermoelectric power generation device 200 of about 200 mm ⁇ 80 mm ⁇ 5 mm was manufactured.
  • the resistance value between the extraction electrodes 82 of the thermoelectric device 200 was measured, it was 16 m ⁇ .
  • thermoelectric power generation device 200 of Example 28 The power generation characteristics of the thermoelectric power generation device 200 of Example 28 were evaluated. First, a 200 mm ⁇ 80 mm single side of the thermoelectric generator 200 was cooled with water through an alumina plate to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the thermoelectric generator 200. With such a configuration, when the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C., the open end electromotive force was 0.28 V, and a high value of 84 ⁇ W / cm K 2 was obtained when the power factor was estimated. From this thermoelectric power generation device 200, a maximum of 1.2 W of electric power could be extracted.
  • the present invention can be used for a thermoelectric power generation device that converts thermal energy into electrical energy.

Landscapes

  • Electromechanical Clocks (AREA)
  • Primary Cells (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Powder Metallurgy (AREA)

Abstract

L’invention concerne un dispositif générateur de puissance thermique comprenant une première électrode et une seconde électrode disposées de telle sorte qu’elles se font face et un stratifié qui est intercalé entre la première électrode et la seconde électrode, connecté électriquement à la première électrode et à la seconde électrode, et stratifié dans la direction perpendiculaire à la direction de prise de la force électromotrice, qui est la direction dans laquelle la première électrode et la seconde électrode se font face.  Le stratifié comprend une couche de matériau thermoélectrique, et une première couche de maintien, et une seconde couche de maintient disposées de façon à maintenir la couche de matériau thermoélectrique entre elles.  La première couche de maintien et la seconde couche de maintien comportent une structure multicouche dans laquelle des métaux et des matériaux isolants sont disposés alternativement, et la direction d’empilement de la structure multicouche est parallèle au plan de stratification du stratifié, tout en étant inclinée vers la direction de prise de la force électromotrice.  Les matériaux isolants de la première couche de maintien et les matériaux isolants de la seconde couche de maintien sont disposés de façon à alterner les uns avec les autres dans la direction d’empilement.  En générant une différence de température dans la direction perpendiculaire non seulement à la direction de stratification du stratifié mais aussi de la direction de prise de la force électromotrice, la puissance électrique est émise via la première électrode et la seconde électrode.
PCT/JP2009/005641 2008-11-21 2009-10-26 Dispositif générateur de puissance thermique et procédé de génération de puissance l’utilisant Ceased WO2010058526A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2009801203138A CN102047458B (zh) 2008-11-21 2009-10-26 热发电器件和使用该器件的发电方法
US12/811,182 US7994415B2 (en) 2008-11-21 2009-10-26 Thermoelectric device and power generation method using the same
JP2010510018A JP4584355B2 (ja) 2008-11-21 2009-10-26 熱発電デバイスおよびそれを用いた発電方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008297545 2008-11-21
JP2008-297545 2008-11-21

Publications (1)

Publication Number Publication Date
WO2010058526A1 true WO2010058526A1 (fr) 2010-05-27

Family

ID=42197969

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/005641 Ceased WO2010058526A1 (fr) 2008-11-21 2009-10-26 Dispositif générateur de puissance thermique et procédé de génération de puissance l’utilisant

Country Status (4)

Country Link
US (1) US7994415B2 (fr)
JP (1) JP4584355B2 (fr)
CN (1) CN102047458B (fr)
WO (1) WO2010058526A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9082928B2 (en) 2010-12-09 2015-07-14 Brian Isaac Ashkenazi Next generation thermoelectric device designs and methods of using same
CN105051925B (zh) * 2013-03-27 2018-07-17 株式会社日立制作所 高效率热电转换装置
CN108242499B (zh) * 2016-12-23 2020-01-14 武汉理工大学 一种无需电极碲化铋热电器件及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001358373A (ja) * 2000-06-15 2001-12-26 Citizen Watch Co Ltd 熱電発電素子およびその製造方法
JP2005277222A (ja) * 2004-03-25 2005-10-06 Yamaha Corp 熱電モジュールの製造方法
WO2008108034A1 (fr) * 2007-03-06 2008-09-12 Panasonic Corporation Procédé de production d'énergie employant un élément de production thermoélectrique, élément de production thermoélectrique et son procédé de fabrication et dispositif de production thermoélectrique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2586959B2 (ja) 1990-07-17 1997-03-05 東亜グラウト工業株式会社 管路の更新方法
JP4078392B1 (ja) 2006-11-10 2008-04-23 松下電器産業株式会社 熱発電素子を用いた発電方法、熱発電素子とその製造方法、ならびに熱発電デバイス
CN201134444Y (zh) * 2007-12-27 2008-10-15 江门金谷电子工业有限公司 一种温差发电装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001358373A (ja) * 2000-06-15 2001-12-26 Citizen Watch Co Ltd 熱電発電素子およびその製造方法
JP2005277222A (ja) * 2004-03-25 2005-10-06 Yamaha Corp 熱電モジュールの製造方法
WO2008108034A1 (fr) * 2007-03-06 2008-09-12 Panasonic Corporation Procédé de production d'énergie employant un élément de production thermoélectrique, élément de production thermoélectrique et son procédé de fabrication et dispositif de production thermoélectrique

Also Published As

Publication number Publication date
JP4584355B2 (ja) 2010-11-17
JPWO2010058526A1 (ja) 2012-04-19
US20100282286A1 (en) 2010-11-11
US7994415B2 (en) 2011-08-09
CN102047458B (zh) 2012-07-25
CN102047458A (zh) 2011-05-04

Similar Documents

Publication Publication Date Title
JP4078392B1 (ja) 熱発電素子を用いた発電方法、熱発電素子とその製造方法、ならびに熱発電デバイス
JP4124807B1 (ja) 熱発電素子を用いた発電方法、熱発電素子とその製造方法、ならびに熱発電デバイス
US20100326487A1 (en) Thermoelectric element and thermoelectric device
WO2013011997A1 (fr) Module de conversion thermoélectrique empilé
US7449628B2 (en) Electric power generation method using thermoelectric power generation element, thermoelectric power generation element and method of producing the same, and thermoelectric power generation device
JP4584355B2 (ja) 熱発電デバイスおよびそれを用いた発電方法
JP5176610B2 (ja) 熱発電デバイス素子
JP5200884B2 (ja) 熱発電デバイス
JP5176609B2 (ja) 熱発電デバイス素子
WO2014200884A1 (fr) Module thermoélectrique et son procédé de réalisation
US20130319491A1 (en) Electricity generation method using thermoelectric generation element, thermoelectric generation element and manufacturing method thereof, and thermoelectric generation device
JP5200885B2 (ja) 熱発電デバイス
JP5176607B2 (ja) 熱発電デバイス素子
JP5176602B2 (ja) 熱発電デバイス素子
JP5200883B2 (ja) 熱発電デバイス
JP5176606B2 (ja) 熱発電デバイス素子
JP5176608B2 (ja) 熱発電デバイス素子
JP4130845B1 (ja) 熱発電素子を用いた発電方法、熱発電素子とその製造方法、ならびに熱発電デバイス

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980120313.8

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2010510018

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 12811182

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09827307

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 1812/MUMNP/2010

Country of ref document: IN

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09827307

Country of ref document: EP

Kind code of ref document: A1