WO2012073946A1 - Elément et module de conversion thermoélectrique - Google Patents

Elément et module de conversion thermoélectrique Download PDF

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WO2012073946A1
WO2012073946A1 PCT/JP2011/077500 JP2011077500W WO2012073946A1 WO 2012073946 A1 WO2012073946 A1 WO 2012073946A1 JP 2011077500 W JP2011077500 W JP 2011077500W WO 2012073946 A1 WO2012073946 A1 WO 2012073946A1
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thermoelectric conversion
silicide
conversion element
transition metal
electrode
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PCT/JP2011/077500
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English (en)
Japanese (ja)
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努 飯田
康彦 本多
多田　光宏
昌保 赤坂
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学校法人東京理科大学
東レ・ダウコーニング株式会社
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Priority to JP2012546882A priority Critical patent/JP5881066B2/ja
Publication of WO2012073946A1 publication Critical patent/WO2012073946A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen

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  • the present invention relates to a thermoelectric conversion element and a thermoelectric conversion module including the thermoelectric conversion element.
  • thermoelectric conversion element capable of mutual conversion between thermal energy and electrical energy forms a pair of electrode layers on both sides of the thermoelectric conversion layer, and maintains one of the electrode layers at a high temperature and the other at a low temperature to form a temperature difference.
  • the heat is converted into electric power by utilizing the Seebeck effect in which an electromotive force is generated corresponding to the temperature difference.
  • thermoelectric conversion materials constituting the thermoelectric conversion layer bismuth-tellurium-based materials, lead-tellurium-based materials, cobalt-antimony-based materials, semiconductor silicide-based materials, and the like are known.
  • semiconductor silicide-based materials such as magnesium silicide are attracting attention because of their low environmental burden (see, for example, Patent Documents 1 to 3).
  • thermoelectric conversion element using magnesium silicide as a thermoelectric conversion material
  • nickel is widely used as an electrode material because there is little mutual diffusion with magnesium silicide and excellent high-temperature durability.
  • nickel when nickel is used as the electrode material, there is a problem that the contact resistance between the thermoelectric conversion layer and the electrode layer becomes relatively high.
  • thermoelectric conversion element provided with the thermoelectric conversion element with which the contact resistance between a thermoelectric conversion layer and an electrode layer was reduced, and this thermoelectric conversion element.
  • thermoelectric conversion element provided with the thermoelectric conversion element with which the contact resistance between a thermoelectric conversion layer and an electrode layer was reduced, and this thermoelectric conversion element.
  • the inventors of the present invention have made extensive studies in order to achieve the above object. As a result, it has been found that the above problem can be solved by using transition metal silicide or a mixture of transition metal silicide and metal material as the material of the electrode layer formed on both sides of the thermoelectric conversion layer made of semiconductor silicide.
  • the invention has been completed. Specifically, the present invention is as follows.
  • thermoelectric conversion element in which a pair of electrode layers are formed on both sides of a thermoelectric conversion layer made of semiconductor silicide, at least one of the pair of electrode layers is a transition metal silicide or a mixture of a transition metal silicide and a metal material.
  • Thermoelectric conversion element consisting of body.
  • the semiconductor silicide is magnesium silicide.
  • the transition metal silicide is at least one selected from the group consisting of nickel silicide, chromium silicide, cobalt silicide, and titanium silicide.
  • thermoelectric conversion module provided with the thermoelectric conversion element of any one of said (1) to (4).
  • thermoelectric conversion element with reduced contact resistance between the thermoelectric conversion layer and the electrode layer, and a thermoelectric conversion module including the thermoelectric conversion element.
  • thermoelectric conversion element which concerns on this invention. It is a figure which shows the one aspect
  • FIG. 3 is a view showing thermoelectric conversion elements manufactured in Examples 1 to 4 and Comparative Example 1.
  • FIG. 3 is a view showing thermoelectric conversion elements manufactured in Examples 1 to 4 and Comparative Example 1.
  • thermoelectric conversion layer 4 is a diagram showing the results of observing the interface between the thermoelectric conversion layer and the electrode layer in the sintered bodies obtained in Examples 1 to 4 and Comparative Example 1 with an optical microscope. It is a figure which shows the structure of the measuring apparatus which measures the IV characteristic of a thermoelectric conversion element.
  • FIG. 4 is a diagram showing IV characteristics of thermoelectric conversion elements manufactured in Examples 1 to 4 and Comparative Example 1.
  • thermoelectric conversion element is a thermoelectric conversion element in which a pair of electrode layers are formed on both sides of a thermoelectric conversion layer made of semiconductor silicide, and at least one of the pair of electrode layers is transition metal silicide or transition metal silicide. And a metal material.
  • FIG. 1 shows an embodiment of a thermoelectric conversion element according to the present invention.
  • a pair of electrode layers 12 a and 12 b are formed on both sides of a prismatic thermoelectric conversion layer 11.
  • thermoelectric conversion material constituting the thermoelectric conversion layer 11 semiconductor silicide such as magnesium silicide (Mg 2 Si) and iron silicide (FeSi 2 ) is used, and these are dopants such as antimony, aluminum, bismuth, silver and copper. May be included.
  • magnesium silicide is preferable because it is thermally stable, has high thermoelectric conversion efficiency, and has high rigidity. An example of a method for synthesizing magnesium silicide will be described in detail later.
  • the average particle diameter of the semiconductor silicide is not particularly limited, but for example, it is preferable to use a semiconductor silicide having a particle diameter of 75 ⁇ m or less.
  • transition metal silicide or a mixture of transition metal silicide and metal material is used as the electrode material constituting at least one of the electrode layers 12a and 12b.
  • the thermoelectric conversion layer and the electrode layer can be compared with a case where a metal material such as nickel is used. The contact resistance between them can be reduced.
  • both the electrode layers 12a and 12b are made of transition metal silicide or a mixture of transition metal silicide and a metal material.
  • a transition metal silicide or a mixture of a transition metal silicide and a metal material may be used for only one of them, and a metal material such as nickel may be used for the other.
  • the electrode layer using the transition metal silicide or the mixture of the transition metal silicide and the metal material is disposed on the high temperature side of the thermoelectric conversion module. There are two reasons for this.
  • the first reason is that it is preferable to use an electrode material having a relatively low resistance value on the high temperature side because an increase in resistance in the electrode is expected in a high temperature state during operation.
  • the second reason is that nickel tends to form an oxide in a high temperature environment, which causes an increase in resistance due to deterioration of the interface between the thermoelectric conversion layer and the electrode layer. This is because the increase in resistance due to such deterioration can be prevented.
  • transition metal silicide examples include nickel silicide (NiSi, NiSi 2 ), chromium silicide (CrSi 2 ), cobalt silicide (CoSi 2 ), titanium silicide (TiSi 2 ), molybdenum silicide (MoSi 2 ), tungsten silicide (WSi 2 ). Etc. Among these, at least one selected from the group consisting of nickel silicide, chromium silicide, and cobalt silicide is preferable, and cobalt silicide is particularly preferable.
  • the average particle diameter of the transition metal silicide is not particularly limited, but it is preferable to use a transition metal silicide having a particle diameter of 2 to 15 ⁇ m, for example.
  • nickel, titanium, copper, aluminum, iron etc. are mentioned as a metal material mixed with the said transition metal silicide as needed.
  • nickel is particularly preferable because of excellent heat resistance.
  • the average particle diameter of the metal material is not particularly limited, but it is preferable to use, for example, a material having a thickness of 2 to 3 ⁇ m. Whether or not a metal material is mixed is arbitrary, but it is preferable to mix a metal material particularly when chromium silicide, cobalt silicide, or titanium silicide is used as the transition metal silicide.
  • the mixing ratio (transition metal silicide / metal material) is preferably 30/70 to 70/30 (mass basis).
  • the mixing ratio (transition metal silicide / metal material) is preferably 30/70 to 50/50 (mass basis).
  • nickel silicide is used as the transition metal silicide, it is preferable whether or not a metal material is mixed, and the mixing ratio (transition metal silicide / metal material) is preferably 30/70 to 100/0 (mass basis). It can be illustrated.
  • thermoelectric conversion element 1 for example, a space corresponding to the shape of the thermoelectric conversion element 1 (for example, a rod-like, columnar, plate-like member having a circular or polygonal cross section) was formed. 1 is manufactured simply by placing and depositing the materials to be used to a desired thickness in accordance with the configuration of the thermoelectric conversion element 1 shown in FIG. Can do.
  • thermoelectric conversion element 1 An example of means for manufacturing the thermoelectric conversion element 1 will be described using the manufacturing apparatus 2 having the configuration shown in FIGS. 2 and 3 (in FIGS. 2 and 3, the state inside the carbon die 21 is easily understood. Thus, a part of the carbon die 21 is omitted).
  • 2 shows a state before the manufacturing apparatus 2 is filled with the constituent material of the thermoelectric conversion element 1
  • FIG. 3 shows a state after the constituent material of the thermoelectric conversion element 1 is filled.
  • the manufacturing apparatus 2 is filled with a carbon die 21 in which a cylindrical space portion 23 is formed, and a space portion 23 (in FIG. 3, the constituent material of the thermoelectric conversion element 1 and the like).
  • the carbon punches 22a and 22b disposed above and below the portion).
  • the carbon punch 22 b disposed below the space portion 23 is fixed to the carbon die 21.
  • the carbon punch 22 a disposed above the space portion 23 is removable, and the material to be sintered such as semiconductor silicide is spaced from above the space portion 23.
  • the unit 23 can be input.
  • the carbon punch 22a disposed above the space portion 23 is removed (state of FIG. 2), and the space portion 23 has the structure shown in FIG.
  • the electrode material layer, the thermoelectric conversion material layer, and the electrode are deposited and deposited in the order of the electrode material, the thermoelectric conversion material, and the electrode material in accordance with the configuration of the thermoelectric conversion element 1 shown in FIG. A material layer is formed.
  • the carbon punch 22a When the material of each layer is charged, it is preferable to press and harden with the carbon punch 22a or the like.
  • the carbon punch 22a is inserted from above the space 23 and the material is sandwiched between the carbon punches 22a and 22b to obtain the state shown in FIG.
  • thermoelectric conversion element 1 having the configuration shown in FIG. 1 can be obtained.
  • a hot press sintering method HP
  • a hot isostatic pressing method HIP
  • a discharge plasma sintering method SPS
  • the spark plasma sintering method is a type of pressure compression sintering using the direct current pulse current method. It is a method of heating and sintering by applying a large pulse current to various materials. -This is a method in which an electric current is passed through a conductive material such as graphite and the material is processed and processed by Joule heating.
  • Specific sintering conditions are preferably a sintering pressure of 5 to 60 MPa, a sintering temperature of 800 to 870 ° C., and a sintering time (holding time) of 2 to 10 minutes. At this time, it is preferable to raise the temperature stepwise up to the sintering temperature (for example, room temperature ⁇ 600 ° C. ⁇ 800 ° C. ⁇ 840 ° C.). Moreover, it is preferable to perform a sintering process in inert gas atmosphere, such as nitrogen gas, argon gas, and helium gas.
  • inert gas atmosphere such as nitrogen gas, argon gas, and helium gas.
  • an insulating material such as SiO 2 is introduced and deposited between the electrode material layer and the carbon punches 22a and 22b in order to prevent melting of the electrode material. It is preferable to form an insulating material layer. Alternatively, the same effect can be achieved by applying boron nitride to the surfaces of the carbon punches 22a and 22b in contact with the electrode material. Further, in order to prevent the semiconductor silicide from adhering to the manufacturing apparatus 2, it is preferable to sandwich carbon paper at the contact portion with the semiconductor silicide.
  • thermoelectric conversion element manufactured as described above for the purpose of reducing the contact resistance between the thermoelectric conversion layer and the electrode layer.
  • the specific method of the annealing treatment is not particularly limited, and a method in which a thermoelectric conversion element is placed in a high-temperature furnace and annealing treatment is performed on the thermoelectric conversion element by heat from a heater provided in the furnace may be used, or rapid thermal annealing Alternatively, the thermoelectric conversion element may be annealed using light energy such as flash lamp annealing.
  • Magnesium silicide as a semiconductor silicide can be synthesized by a conventional method using magnesium, silicon, and, if necessary, a dopant.
  • the temperature at the time of synthesis is set to a temperature equal to or higher than the melting point of magnesium silicide (1085 ° C.),
  • a melt synthesis method in which the entire system is synthesized in a melted state is preferable because uniform magnesium silicide can be obtained.
  • This melt synthesis method includes a mixing step of mixing magnesium, silicon, and, if necessary, a dopant to obtain a composition raw material, and a heating and melting step of heating and melting the composition raw material.
  • the mixing step magnesium and silicon are mixed at an atomic weight ratio of about 2: 1, and a dopant is further mixed as necessary to obtain a composition raw material.
  • the atomic weight ratio of the dopant is preferably 0.10 to 2.00 at%.
  • magnesium powder having a purity of 99.5% or more can be used.
  • silicon high-purity silicon powder having a purity of 99.9999% or more can be used.
  • a purified silicon powder obtained by purifying silicon sludge discharged when grinding or polishing a silicon ingot or a silicon wafer can be used (see International Publication No. 2008/75789).
  • the dopant include antimony, aluminum, bismuth, silver, copper and the like.
  • the composition raw material obtained in the mixing step is heat-treated under a temperature condition not lower than the melting point of magnesium silicide (1085 ° C.) and lower than the melting point of silicon (1410 ° C.) to melt and synthesize magnesium silicide.
  • the pressure condition may be atmospheric pressure, but is preferably 1.33 ⁇ 10 ⁇ 3 Pa to atmospheric pressure.
  • the heating condition is 1085 ° C. or higher and lower than 1410 ° C., for example, 2 to 10 hours. At this time, it is preferable to use a temperature raising condition of 150 to 250 ° C./h until reaching 150 ° C., and a temperature raising condition of 350 to 450 ° C./h until reaching 1100 ° C.
  • the atmospheric condition is preferably a reducing atmosphere in order to avoid the production of magnesium oxide and silicon oxide as much as possible.
  • the reducing atmosphere gas include 100% by volume of hydrogen gas and inert gas such as nitrogen gas and argon gas containing hydrogen gas. When an inert gas containing hydrogen gas is used as the reducing atmosphere gas, the hydrogen gas in the inert gas is preferably 5% by volume or more.
  • the heating and melting step includes an opening and a lid that covers the opening, a contact surface of the edge of the opening with the lid, and a contact surface of the lid with the opening.
  • a heat-resistant container that has been polished.
  • the polishing treatment of the contact surface to the lid portion at the edge of the opening and the contact surface to the opening portion of the lid portion is not particularly limited, and it is only necessary that the polishing treatment is performed.
  • a surface roughness Ra of the contact surface is preferably 0.2 to 1.0 ⁇ m to form a close contact state, and more preferably 0.2 to 0.5 ⁇ m.
  • heat-resistant containers examples include sealed containers made of alumina, magnesia, zirconia, platinum, iridium, silicon carbide, boron nitride, pyrolytic boron nitride, pyrolytic graphite, quartz, and the like.
  • the dimensions of the heat-resistant container include those having a container body having an inner diameter of 12 to 300 mm, an outer diameter of 15 to 320 mm, a height of 50 to 250 mm, and a lid portion having a diameter of 15 to 320 mm.
  • the upper surface of the lid portion is directly or indirectly adjusted as necessary. It can be pressurized with a weight.
  • the pressure during the pressurization is, for example, 1 to 10 kg / cm 2 .
  • the magnesium silicide synthesized in this manner is preferably finely pulverized into particles having a narrow particle size distribution.
  • the magnesium silicide is not particularly limited, however, for example, those disclosed in the specifications of International Publication No. 2008/077589, International Application No. PCT / JP2010 / 061185, International Application No. PCT / JP2010 / 062509, and the like are preferable. Can be used. In the present invention, it is particularly preferable to use magnesium silicide having a polycrystalline structure as described in International Publication No. 2008/0775789.
  • thermoelectric conversion module includes the thermoelectric conversion element according to the present invention.
  • One mode of a thermoelectric conversion module including the thermoelectric conversion element 1 described above is shown in FIG.
  • the thermoelectric conversion element 1 uses semiconductor silicide as a thermoelectric conversion material, and can be used mainly as an n-type semiconductor element.
  • the electrode layer 12a side is heated in the thermoelectric conversion module 3 shown in FIG. 4, the electrode layer 12a side becomes higher potential than the electrode layer 12b side due to the temperature difference.
  • a current flows from the electrode layer 12a side to the electrode layer 12b side.
  • the electrode layer 12a disposed on at least the high temperature side of the electrode layers 12a and 12b is preferably made of a transition metal silicide or a mixture of a transition metal silicide and a metal material.
  • thermoelectric conversion module 4 The other aspect of the thermoelectric conversion module provided with the thermoelectric conversion element 1 is shown in FIG.
  • thermoelectric conversion module 4 shown in FIG. 5 a plurality of thermoelectric conversion elements 1 as n-type semiconductor elements are arranged in parallel via electrodes 32.
  • the electromotive force and power obtained can be increased by using a plurality of thermoelectric conversion elements 1.
  • FIG. 6 shows still another aspect of the thermoelectric conversion module including the thermoelectric conversion element 1.
  • the thermoelectric conversion module 5 shown in FIG. 6 includes a thermoelectric conversion element 1 as an n-type semiconductor element and a thermoelectric conversion element 40 as a p-type semiconductor element arranged in a ⁇ shape via an electrode 33.
  • the thermoelectric conversion element 40 side has a higher potential than the thermoelectric conversion element 1 side due to the temperature difference.
  • a current flows from the thermoelectric conversion element 40 to the thermoelectric conversion element 1 by connecting the load 31 between the thermoelectric conversion element 40 and the thermoelectric conversion element 1.
  • Example 1 magnesium silicide containing no dopant synthesized by a melt synthesis method (manufactured by Union Material, TYPE: MSGI-SG-UN, LOT: 10A233) is automatically used as a semiconductor silicide so as to have an average particle size of 75 ⁇ m. What was pulverized in a mortar was used. The magnesium silicide does not contain unreacted substances such as unreacted silicon and magnesium.
  • NiSi nickel silicide
  • SiO 2 powder manufactured by High Purity Chemical Laboratory; purity 99.9%, average particle size 63 ⁇ m
  • the carbon punch 22a ( ⁇ 15 mm ⁇ 20 mm) is removed from above the space portion 23 of the carbon die 21 ( ⁇ 15 mm ⁇ 30 mm), and the upper portion of the manufacturing apparatus 2 is opened, so that the magnesium silicide powder is placed in the space.
  • the portion 23 was charged and deposited to form a thermoelectric conversion material layer.
  • nickel silicide powder and SiO 2 powder are input and deposited in this order to form an electrode layer and an insulating material layer, and then a carbon punch 22a is inserted from above the space 23 to sandwich the material. State 3 was assumed.
  • carbon paper was sandwiched between the contact portions with magnesium silicide. Further, a carbon felt was wound around the carbon die 21 in order to lower the cooling rate during cooling.
  • sintering was performed in a vacuum atmosphere using a discharge plasma sintering apparatus (manufactured by ELENIX, “PAS-III-Es”) to obtain a sintered body.
  • the sintering conditions are as follows. Sintering temperature: 840 ° C Sintering pressure: 30.0 MPa Temperature rising rate: 300 ° C / min ⁇ 2min (up to 600 ° C) 100 ° C / min ⁇ 2min (600-800 ° C) 10 °C / min ⁇ 4min (800 ⁇ 840 °C) 0 ° C / min ⁇ 5min (840 ° C) Cooling conditions: Vacuum cooling Atmosphere: Ar 60 Pa (vacuum when cooling)
  • thermoelectric conversion element 6 having an electrode layer thickness of 0.2 to 0.25 mm was obtained. Further, the central portion obtained by dividing the electrode layer into three parts was removed to obtain a thermoelectric conversion element 6 having a shape as shown in FIG. In the thermoelectric conversion element 6 shown in FIG. 7, electrode layers 14 a and 14 b are formed on both ends of the upper surface of the thermoelectric conversion layer 13.
  • thermoelectric conversion element 6 having a shape as shown in FIG. 7 was obtained in the same manner as in Example 1 except that a mixture of 3 ⁇ m) and 1: 1 (mass basis) was used.
  • Example 3 Cobalt silicide (CoSi 2 ) powder (manufactured by Furuuchi Chemical; purity 99%, average particle size 3.91 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 3 ⁇ m) as electrode materials 7 was obtained in the same manner as in Example 1 except that a mixture obtained by mixing 1: 1 and (by mass) was obtained.
  • thermoelectric conversion element 6 having a shape as shown in FIG. 7 was obtained in the same manner as in Example 1 except that a mixture of 3 ⁇ m) and 1: 1 (mass basis) was used.
  • thermoelectric conversion element 6 having the shape as shown in FIG. 7 was used in the same manner as in Example 1 except that nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 3 ⁇ m) was used as the electrode material. Got.
  • transition metal silicide nickel silicide
  • chrome silicide, cobalt silicide, titanium silicide nickel silicide
  • nickel nickel silicide
  • thermoelectric conversion element 6 obtained in Examples 1 to 4 and Comparative Example 1 using a measuring apparatus 7 (“Tektronix 370A” manufactured by Sony Tektrinics) having a curve tracer 52 whose schematic configuration is shown in FIG. The IV characteristics were measured.
  • a test method as shown in FIG. 9, the tungsten electrodes 51a and 51b of the measuring device 7 are brought into contact with the electrode layers 14a and 14b of the thermoelectric conversion element 6 and a bias voltage is applied, and the obtained linear result is obtained. Ohmic contact was assumed. The results are shown in FIG.
  • thermoelectric conversion elements of Examples 1 to 3 using transition metal silicide (nickel silicide) or a mixture of transition metal silicide (chromium silicide, cobalt silicide) and nickel as electrode materials The resistance value was low compared with the thermoelectric conversion element of Comparative Example 1 using nickel as a material. From this, it was confirmed that the contact resistance can be lowered by using transition metal silicide or a mixture of transition metal silicide and metal material as the electrode material.
  • Example 5 A prismatic thermoelectric conversion element (length 1.9 mm ⁇ width 15 mm ⁇ height 2.1 mm (electrode) as shown in FIG. A layer thickness of 0.2 to 0.25 mm) was produced. A predetermined electrode material (nickel silicide) was used for both of the electrode layers 12a and 12b in FIG.
  • Example 6 As electrode materials, chromium silicide (CrSi 2 ) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 3 ⁇ m) A prismatic thermoelectric conversion element was produced in the same manner as in Example 5 except that a mixture obtained by mixing 1: 1) was used.
  • Example 7 As electrode materials, cobalt silicide (CoSi 2 ) powder (manufactured by Furuuchi Chemical; purity 99%, average particle size 3.91 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 3 ⁇ m) A prismatic thermoelectric conversion element was produced in the same manner as in Example 5 except that a mixture prepared by mixing 1: 1 at a mass (based on mass) was used.
  • thermoelectric conversion element was produced in the same manner as in Example 5 except that nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 3 ⁇ m) was used as the electrode material.
  • thermoelectric conversion elements of Examples 5 to 7 and Comparative Example 2 were the same as those described above except that the tungsten electrodes of the measuring device were brought into contact with the electrode layers 12a and 12b (see FIG. 1). Measured with The measurement results are shown in Table 2.
  • thermoelectromotive force of the thermoelectric conversion elements of Examples 5 to 7 and Comparative Example 2 was set to 373 K on the low temperature side using a thermoelectromotive force / thermal conductivity measuring device (“ZEM2” manufactured by ULVAC-RIKO). The high temperature side was set to 873 K, and the maximum output value (mW) was measured. The measurement results are shown in Table 2.
  • thermoelectric conversion elements of Examples 5 to 7 had smaller resistance values and larger maximum output values than the thermoelectric conversion elements of Comparative Example 2.
  • Example 8 As electrode materials, cobalt silicide (CoSi 2 ) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 2) 3 ⁇ m) was used in the same manner as in Example 1 except that a mixture obtained by mixing 33:67 (based on mass) was used to obtain a thermoelectric conversion element 6 having a shape as shown in FIG.
  • CoSi 2 cobalt silicide
  • Example 9 As electrode materials, cobalt silicide (CoSi 2 ) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 2) 3 ⁇ m) was used in the same manner as in Example 1 except that a mixture obtained by mixing at 66:34 (mass basis) was used to obtain a thermoelectric conversion element 6 having a shape as shown in FIG.
  • CoSi 2 cobalt silicide
  • Example 10 As electrode materials, chromium silicide (CrSi 2 ) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 2) 3 ⁇ m) was used in the same manner as in Example 1 except that a mixture obtained by mixing 33:67 (based on mass) was used to obtain a thermoelectric conversion element 6 having a shape as shown in FIG.
  • CrSi 2 chromium silicide
  • Example 11 As electrode materials, chromium silicide (CrSi 2 ) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 2) 3 ⁇ m) was used in the same manner as in Example 1 except that a mixture obtained by mixing at 66:34 (mass basis) was used to obtain a thermoelectric conversion element 6 having a shape as shown in FIG.
  • CrSi 2 chromium silicide
  • Example 12 Nickel silicide (NiSi) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High-Purity Chemical Laboratory; purity 99.9%, particle size 2 to 3 ⁇ m) as electrode materials 7) was used in the same manner as in Example 1 except that a mixture in which 66:34 (mass basis) was mixed was obtained, and a thermoelectric conversion element 6 having a shape as shown in FIG. 7 was obtained.
  • NiSi Nickel silicide
  • Example 13 As electrode materials, titanium silicide (TiSi 2 ) powder (manufactured by Toshima Seisakusho; purity 99.9%, average particle size 6.0 ⁇ m) and nickel powder (manufactured by High Purity Chemical Laboratory; purity 99.9%, particle size 2 to 2) 3 ⁇ m) was used in the same manner as in Example 1 except that a mixture obtained by mixing 33:67 (based on mass) was used to obtain a thermoelectric conversion element 6 having a shape as shown in FIG.
  • TiSi 2 titanium silicide
  • NiSi 2 nickel powder
  • thermoelectric conversion elements 6 obtained in Examples 8 to 13 was performed by the above-described method, and the resistance value was calculated from the results and the like. Using these results, the relationship between the mixing ratio of the transition metal silicide and the metal material and the resistance value (m ⁇ ) is shown in Table 3. Table 3 also includes the resistance values of Examples 1 to 3 shown in Table 1 above.

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Abstract

L'invention concerne un élément de conversion thermoélectrique présentant une résistance de contact réduite entre une couche de conversion thermoélectrique et une couche d'électrode, ainsi qu'un module de conversion thermoélectrique pourvu de l'élément de conversion thermoélectrique. Ledit élément comprend deux couches d'électrode formées sur les côtés d'une couche de conversion thermoélectrique contenant un siliciure semi-conducteur. L'élément de conversion thermoélectrique selon l'invention se caractérise en ce qu'au moins une des deux couches d'électrode contient un siliciure de métal de transition ou un mélange d'un siliciure de métal de transition et d'un matériau métallique. Le siliciure semi-conducteur peut être du siliciure de magnésium et analogue et le siliciure de métal de transition peut être du siliciure de nickel, du siliciure de chrome, du siliciure de cobalt, du siliciure de titane et analogue.
PCT/JP2011/077500 2010-11-30 2011-11-29 Elément et module de conversion thermoélectrique WO2012073946A1 (fr)

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JP2015050372A (ja) * 2013-09-03 2015-03-16 学校法人明星学苑 熱電変換モジュールの製造方法
NL2017871B1 (en) * 2016-11-25 2018-06-08 Rgs Dev B V Thermoelectric conversion device
WO2019177147A1 (fr) 2018-03-16 2019-09-19 三菱マテリアル株式会社 Élément de conversion thermoélectrique
JP2019165215A (ja) * 2018-03-16 2019-09-26 三菱マテリアル株式会社 熱電変換素子
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KR20190118183A (ko) * 2018-03-30 2019-10-17 제이엑스금속주식회사 포토다이오드 및 광 감응 디바이스
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