WO2023136155A1 - Module de régulation de température - Google Patents

Module de régulation de température Download PDF

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Publication number
WO2023136155A1
WO2023136155A1 PCT/JP2022/048456 JP2022048456W WO2023136155A1 WO 2023136155 A1 WO2023136155 A1 WO 2023136155A1 JP 2022048456 W JP2022048456 W JP 2022048456W WO 2023136155 A1 WO2023136155 A1 WO 2023136155A1
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WIPO (PCT)
Prior art keywords
temperature control
control module
peltier element
vapor chamber
thermoelectric semiconductor
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PCT/JP2022/048456
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English (en)
Japanese (ja)
Inventor
智士 木田
智則 篠田
拓 根本
桜子 田村
邦久 加藤
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リンテック株式会社
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Publication of WO2023136155A1 publication Critical patent/WO2023136155A1/fr

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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25BREFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B21/00Machines, plants or systems, using electric or magnetic effects
    • F25B21/02Machines, plants or systems, using electric or magnetic effects using Peltier effect; using Nernst-Ettinghausen effect
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/10Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
    • H10N10/13Thermoelectric 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 heat-exchanging means at the junction
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/85Thermoelectric active materials
    • H10N10/851Thermoelectric active materials comprising inorganic compositions
    • H10N10/852Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80Constructional details
    • H10N10/85Thermoelectric active materials
    • H10N10/857Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material

Definitions

  • the present invention relates to temperature control modules.
  • Peltier elements have been proposed to use Peltier elements, vapor chambers, or temperature control modules that combine these to control the temperature of specific parts in various electronic devices. For example, by arranging a Peltier device or a vapor chamber in the vicinity of a part that serves as a heat source, it can be expected to promote cooling of the heat source. Also, by placing a Peltier element near a particular component, it is possible to heat this component if necessary.
  • Patent Document 1 discloses a thermo-module including a thermo-element that absorbs heat on the upper surface and generates heat on the lower surface due to the Peltier effect, a flat plate-shaped heat pipe attached to the cooling part side of the thermo-module, and the thermo-module.
  • a cold plate is described that has a heat pipe radiator provided on the heat generating side.
  • Patent Document 2 a plurality of battery cells, a plate-shaped vapor chamber interposed between a pair of battery cells, and a thermoelectric element arranged so as to be in close contact with an end surface of the vapor chamber are provided.
  • a battery pack temperature control and power supply system is described.
  • Patent Document 3 a plurality of Peltier modules are arranged along a direction perpendicular to the surface direction, and a heat absorption channel or heat dissipation channel is arranged between a pair of Peltier modules, and the heat absorption surfaces of the adjacent Peltier modules are arranged. and a cooling system in which heat dissipating surfaces face each other. Also, it is described that the heat absorption flow path and the heat radiation flow path are formed of vapor chambers.
  • temperature control modules As the fields of application of temperature control modules expand, we are working to enable them to be installed even in devices with limited installation space, such as thin and small portable electronic devices such as smartphones and laptop computers. There is a demand for a temperature control module that is thinner and has higher cooling performance.
  • JP-A-2-176377 JP 2017-126418 A Japanese Patent Application Laid-Open No. 2020-200980
  • each Peltier module has a thickness of 2 to 3 mm, and a plurality of Peltier modules and a plurality of heat absorption channels or heat dissipation channels are repeatedly laminated. Therefore, it is difficult to reduce the thickness of the entire system.
  • an object of the present invention is to provide a thin temperature control module with high cooling performance.
  • the present inventors have made intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by setting the total thickness of the Peltier device and the vapor chamber used in the temperature control module within a predetermined range. He found the headline and completed the present invention. That is, the present invention provides the following [1] to [6]. [1] A Peltier element and a vapor chamber stacked on the Peltier element, A temperature control module, wherein the total thickness of the Peltier element and the vapor chamber is 1 mm or less. [2] A temperature control module comprising a Peltier element and a vapor chamber stacked on the Peltier element, wherein the temperature control module has a thickness of 1 mm or less.
  • thermoelectric conversion layer containing a plurality of thermoelectric conversion elements
  • the plurality of thermoelectric conversion elements is a fired body of a coating film of a composition containing a thermoelectric semiconductor material.
  • the temperature control module according to [2].
  • the composition containing the thermoelectric semiconductor material contains thermoelectric semiconductor particles, a polymer component, and an ionic compound.
  • the Peltier element includes a thermoelectric conversion layer containing a plurality of thermoelectric conversion elements, and the plurality of thermoelectric conversion elements contain a bismuth-tellurium compound.
  • the present invention can provide a thin temperature control module with high cooling performance.
  • a temperature control module includes a Peltier element and a vapor chamber stacked on the Peltier element, and the total thickness of the Peltier element and the vapor chamber is 1 mm or less. .
  • the temperature control module has a high cooling performance by being equipped with a Peltier device and a vapor chamber. Moreover, since the total thickness of the Peltier element and the vapor chamber is 1 mm or less, the temperature control module can be thin. In addition, by having the above configuration, the temperature control module is lightweight, and the temperature control module can be easily made flexible.
  • a thin Peltier element and a thin vapor chamber each having a thickness of less than 1 mm are used.
  • a thin Peltier element can be obtained, for example, by using a Peltier element having a thermoelectric conversion layer formed by a coating method as described later.
  • the thin vapor chamber has, for example, a configuration in which two sheets having a plurality of ridges formed thereon are overlapped to enclose the working fluid, as shown in the embodiment described later, and the working fluid is condensed. This can be realized by using a vapor chamber in which a plurality of condensed liquid flow paths through which liquid flows and a vapor flow path through which vapor obtained by vaporizing the working fluid flows are formed.
  • a temperature control module is a temperature control module comprising a Peltier element and a vapor chamber stacked on the Peltier element, wherein the temperature control module has a thickness of 1 mm or less. is.
  • the temperature control module according to the second embodiment can be provided with other layers such as intervening layers in addition to the Peltier element and the vapor chamber. By making the total thickness of 1 mm or less, for example, it is possible to install even in a device with a limited installation space in the equipment, or the thickness of the entire equipment can be reduced and miniaturized. In addition, it becomes easier to reduce the weight of the temperature control module, and it becomes easier to give flexibility.
  • the intervening layer include an adhesive layer, an insulator layer, and a sealing material layer.
  • a specific layer in the Peltier element may also be used as the intervening layer.
  • the sum of the thickness of the Peltier element including the specific layer that also serves as the intervening layer and the thickness of the vapor chamber should be 1 mm or less, and the thickness of the entire temperature control module should be 1 mm or less.
  • the total thickness of the Peltier element and the vapor chamber may be 1 mm or less.
  • the temperature control module may be a cooling module that exclusively performs cooling, or may be a module that can switch between cooling and heating.
  • a Peltier element is an electronic component containing a thermoelectric semiconductor that exhibits the Peltier effect.
  • the Peltier element preferably has a thermoelectric conversion layer including a plurality of P-type thermoelectric semiconductor elements and a plurality of N-type thermoelectric semiconductor elements arranged alternately. The top surfaces of the first set of adjacent P-type thermoelectric semiconductor elements and the N-type thermoelectric semiconductor elements are electrically connected, and the bottom surfaces of the first set of N-type thermoelectric semiconductor elements and the second set of P-type thermoelectric semiconductor elements are electrically connected.
  • thermoelectric semiconductor element of the second set and the upper surface of the N-type thermoelectric semiconductor element paired with the P-type thermoelectric semiconductor element of the second set and forming the second set together are electrically connected, The lower surfaces of the second set of N-type thermoelectric semiconductor elements and the lower surfaces of the third set of P-type thermoelectric semiconductor elements are electrically connected, and the same configuration is repeated thereafter.
  • an endothermic phenomenon occurs at the electrical junction where the current flows in the order of N ⁇ P, and the current flows in the order of P ⁇ N.
  • a heat dissipation phenomenon occurs at the electrical junction where . Therefore, one surface of the Peltier element absorbs heat and the other surface generates heat, and the object to be cooled can be cooled by bringing the heat absorbing surface of the Peltier element close to or in contact with the object. can.
  • the temperature control module is provided with a thermoelectric conversion layer including a plurality of thermoelectric conversion elements as described above as Peltier elements, and the plurality of thermoelectric conversion elements further includes a thermoelectric semiconductor material. It is more preferable to use a sintered body of a coating film of the composition.
  • a Peltier element which is a baked body of a coating film of a composition containing a thermoelectric semiconductor material, as the thermoelectric conversion element, the thickness of the Peltier element can be easily reduced to less than 1 mm.
  • the thickness of the Peltier element is preferably 50 ⁇ m or more, more preferably 75 ⁇ m or more, and still more preferably 150 ⁇ m or more.
  • the thickness of the Peltier element is preferably 650 ⁇ m or less, more preferably 550 ⁇ m or less, and even more preferably 450 ⁇ m or less. In other words, the thickness of the Peltier element is preferably 50 ⁇ m or more and less than 1 mm.
  • the composition containing the thermoelectric semiconductor material may contain a polymer component, an ionic compound and thermoelectric semiconductor particles. A coating film formed using such a composition is suitable for forming a thermoelectric conversion layer having good thermoelectric conversion properties by coating.
  • the thermoelectric conversion layer formed from the coating film may be provided on a substrate, but it is also possible to peel it off from the support after forming the thermoelectric conversion layer on the support, and the presence of the substrate is not required.
  • the coating film is formed, for example, by gravure printing or the like, and may be formed by means such as inkjet printing. Adjacent thermoelectric semiconductor elements may be separated from each other, and a gap between the adjacent thermoelectric semiconductor elements may be filled with a reinforcing material. Various insulators, etc., which will be described later, can be used as the reinforcing material. Materials for forming the thermoelectric conversion layer, formation by coating, and the like will be described later.
  • the Peltier element can be provided with other layers as required.
  • a covering layer consisting of a single layer or multiple layers may be arranged to cover the thermoelectric conversion layer on at least one main surface to protect the thermoelectric conversion layer.
  • the covering layer can also include a sealing layer. If the coating layer is a single layer, the coating layer itself can also serve as the sealing layer, and if the coating layer consists of a plurality of layers, any layer can contain the sealing layer.
  • the covering layer includes a sealing layer, it is possible to more effectively suppress permeation of water vapor in the atmosphere, and it becomes easier to maintain the performance of the Peltier element for a long period of time.
  • a vapor chamber is a heat spreading device comprising a pair of opposed flat plates and a working fluid enclosed between the pair of flat plates.
  • the working fluid transports heat by refluxing with a phase change, transports and diffuses the heat in the heat source, and cools the heat source.
  • a conventionally known vapor chamber can be used as the vapor chamber constituting the temperature control module.
  • a plurality of condensed liquid flow paths having a configuration in which two sheets having unevenness formed thereon are superimposed to enclose a working fluid, and a liquid condensed from the working fluid flows;
  • a vapor chamber can be used in which a vapor channel through which vapor obtained by vaporizing the working fluid flows is formed.
  • a mesh wick may be arranged between a pair of flat plates to enclose the working fluid, and the working fluid condensed after vaporization may be circulated by the mesh wick.
  • the material of the pair of flat plates and the pair of sheets constituting the vapor chamber is not particularly limited, but metals with high thermal conductivity are preferred, such as copper and copper alloys.
  • the type of working fluid enclosed in the closed space of the vapor chamber is not particularly limited. 56°C), naphthalene (boiling point: 218°C), and the like can be used.
  • the operating temperature range of the vapor chamber is a relatively low temperature range when ethanol or acetone is used as the working fluid (for example, about -10 to +130°C for ethanol). It is a relatively high temperature range (approximately 250 to 400°C). When the working fluid is pure water, the temperature is in an intermediate temperature range of about 30 to 200.degree.
  • the stacking order of the vapor chamber and the Peltier element is not particularly limited, and the Peltier element may be stacked on the vapor chamber, or the vapor chamber may be stacked on the Peltier element. Moreover, both may be laminated
  • the area of the Peltier element should be equal to or greater than that of the vapor chamber, or the area of the Peltier element smaller than that of the vapor chamber should correspond to the area of the vapor chamber. It is preferable to arrange a plurality of
  • FIG. 1 is a schematic cross-sectional view showing an example of a temperature control module according to this embodiment.
  • a temperature control module 1A shown in FIG. 1 has a configuration in which a Peltier element 40 is stacked on one main surface (lower surface in FIG. 1) of a vapor chamber 30. As shown in FIG.
  • the temperature control module 1A is flat.
  • the shape of the temperature control module 1A when viewed from above is not particularly limited, and may be rectangular, square, polygonal, circular, elliptical, or the like.
  • the main surface of the Peltier element 40 opposite to the vapor chamber 30 lower surface in FIG.
  • the temperature control module 1A is in contact with the object of temperature control.
  • a member 50 (hereinafter referred to as a temperature-controlled member 50) is installed.
  • the total thickness D1 of the thickness D3 of the Peltier element 40 and the thickness D2 of the vapor chamber 30 is 1 mm or less.
  • the thickness D1 is also the thickness D of the temperature control module 1A. Since the thickness D1 is 1 mm or less, the temperature control module 1A can be made thin, and the temperature control module can be arranged in a narrow space. In addition, it is easy to achieve weight reduction and flexibility.
  • the area of the Peltier element 40 is smaller than the area of the vapor chamber 30 when viewed from above.
  • a Peltier element 40 is arranged in contact with the bottom surface of the vapor chamber 30 near the center. Since the area of the vapor chamber 30 is larger than the area of the Peltier element 40, the heat emitted from the Peltier element 40 can be efficiently diffused in the planar direction.
  • the Peltier element 40 includes a thermoelectric conversion layer 48 including a plurality of P-type thermoelectric conversion elements 43 and a plurality of N-type thermoelectric conversion elements 44 arranged alternately.
  • the P-type thermoelectric conversion elements 43 and the N-type thermoelectric conversion elements 44 are alternately electrically connected by first connection electrodes 41 and second connection electrodes 42 .
  • An insulator layer 46 is provided around the P-type thermoelectric conversion elements 43 and the N-type thermoelectric conversion elements 44 .
  • a filler layer 45 is provided around and on the top surface of the first connection electrode 41 located on the top surface side of the Peltier element 40 .
  • a coating layer 47 is provided on the lower surface side of the Peltier element 40 so as to cover the second connection electrodes 42 , the P-type thermoelectric conversion elements 43 and the N-type thermoelectric conversion elements 44 .
  • the vapor chamber 30 includes a first sheet 10 and a second sheet 20 on which a plurality of ridges are formed at positions corresponding to each other.
  • the first sheet 10 and the second sheet 20 are joined so that the plurality of ridges 13 of the first sheet 10 and the plurality of ridges 23 of the second sheet 20 overlap each other, and a closed space is formed between them.
  • a working fluid is enclosed in 31 .
  • a detailed configuration of the vapor chamber 30 will be described later.
  • the temperature control module 1A for example, when the temperature control target member 50 is brought into contact with the lower surface of the Peltier element 40 of the temperature control module 1A to cool the temperature control target member 50, the Peltier element 40 is energized to absorb heat from the lower surface. A temperature difference is generated in the Peltier element 40 with the side and the upper surface as heat radiation sides. When the heat absorbed from the temperature controlled member 50 is radiated from the upper surface side of the Peltier device 40 , this heat is diffused in the planar direction by the vapor chamber 30 . Thus, although the temperature control module 1A is thin, it exhibits high cooling performance.
  • the lower surface of the Peltier element 40 is turned to the heat-generating side by energizing the Peltier element 40 in the direction opposite to the case where the lower surface is on the heat-absorbing side. Therefore, the temperature control target member 50 can be warmed. In this way, temperature control can be performed on the temperature-controlled member 50 .
  • FIG. 2 is a schematic cross-sectional view showing another example of the temperature control module according to this embodiment.
  • the temperature control module 1B shown in FIG. 2 has a configuration in which an intervening layer 60 is provided between the Peltier element 40 and the vapor chamber 30. As shown in FIG. Other configurations are the same as those of the temperature control module 1A.
  • the thickness D of the temperature control module 1B is 1 mm or less.
  • the sum of the thickness D4 of the intervening layer 60, the thickness D2 of the vapor chamber 30, and the thickness D3 of the Peltier element 40 is 1 mm or less. With such a thickness, even if the intervening layer 60 is provided, it is possible to prevent the temperature control module 1B from becoming thick.
  • the thickness of the intervening layer 60 is usually about 20-200 ⁇ m, preferably about 35-150 ⁇ m.
  • the intervening layer 60 is regarded as a part of the Peltier element 40, or when the filler layer 45 and the intervening layer 60 are integrally provided in the Peltier element 40, the thickness of the Peltier element D3 and the thickness D2 of the vapor chamber is 1 mm or less.
  • the intervening layer 60 is directly provided on the upper surfaces of the electrode 41 and the filler layer 45 in the Peltier element 40. As shown in FIG. However, the present invention is not limited to this, and the filler layer 45 also covers the upper surface of the electrode 41 as in the temperature control module 1A shown in FIG. may
  • FIG. 3 is a schematic cross-sectional view showing another example of the temperature control module according to this embodiment.
  • a temperature control module 1C shown in FIG. 3 has a configuration in which a first Peltier element 40 is arranged on part of one main surface (lower surface in FIG. 3) of a vapor chamber 30, like the temperature control module 1A.
  • the second Peltier element 70 is arranged over the entire other main surface (upper surface in FIG. 3) of the vapor chamber 30 . That is, the area of the second Peltier element 70 when viewed from above is larger than the area of the vapor chamber 30 .
  • the second Peltier element 70 includes a thermoelectric conversion layer 78 including a plurality of P-type thermoelectric conversion elements 73 and a plurality of N-type thermoelectric conversion elements 74, a first connection electrode 71, a first 2 connection electrodes 72 , an insulator layer 76 , a filler layer 75 and a coating layer 77 .
  • the second Peltier element 70 is energized so that the surface facing the vapor chamber 30 is the heat absorbing side and the opposite surface is the heat radiating side. can absorb heat from the bottom side of the second Peltier element 70 and dissipate heat from the top side. Therefore, the temperature control module 1C can further improve the cooling performance.
  • the thickness D of the temperature control module 1C is 1 mm or less, and the sum of the thickness D31 of the first Peltier element 40, the thickness D2 of the vapor chamber 30, and the thickness D32 of the second Peltier element 70 is 1 mm or less. . By setting it as such thickness, even if the 2nd Peltier element 70 is provided, the temperature control module 1C can be prevented from becoming thick.
  • an intervening layer may be provided between at least one of the Peltier element 40 and the vapor chamber 30 and between the vapor chamber 30 and the Peltier element 70 .
  • FIG. 4 is a schematic cross-sectional view showing another example of the temperature control module according to this embodiment.
  • a temperature control module 1D shown in FIG. 4 has a configuration obtained by removing the first Peltier element 40 from the temperature control module 1C.
  • temperature control module 1D has a configuration in which Peltier element 70 is arranged over one main surface (upper surface in FIG. 4) of vapor chamber 30 .
  • heat is diffused in the planar direction by the vapor chamber 30 by bringing the temperature control target member 50 into contact with the lower surface of the vapor chamber 30 .
  • the heat emitted from the vapor chamber 30 can be absorbed from the lower surface side of the Peltier element 70 and radiated to the upper surface side.
  • the thickness D of the temperature control module 1D is 1 mm or less, and the sum of the thickness D3 of the Peltier element and the thickness D2 of the vapor chamber is 1 mm or less.
  • FIG. 5 is a schematic cross-sectional view showing another example of the temperature control module according to this embodiment, and FIG. 6 is a bottom view thereof.
  • a cross section taken along line VV in FIG. 6 corresponds to the cross sectional view in FIG.
  • a region (planned installation region) 32 in which the temperature controlled member 50 is provided is secured on the lower surface of the vapor chamber 30.
  • a plurality of third Peltier elements 80 are arranged in a region other than the planned installation region 32 on the lower surface of the vapor chamber 30 .
  • the temperature control module of this configuration example includes a Peltier element and a vapor chamber stacked on the Peltier element, and the temperature control of the surface of the vapor chamber on which the member to be temperature controlled is installed.
  • the temperature control module one or more, preferably a plurality, of the Peltier elements are arranged on a region different from the planned installation region of the target member.
  • a plurality two in the example of FIGS. 5 and 6) of It can be said that the temperature control module 1D has a configuration in which the third Peltier element 80 is arranged and the second Peltier element 70 is removed from the temperature control module 1D.
  • the third Peltier element 80 is located at a position corresponding to the region where the vaporized working fluid flows and moves in the vapor flow path 31 in the configuration example of the vapor chamber to be described later. is installed in The heat radiated from the vaporized working fluid through the second sheet 20 of the vapor chamber can be absorbed from the upper surface side of the third Peltier element 80 and radiated to the lower surface side.
  • the Peltier element 80 includes first and second connection electrodes 81 and 82, a P-type thermoelectric conversion element 83, an N-type thermoelectric conversion element 84, a filler layer 85, an insulator layer 86, a coating layer 87, and a thermoelectric conversion layer. 88. Since these are the same as the Peltier element 40 described above, detailed description thereof will be omitted.
  • the temperature control module From the viewpoint of setting the total thickness of the Peltier element and the vapor chamber to 1 mm or less, or from the viewpoint of setting the thickness of the temperature control module to 1 mm or less, the temperature control module, as in Configuration Examples 1, 2, or 4, It is preferable to have only one vapor chamber 30 and one Peltier element 40 . With such a configuration, the number of parts is smaller than that of the temperature control module 1C having at least one of the vapor chamber 30 and the Peltier element 40, and thus the thickness can be easily reduced. Therefore, even if the thickness of the vapor chamber 30 or the Peltier element exceeds 350 ⁇ m, for example, the total thickness of the Peltier element and the vapor chamber or the thickness of the temperature control module can easily be 1 mm or less. be.
  • the Peltier element when the Peltier element is arranged in a region where the temperature-controlled member is not provided on the other main surface of the vapor chamber of the temperature control module, the Peltier element is arranged in the thickness direction of the temperature control module. , exists at the same level as the member to be temperature controlled. This is preferable because the Peltier element does not increase the total thickness of the temperature control module and the temperature control member.
  • the vapor chamber 30 includes a first sheet 10 and a second sheet 20. As shown in FIGS. As described above, the first sheet 10 and the second sheet 20 are formed with a plurality of ridges at positions corresponding to each other.
  • FIG. 7 is a schematic plan view showing an example of the first sheet 10 of the vapor chamber 30, in which the vapor chamber 30 has a rectangular shape. 7 corresponds to the cross-sectional view of the vapor chamber 30 shown in FIGS. 1-4. 7 corresponds to the cross-sectional view of the vapor chamber 30 shown in FIG.
  • FIG. 7 shows a first Peltier element 40 in contact with the vapor chamber 30 directly or through an intervening layer as shown in FIGS. 1 to 3, a temperature controlled member 50 shown in FIGS.
  • the contact positions of the third Peltier elements 80 shown in 5 and 6 are indicated by dashed lines.
  • the peripheral edge portion 11 of the first sheet 10 is an annular ridge, and a plurality of protrusions are provided along the peripheral edge portion 11 on the upper surface of the peripheral edge portion 11 (the surface facing the second sheet 20 ).
  • grooves 14 are formed.
  • a plurality of ridges 13 are formed inside the peripheral edge portion 11, and recesses 12 are formed between the peripheral edge portion 11 and the ridges 13 and between a pair of adjacent ridges 13. .
  • a plurality of grooves 15 are formed in each of the ridges 13 along the ridges 13 .
  • An end portion of the first sheet 10 is provided with an inlet forming portion 18 protruding from the peripheral edge portion 11 .
  • the inlet forming portion 18 constitutes part of an inlet for introducing the working fluid.
  • groove-like liquid communication openings 16 are provided at predetermined intervals on the upper surface of the peripheral edge portion 11 so as to intersect with the grooves 14 , and the upper surface of the ridges 13 are provided with grooves in the direction intersecting with the grooves 15 .
  • shaped liquid communication openings 17 are provided at predetermined intervals. In FIG. 7, the grooves 14 and 15 and the liquid communication openings 16 and 17 are simply illustrated with solid lines.
  • the second sheet 20 has the same configuration as the first sheet 10 except that the grooves 14 and 15 are not provided at positions corresponding to the peripheral edge portion 11 and the plurality of ridges 13 of the first sheet 10.
  • a peripheral edge portion 21 and a plurality of ridges 23 are provided (see FIGS. 1 to 4).
  • a concave portion 22 is formed between the peripheral portion 21 and the ridge 23 and between a pair of adjacent ridges 23 .
  • there is an injection port forming portion having a recess at a portion corresponding to the injection port forming portion 18 of the first sheet 10 so as to communicate with the space between the peripheral edge portion 21 of the second sheet 20 and the plurality of ridges 23 .
  • an injection port 24 for injecting the working fluid is formed. Then, the first sheet 10 and the second sheet 20 are diffusion-bonded so that the peripheral edge portion 11 and the plurality of ridges 13 of the first sheet 10 overlap the peripheral edge portion 21 and the plurality of ridges 23 of the second sheet 20.
  • a sealed space 31 surrounded by the ridges 13, 23 and the peripheral edges 11, 21 is formed by joining them by brazing or the like.
  • a working fluid is enclosed in the closed space 31 .
  • This closed space 31 functions as a steam flow path as described later.
  • the working fluid is filled, the working fluid is injected from the filling port 24 after the closed space 31 is decompressed by evacuating from the filling port 24 . After the injection is completed, the injection port 24 is sealed by laser bonding or caulking.
  • the temperature-controlled member 50 which is a heat source, or the Peltier element 40, which is in contact with the heat source and dissipates heat to the outside (hereinafter collectively referred to as the “heat source”)
  • the heat source contacts a predetermined portion of the vapor chamber 30, the heat is generated. propagates through the first sheet 10 by heat conduction, and the condensate present in the closed space near the heat source receives heat. The condensate that has received this heat absorbs the heat and evaporates. This cools the heat source.
  • the vaporized working fluid turns into steam and flows through the steam flow path 31 as indicated by the black arrows in FIG. Because this flow occurs away from the heat source, the steam moves away from the heat source.
  • the steam in the steam channel 31 leaves the heat source and moves toward the peripheral edge of the vapor chamber 30 where the temperature is relatively low. Cooled.
  • the working fluid that has lost heat while moving through the steam flow path 31 condenses and liquefies. This condensate adheres to the wall surface of the steam channel 31 .
  • the condensate is distributed from the liquid communication openings 16, 17 and the like to the grooves 14, 15 which become the condensate flow path so as to be pushed by the steam. to move.
  • the condensate that has entered the grooves 14 and 15 that serve as condensate flow paths approaches the heat source as indicated by the white thin line arrows in FIG. to move. Then, it is vaporized again by the heat from the heat source, and the above operations and state changes are repeated.
  • the vapor chamber 30 the high capillary force in the condensate flow path allows the condensate to recirculate well, and the vapor chamber 30 has a high heat transfer capacity even though it is thin. Therefore, the temperature control module obtained by stacking the Peltier elements 40, 70, 80 in the vapor chamber 30 exhibits a high cooling capacity.
  • a method of removing material to a predetermined depth by half-etching a metal sheet having a corresponding external size can be used. can.
  • the cross-sectional shape of the ridges is not limited to those having vertical flat sides as shown in FIGS.
  • the cross-sectional shape of the concave portion is not limited to those in which the bottom is horizontal and the wall is vertical, as shown in FIGS. It can have any shape, such as a shape or an elliptical shape.
  • the width, length, height, depth, etc. of the ridges and recesses are not particularly limited, and may be appropriately set so that the vapor chamber operates well.
  • the first sheet and the second sheet may differ in the configuration of the protrusions other than the presence or absence of grooves, or the protrusions of the second sheet may also be formed with grooves.
  • the thickness of the vapor chamber is preferably 500 ⁇ m or less, preferably 400 ⁇ m or less, more preferably 350 ⁇ m or less. Also, the lower limit of the thickness of the vapor chamber is usually about 100 ⁇ m. In other words, the thickness of the vapor chamber is preferably between 100 and 500 ⁇ m.
  • thermoelectric conversion element used for the Peltier element contains a thermoelectric semiconductor material.
  • Thermoelectric semiconductor materials are usually fired to obtain Peltier elements.
  • the thermoelectric conversion element is preferably formed by applying a composition containing a thermoelectric semiconductor material (hereinafter also referred to as a "composition containing a thermoelectric semiconductor material" or a “thermoelectric semiconductor composition”) to the surface of a support or the like. It is a sintered body of the coating film. Since the thermoelectric conversion element is a fired body of the coating film of the thermoelectric semiconductor composition, a sheet-like thermoelectric conversion module can be easily produced, and a thermoelectric conversion element with improved flexibility can be easily obtained.
  • the thickness of the thermoelectric conversion element is preferably 10 ⁇ m or more, more preferably 25 ⁇ m or more, still more preferably 35 ⁇ m or more, and is preferably 800 ⁇ m or less, more preferably 500 ⁇ m or less, still more preferably 300 ⁇ m or less. In other words, the thickness of the thermoelectric conversion element is preferably 10-800 ⁇ m. When the thickness of the thermoelectric conversion element is within the above range, it is easy to manufacture the thermoelectric conversion element exhibiting good thermoelectric conversion performance with high productivity.
  • thermoelectric semiconductor composition used for producing the thermoelectric conversion layer contains at least a thermoelectric semiconductor material, preferably thermoelectric semiconductor particles made of the thermoelectric semiconductor material and a resin, more preferably thermoelectric semiconductor particles, a polymer component and ions compounds.
  • the ionic compound preferably contains at least one of an ionic liquid and an inorganic ionic compound, and more preferably contains an ionic liquid.
  • thermoelectric semiconductor material The thermoelectric semiconductor material contained in the P-type thermoelectric semiconductor element and the N-type thermoelectric semiconductor element is not particularly limited as long as it is a material that can generate a thermoelectromotive force by applying a temperature difference.
  • Bismuth-tellurium thermoelectric semiconductor materials such as bismuth telluride and N-type bismuth telluride; Telluride thermoelectric semiconductor materials such as GeTe and PbTe; Antimony-tellurium thermoelectric semiconductor materials; Zinc such as ZnSb, Zn 3 Sb 2 and Zn 4 Sb 3 - antimony-based thermoelectric semiconductor materials ; silicon - germanium-based thermoelectric semiconductor materials such as SiGe ; bismuth-selenide-based thermoelectric semiconductor materials such as Bi2Se3 ; silicide-based thermoelectric semiconductor materials; oxide-based thermoelectric semiconductor materials; Heusler materials such as FeVAl, FeVAlSi, and FeVTiAl; sulfide-based thermoelectric semiconductor materials such as TiS2 ; skutterudite materials; carbon materials such as carbon nanotubes (CNT); Used.
  • CNT carbon nanotubes
  • thermoelectric conversion performance can be easily obtained.
  • silicide-based thermoelectric semiconductor materials are preferable from the viewpoint of not containing rare metals whose supply is unstable due to geopolitical issues, and facilitate the functioning of thermoelectric conversion modules in high-temperature environments.
  • the skutterudite material is preferred from the viewpoint of being able to do so.
  • the thermoelectric semiconductor material is P-type bismuth telluride or A bismuth-tellurium-based thermoelectric semiconductor material such as N-type bismuth telluride is preferred.
  • the Peltier device may include a thermoelectric conversion layer containing a plurality of thermoelectric conversion elements, and the plurality of thermoelectric conversion elements may contain a bismuth-tellurium compound.
  • thermoelectric semiconductor materials When using a vapor chamber in which the working fluid has a boiling point of over 150° C., for example, silicide-based thermoelectric semiconductor materials, telluride-based thermoelectric semiconductor materials such as PbTe, silicon-germanium-based thermoelectric semiconductor materials such as SiGe, and skutterudite materials are used. It is preferable to use P-type bismuth telluride has holes as carriers and a positive Seebeck coefficient, and is preferably represented by, for example, Bi X Te 3 Sb 2-X . In this case, X preferably satisfies 0 ⁇ X ⁇ 0.8, more preferably 0.4 ⁇ X ⁇ 0.6.
  • N-type bismuth telluride has electrons as carriers and a negative Seebeck coefficient.
  • Y is 0 or more and 3 or less, the Seebeck coefficient and electrical conductivity are increased, and the properties as an N-type thermoelectric conversion material are maintained, which is preferable.
  • thermoelectric semiconductor material used for the thermoelectric conversion layer is preferably in the form of particles having a predetermined size. Preferably.
  • the content of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. More preferably 50 to 96% by mass, still more preferably 70 to 95% by mass. If the amount of the thermoelectric semiconductor particles is within the above range, the Seebeck coefficient (absolute value of the Peltier coefficient) is large, and the decrease in electrical conductivity is suppressed, and only the thermal conductivity decreases, so high thermoelectric performance is exhibited. In addition, a film having sufficient film strength and moderate flexibility can be obtained, which is preferable.
  • the average particle size of the thermoelectric semiconductor particles is preferably 10 nm to 200 ⁇ m, more preferably 10 nm to 30 ⁇ m, even more preferably 50 nm to 10 ⁇ m, particularly preferably 1 to 6 ⁇ m. Within the above range, uniform dispersion is facilitated, and electrical conductivity can be increased.
  • the method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor particles is not particularly limited, and includes jet mills, ball mills, bead mills, colloid mills, conical mills, disk mills, edge mills, milling mills, hammer mills, pellet mills, Willie mills, and roller mills. It may be pulverized to a predetermined size by a known fine pulverizer such as. In this specification, the average particle size of the thermoelectric semiconductor particles is obtained by measuring with a laser diffraction particle size analyzer (manufactured by CILAS, model 1064), and is represented by the median value of the particle size distribution. is.
  • thermoelectric semiconductor particles are preferably heat-treated in advance (the "heat treatment” referred to here is different from the “annealing treatment” performed in the annealing treatment step of the present invention).
  • the heat treatment is not particularly limited, but before preparing the thermoelectric semiconductor composition, in an inert gas atmosphere such as nitrogen, argon, etc., in which the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles. It is preferably carried out under a reducing gas atmosphere such as hydrogen or under vacuum conditions, more preferably under a mixed gas atmosphere of an inert gas and a reducing gas.
  • a reducing gas atmosphere such as hydrogen or under vacuum conditions
  • the specific temperature conditions depend on the thermoelectric semiconductor particles used, it is usually preferred that the temperature is below the melting point of the particles and 100 to 1,500° C. for several minutes to several tens of hours.
  • thermoelectric semiconductor composition The polymer component that can be contained in the thermoelectric semiconductor composition has the effect of physically bonding between the thermoelectric semiconductor materials (thermoelectric semiconductor particles), and the Peltier element, which is a thermoelectric conversion module, can be formed into a thin film by coating or the like. make it easier.
  • a heat-resistant resin or a binder resin is preferable as the polymer component.
  • the heat-resistant resin maintains various physical properties such as mechanical strength and thermal conductivity as a resin when crystal growth of thermoelectric semiconductor particles is performed by annealing a thin film made of a thermoelectric semiconductor composition.
  • Polyamide resins, polyamideimide resins, polyimide resins, and epoxy resins are preferred as the heat-resistant resins because they have higher heat resistance and do not adversely affect the crystal growth of the thermoelectric semiconductor particles in the thin film, and are excellent in flexibility. Polyamide resins, polyamideimide resins, and polyimide resins are more preferable.
  • the heat-resistant resin preferably has a decomposition temperature of 300°C or higher. If the decomposition temperature is within the above range, flexibility can be maintained without losing the function as a binder even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the heat-resistant resin preferably has a mass reduction rate of 10% or less, more preferably 5% or less, and even more preferably 1% or less at 300°C as measured by thermogravimetry (TG). If the mass reduction rate is within the above range, even when the thin film made of the thermoelectric semiconductor composition is annealed, the bendability of the tip of the thermoelectric semiconductor material can be maintained without losing its function as a binder, as will be described later. can be done.
  • the content of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, still more preferably 2 to 15% by mass. is.
  • the content of the heat-resistant resin is within the above range, it functions as a binder for the thermoelectric semiconductor material, making it easier to form a thin film, and a film having both high thermoelectric performance and film strength can be obtained, resulting in a thermoelectric semiconductor material.
  • a resin portion exists on the outer surface of the chip.
  • the binder resin also facilitates peeling from the base material such as glass, alumina, silicon, etc. used when manufacturing the thermoelectric conversion element after the annealing treatment described later.
  • the binder resin refers to a resin in which 90% by mass or more decomposes at a baking (annealing) temperature or higher, more preferably a resin in which 95% by mass or more decomposes, and a resin in which 99% by mass or more decomposes. is particularly preferred.
  • a resin that maintains various physical properties such as mechanical strength and thermal conductivity without impairing when crystal growth of thermoelectric semiconductor particles is performed by baking (annealing) a coating film (thin film) made of a thermoelectric semiconductor composition. more preferred.
  • the binder resin As the binder resin, if a resin that decomposes 90% by mass or more at a firing (annealing) temperature or higher, that is, a resin that decomposes at a lower temperature than the heat-resistant resin described above, the binder resin is decomposed by firing, resulting in a fired body.
  • the content of the binder resin, which is an insulating component contained therein, is reduced, and the crystal growth of the thermoelectric semiconductor particles in the thermoelectric semiconductor composition is promoted. As a result, voids in the thermoelectric semiconductor material layer can be reduced and the filling rate can be improved.
  • Whether or not a resin decomposes at a predetermined value (for example, 90% by mass) at a firing (annealing) temperature or higher is determined by thermogravimetric measurement (TG) at the mass reduction rate at the firing (annealing) temperature (before decomposition The value obtained by dividing the mass after decomposition by the mass).
  • TG thermogravimetric measurement
  • thermoplastic resin or a curable resin can be used as such a binder resin.
  • thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polyisobutylene, and polymethylpentene; polycarbonates; thermoplastic polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polystyrene, acrylonitrile-styrene copolymers, and polyacetic acid.
  • thermosetting resins include epoxy resins and phenol resins.
  • photocurable resins include photocurable acrylic resins, photocurable urethane resins, and photocurable epoxy resins. These may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of the electrical resistivity of the thermoelectric semiconductor material in the thermoelectric conversion layer, thermoplastic resins are preferred, cellulose derivatives such as polycarbonate and ethyl cellulose are more preferred, and polycarbonate is particularly preferred.
  • the binder resin is appropriately selected according to the temperature of the baking (annealing) treatment for the thermoelectric semiconductor material in the baking (annealing) treatment step. From the viewpoint of the electrical resistivity of the thermoelectric semiconductor material in the thermoelectric conversion layer, it is preferable to perform the baking (annealing) treatment at a temperature higher than the final decomposition temperature of the binder resin.
  • the term “final decomposition temperature” refers to the temperature at which the mass reduction rate at the firing (annealing) temperature by thermogravimetry (TG) is 100% (the mass after decomposition is 0% of the mass before decomposition). say.
  • the final decomposition temperature of the binder resin is usually 150-600°C, preferably 200-560°C, more preferably 220-460°C, and particularly preferably 240-360°C. If a binder resin having a final decomposition temperature within this range is used, it functions as a binder for the thermoelectric semiconductor material and facilitates the formation of a thin film during printing.
  • the content of the binder resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 0.5 to 5% by mass. % by mass.
  • the electrical resistivity of the thermoelectric semiconductor material in the thermoelectric conversion layer can be reduced.
  • the content of the binder resin in the thermoelectric semiconductor material is preferably 0-10% by mass, more preferably 0-5% by mass, and particularly preferably 0-1% by mass. If the content of the binder resin in the thermoelectric semiconductor material is within the above range, the electrical resistivity of the thermoelectric semiconductor material in the thermoelectric conversion layer can be reduced.
  • the ionic liquid that can be contained in the thermoelectric semiconductor composition is a molten salt formed by combining a cation and an anion, and refers to a salt that can exist as a liquid in any temperature range from -50°C to less than 400°C.
  • an ionic liquid is an ionic compound having a melting point in the range of -50°C or higher and lower than 400°C.
  • the melting point of the ionic liquid is preferably ⁇ 25° C. or higher and 200° C. or lower, more preferably 0° C. or higher and 150° C. or lower.
  • Ionic liquids have characteristics such as extremely low vapor pressure and non-volatility, excellent thermal and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, it can effectively suppress the decrease in electrical conductivity between thermoelectric semiconductor materials as a conductive auxiliary agent.
  • the ionic liquid exhibits high polarity based on an aprotic ionic structure and is excellent in compatibility with heat-resistant resins, so that the electric conductivity of the thermoelectric semiconductor material can be made uniform.
  • ionic liquids can be used.
  • nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and their derivatives; tetraalkylammonium-based amine-based cations and their derivatives; Phosphine-based cations and derivatives thereof; cation components such as lithium cations and derivatives thereof, Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , (FSO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C ⁇ , AsFSO 2 ) 2 N
  • the cation component of the ionic liquid is pyridinium cation and its derivatives from the viewpoint of high-temperature stability, compatibility with thermoelectric semiconductor materials and resins, suppression of decrease in electrical conductivity in the gaps of thermoelectric semiconductor materials, etc. , imidazolium cations and derivatives thereof.
  • ionic liquids in which the cationic component contains pyridinium cations and derivatives thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 3-methyl-hexylpyridinium chloride.
  • ionic liquids containing imidazolium cations and derivatives thereof as cationic components include [1-butyl-3-(2-hydroxyethyl)imidazolium bromide], [1-butyl-3-(2 -hydroxyethyl)imidazolium tetrafluoroborate], 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl-3-methylimidazolium chloride, 1-hexyl-3 -methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium tetrafluor
  • the above ionic liquid preferably has an electrical conductivity of 10 ⁇ 7 S/cm or more. If the ionic conductivity is within the above range, it can effectively suppress the decrease in electrical conductivity between thermoelectric semiconductor materials as a conductive auxiliary agent.
  • the above ionic liquid preferably has a decomposition temperature of 300°C or higher. If the decomposition temperature is within the above range, the effect as a conductive aid can be maintained even when a thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the above ionic liquid preferably has a mass reduction rate of 10% or less at 300° C. by thermogravimetry (TG), more preferably 5% or less, and even more preferably 1% or less. . If the mass reduction rate is within the above range, the effect as a conductive aid can be maintained even when the thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • TG thermogravimetry
  • the content of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01-50% by mass, more preferably 0.5-30% by mass, and still more preferably 1.0-20% by mass. If the blending amount of the ionic liquid is within the above range, the decrease in electrical conductivity is effectively suppressed, and a film having high thermoelectric performance can be obtained.
  • the inorganic ionic compound that can be included in the thermoelectric semiconductor composition is a compound composed of at least cations and anions. Inorganic ionic compounds exist in a solid state over a wide temperature range of 400 to 900°C and have characteristics such as high ionic conductivity. can be suppressed.
  • a metal cation is used as the cation constituting the inorganic ionic compound.
  • metal cations include alkali metal cations, alkaline earth metal cations, typical metal cations and transition metal cations, with alkali metal cations and alkaline earth metal cations being more preferred.
  • alkali metal cations include Li + , Na + , K + , Rb + , Cs + and Fr + .
  • Alkaline earth metal cations include, for example, Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
  • Examples of anions constituting the inorganic ionic compound include F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , OH ⁇ , CN ⁇ , NO 3 ⁇ , NO 2 ⁇ , ClO ⁇ , ClO 2 ⁇ , ClO 3 ⁇ , ClO 4 ⁇ , CrO 4 2 ⁇ , HSO 4 ⁇ , SCN ⁇ , BF 4 ⁇ , PF 6 ⁇ and the like.
  • thermoelectric conversion layer As the inorganic ionic compound contained in the thermoelectric conversion layer, a known or commercially available one can be used.
  • cation components such as potassium cations, sodium cations, or lithium cations, chloride ions such as Cl ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , and ClO 4 ⁇ , bromide ions such as Br ⁇ Iodide ions, fluoride ions such as BF 4 ⁇ and PF 6 ⁇ , halide anions such as F(HF) n ⁇ , and anion components such as NO 3 ⁇ , OH ⁇ , CN ⁇ and the like.
  • chloride ions such as Cl ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , and ClO 4 ⁇
  • bromide ions such as Br ⁇ Iodide ions
  • fluoride ions such as BF 4 ⁇ and PF 6 ⁇
  • halide anions such as
  • the cation component of the inorganic ionic compound is potassium. , sodium, and lithium.
  • the anion component of the inorganic ionic compound preferably contains a halide anion, and more preferably contains at least one selected from Cl ⁇ , Br ⁇ and I ⁇ .
  • inorganic ionic compounds whose cationic component contains potassium cations include KBr, KI, KCl, KF, KOH, K2CO3 , and the like . Among these, KBr and KI are preferred.
  • Specific examples of inorganic ionic compounds containing sodium cations as cationic components include NaBr, NaI, NaOH, NaF, Na 2 CO 3 and the like. Among these, NaBr and NaI are preferred.
  • Specific examples of inorganic ionic compounds containing lithium cations as cationic components include LiF, LiOH, LiNO 3 and the like. Among these, LiF and LiOH are preferred.
  • the above inorganic ionic compound preferably has an electrical conductivity of 10 ⁇ 7 S/cm or more, more preferably 10 ⁇ 6 S/cm or more. If the electrical conductivity is within the above range, it can effectively suppress the decrease in electrical conductivity between thermoelectric semiconductor materials as a conductive auxiliary agent.
  • the above inorganic ionic compound preferably has a decomposition temperature of 400°C or higher. If the decomposition temperature is within the above range, the effect as a conductive aid can be maintained even when a thin film made of the thermoelectric semiconductor composition is annealed, as will be described later.
  • the above-mentioned inorganic ionic compound preferably has a mass reduction rate at 400°C measured by thermogravimetry (TG) of 10% or less, more preferably 5% or less, and preferably 1% or less. More preferred. If the mass reduction rate is within the above range, even when the thin film made of the thermoelectric semiconductor composition is annealed, it is easy to maintain the effect as a conductive additive, as will be described later.
  • TG thermogravimetry
  • the content of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, still more preferably 1.0 to 10% by mass. If the blending amount of the inorganic ionic compound is within the above range, the decrease in electrical conductivity can be effectively suppressed, and as a result, a film with improved thermoelectric performance can be obtained.
  • the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably is 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
  • thermoelectric semiconductor composition The method for preparing the thermoelectric semiconductor composition is not particularly limited, and the thermoelectric semiconductor material, the heat-resistant resin, and the One or both of the ionic liquid and the inorganic ionic compound used as necessary, other additives, and a solvent may be added and mixed and dispersed to prepare the thermoelectric semiconductor composition.
  • a solvent may be used when preparing the thermoelectric semiconductor composition. Examples of the solvent used include solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve. These solvents may be used singly or in combination of two or more.
  • the solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.
  • thermoelectric conversion elements are formed by a coating method
  • an adhesive layer is formed so as to cover the connection electrodes on the main surface facing the vapor chamber, and the Peltier element is attached to the vapor chamber by the adhesive layer (
  • the adhesive layer corresponds to the aspect in which the intervening layer 60 and the filler layer 45 are combined).
  • thermoelectric conversion element When manufacturing a temperature control module having a coating type Peltier element, the thermoelectric conversion element is not particularly limited, but may be, for example, on a base material such as glass, alumina, silicon, or a resin film, or on a sacrificial layer to be described later. It can be obtained by coating the thermoelectric semiconductor composition on the base material on the side where the thermoelectric semiconductor composition is applied to obtain a coating film, drying the coating film, and appropriately separating the coating film from the base material. By forming in this way, a large number of thermoelectric conversion elements can be obtained simply and at low cost.
  • the resin film a film having heat resistance is preferable, and a film made of a polyamide resin, a polyamideimide resin, a polyimide resin, or the like is preferable.
  • thermoelectric semiconductor compositions include screen printing, flexographic printing, gravure printing, spin coating, dip coating, die coating, spray coating, bar coating, and doctor blade.
  • a known method such as a method can be mentioned, and there is no particular limitation.
  • a screen printing method, a slot die coating method, or the like which enables simple pattern formation using a screen plate having a desired pattern, is preferably used.
  • the thermoelectric conversion element is formed by drying the obtained coating film, and as the drying method, a conventionally known drying method such as hot air drying method, hot roll drying method, infrared irradiation method, etc. can be used.
  • the heating temperature is usually 80 to 150° C., and the heating time varies depending on the heating method, but is usually several seconds to several tens of minutes.
  • the heating temperature is not particularly limited as long as it is within a temperature range that allows the solvent used to be dried.
  • the thickness of the coating film made of the thermoelectric semiconductor composition is not particularly limited, but is preferably 100 nm to 1,000 ⁇ m, more preferably 100 nm to 1,000 ⁇ m, more preferably from the viewpoint of thermoelectric performance and film strength, and from the viewpoint of thinning the Peltier element. 300 nm to 600 ⁇ m, more preferably 5 to 400 ⁇ m.
  • the coating film of the thermoelectric semiconductor composition is preferably further annealed to form a fired body.
  • the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thin film can be crystal-grown, thereby further improving the thermoelectric performance.
  • Annealing treatment is not particularly limited, but is usually performed under an inert gas atmosphere such as nitrogen or argon with a controlled gas flow rate, under a reducing gas atmosphere, or under vacuum conditions. Depending on the temperature and the like, it is carried out at 100 to 500° C. for several minutes to several tens of hours. Furthermore, in the annealing treatment, the thermoelectric semiconductor composition may be pressed to increase the density of the thermoelectric semiconductor composition.
  • a resin such as polymethyl methacrylate or polystyrene, or a releasing agent such as a fluorine-based releasing agent or a silicone-based releasing agent can be used.
  • the thermoelectric conversion element formed on a base material such as glass can be easily separated from the glass or the like after annealing. Formation of the sacrificial layer is not particularly limited, and can be performed by known methods such as flexographic printing and spin coating.
  • thermoelectric conversion elements In order to ensure insulation between the obtained thermoelectric conversion elements, an insulator is filled between the thermoelectric conversion elements.
  • the insulator ensures insulation between the P-type thermoelectric conversion element and the N-type thermoelectric conversion element, insulation between the P-type thermoelectric conversion elements or between the N-type thermoelectric conversion elements, and mechanical It acts as a stiffener that allows it to maintain its physical strength.
  • the insulator is not particularly limited as long as it can maintain insulation and strength, and examples thereof include insulating resins and ceramics.
  • insulating resins include polyimide-based resins, silicone-based resins, rubber-based resins, acrylic-based resins, olefin-based resins, maleimide-based resins, epoxy-based resins, and the like. From the viewpoint of heat resistance and mechanical strength, it is preferably selected from polyimide resins, silicone resins, acrylic resins, maleimide resins and epoxy resins.
  • the insulating resin is preferably a curable resin or a foaming resin.
  • the insulating resin may further contain a filler.
  • a hollow filler is preferable as the filler.
  • the hollow filler is not particularly limited, and known fillers can be used.
  • inorganic hollow fillers such as glass balloons, silica balloons, shirasu balloons, fly ash balloons, and metal silicate balloons (hollow bodies) can be used.
  • Fillers, and organic resin-based hollow fillers such as acrylonitrile, vinylidene chloride, phenolic resins, epoxy resins, and urea resins, which are balloons (hollow bodies), can be used.
  • the thermal conductivity of the insulating resin is lowered, and the thermoelectric performance is further improved.
  • ceramics include materials containing aluminum oxide (alumina), aluminum nitride, zirconium oxide (zirconia), silicon carbide, etc. as a main component (50% by mass or more in ceramics).
  • a rare earth compound can also be added.
  • a known method can be used to fill the insulator. For example, using a liquid resin, a method of spreading and filling the resin on the support surface on which the chips of the P-type thermoelectric semiconductor material and the chips of the N-type thermoelectric semiconductor material are alternately arranged, using a coating member such as a squeegee, Further, a method of filling by spin coating after dripping from approximately the center of the support to the outside, a method of filling by immersing the support together with a liquid resin storage tank or the like and pulling it up, and further, Using a sheet-shaped insulating resin, the sheet-shaped insulating resin is attached to the surface of the support on which the chips of the P-type thermoelectric semiconductor material and the chips of the N-type thermoelectric semiconductor material are alternately arranged, and heated and/or A method of melting and filling a sheet-shaped insulating resin by pressurization can be used. After filling, heat curing or the like is performed.
  • a coating member such as a sque
  • the support is not particularly limited, and examples thereof include glass, silicon, ceramics, metals, plastics, and the like. It is preferably selected from glass, plastic and silicon. Glass, silicon, ceramics, or metal is preferable when annealing treatment or the like is performed at a high temperature. Note that the support is peeled off after an integrated product of a plurality of thermoelectric conversion elements and insulators positioned therebetween is obtained.
  • the substrate having the sacrificial layer described above can be used as the support, and the thermoelectric conversion element may be transferred from the substrate having the sacrificial layer to another support.
  • connection electrodes used for connecting a pair of thermoelectric conversion elements or for external connection are formed.
  • the connection electrode is preferably formed of at least one film selected from the group consisting of a vapor deposited film, a plated film, a conductive composition and a metal foil.
  • the metal material used for the connection electrode is not particularly limited, and examples thereof include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, solder, and alloys containing any of these metals.
  • connection electrodes As a method for forming the connection electrodes, after providing an electrode without a pattern formed on the above-described integrated product of the plurality of thermoelectric conversion elements and the insulating layer (hereinafter also simply referred to as "integrated product"), A method of processing into a predetermined pattern shape by a known physical treatment or chemical treatment mainly based on photolithography, or a combination thereof, or a conductive composition comprising the above-mentioned metal material or the like A method of directly forming an electrode pattern by using a paste, a screen printing method, an inkjet method, or the like can be used.
  • Methods for forming electrodes without a pattern include PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion plating, or CVD (chemical vapor deposition) such as thermal CVD and atomic layer deposition (ALD). vapor phase growth method), or various coatings such as dip coating method, spin coating method, spray coating method, gravure coating method, die coating method, doctor blade method, wet process such as electrodeposition method, silver salt method , electroplating method, electroless plating method, lamination of metal foil, etc., and are appropriately selected according to the material of the electrode. For lamination of metal foils, solder may be used to bond them to a thermoelectric material or the like.
  • connection electrodes are required to have high electrical conductivity and high thermal conductivity. Therefore, it is more preferable to use electrodes formed by a plating method or a vacuum film forming method.
  • a vacuum deposition method such as a vacuum deposition method or a sputtering method, an electroplating method, or an electroless plating method is preferable because high electrical conductivity and high thermal conductivity can be easily realized.
  • the pattern can be easily formed through a hard mask such as a metal mask, depending on the size of the formed pattern and the required dimensional accuracy.
  • the thickness of the connection electrode layer is preferably 10 nm to 200 ⁇ m, more preferably 30 nm to 150 ⁇ m, and even more preferably 50 nm to 120 ⁇ m. If the thickness of the layer of the connection electrode is within the above range, the electrical conductivity is high, the resistance is low, and sufficient strength is obtained as the connection electrode.
  • An adhesive layer is provided on at least one surface of a Peltier device, which is a thermoelectric conversion module. That is, an adhesive layer is provided on the first connection electrodes including the gaps between adjacent first connection electrodes. Then, by bonding the Peltier element to the vapor chamber with this adhesive layer, for example, the Peltier element can be easily installed. In addition, weather resistance can be improved by including a gap between the first connection electrodes. Furthermore, insulation between the vapor chamber and the connection electrodes of the Peltier element can be ensured. Note that the adhesive layer may be formed in advance on the surface of the vapor chamber.
  • the adhesive layer is not particularly limited as long as it can be easily adhered to the vapor chamber, but it preferably contains an adhesive resin, and if desired, a cross-linking agent, a tackifier, a polymerizable compound, and a polymerization initiator.
  • Adhesive additives such as silane coupling agents, antistatic agents, antioxidants, UV absorbers, light stabilizers, softeners, fillers, refractive index modifiers, colorants and the like may be contained.
  • boron nitride filler, alumina filler, or the like may be used as the filler.
  • adhesive resin is a concept that includes adhesive resins. It also includes a resin that exhibits adhesiveness when used in combination, and also includes a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water.
  • adhesive resins examples include acrylic resins, urethane resins, rubber resins such as polyisobutylene resins, polyester resins, olefin resins, silicone resins, epoxy resins, and polyvinyl ether resins.
  • the thickness of the adhesive layer is not particularly limited, it is preferably 1 to 50 ⁇ m, more preferably 2 to 30 ⁇ m.
  • the adhesive layer may be directly formed on the electrode on the integrated body by a known method from an adhesive composition containing an adhesive resin.
  • methods for forming the adhesive layer include spin coating, spray coating, bar coating, knife coating, roll coating, roll knife coating, blade coating, die coating, and gravure coating.
  • the release film may include a release substrate and a release agent layer formed by coating a release agent on the release substrate. is preferred.
  • the release film may have a release agent layer on only one side of the release substrate, or may have a release agent layer on both sides of the release substrate.
  • the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
  • paper substrates include glassine paper, coated paper, and cast-coated paper.
  • Plastic films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
  • release agents include olefin-based resins, rubber-based elastomers (eg, butadiene-based resins, isoprene-based resins, etc.), long-chain alkyl-based resins, alkyd-based resins, fluorine-based resins, and silicone-based resins.
  • An adhesive layer having a release film is produced, for example, through the following steps. First, an adhesive composition is applied onto a release film to form a coating film. The coating is then dried to form an adhesive layer. Next, it can be produced by bonding the adhesive layer on the release film and the electrode on the integrated product.
  • the Peltier element By bonding the Peltier element to the vapor chamber with the adhesive layer, the Peltier element is installed on the back surface of the vapor chamber.
  • thermoelectric conversion elements can be fabricated not on the substrate but on a flat plate or sheet that constitutes the vapor chamber.
  • a passivation film is formed on the flat plate or sheet constituting the vapor chamber as necessary, and then the passivation film is formed on the surface of the flat plate or sheet constituting the vapor chamber.
  • a connection electrode on the lower surface side is formed directly or on the passivation film, a thermoelectric semiconductor material composition is further applied, and drying or annealing treatment is performed as necessary to produce a thermoelectric conversion element.
  • connection electrodes on the upper surface side are formed.
  • an adhesive layer is formed on the connection electrodes on the upper surface side, if necessary.
  • the adhesive layer is curable, it is easy to lose the adhesiveness of the adhesive layer on the upper surface side by curing the adhesive layer.
  • another flat plate or sheet is joined, the working fluid is injected, and the injection port is sealed to complete the vapor chamber, thereby obtaining the temperature control module.
  • Peltier elements are arranged on both sides of the vapor chamber, respectively, as in the temperature control module 1C shown in FIG.
  • the vapor chamber may be assembled by joining the sheet and the second sheet.
  • the temperature control module of the present invention is a thin temperature control module with high cooling performance, it is used for applications that require installation in a narrow space, especially portable electronic devices in which components with high heat generation temperature are arranged in a narrow space. Suitable for applications such as In addition, the temperature control module can be made suitable for applications that require weight reduction, applications that require flexibility, and the like. This application is based on a Japanese patent application (Japanese Patent Application No. 2022-002595) filed on January 11, 2022, the entirety of which is incorporated by reference.
  • thermoelectric conversion layer 50 Temperature controlled member 60: Intervening layer D: thickness of temperature control module D1: total thickness of Peltier element and vapor chamber D2: thickness of vapor chamber D3: thickness of

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Control Of Temperature (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
  • Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)

Abstract

L'invention concerne un module de régulation de température présentant une capacité de refroidissement élevée et un profil mince, le module de régulation de température comprenant un élément Peltier et une chambre à vapeur stratifiée sur l'élément Peltier, l'épaisseur totale de l'élément Peltier et de la chambre à vapeur étant inférieure ou égale à 1 mm.
PCT/JP2022/048456 2022-01-11 2022-12-28 Module de régulation de température WO2023136155A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022002595 2022-01-11
JP2022-002595 2022-01-11

Publications (1)

Publication Number Publication Date
WO2023136155A1 true WO2023136155A1 (fr) 2023-07-20

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PCT/JP2022/048456 WO2023136155A1 (fr) 2022-01-11 2022-12-28 Module de régulation de température

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Country Link
TW (1) TW202338544A (fr)
WO (1) WO2023136155A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160181504A1 (en) * 2014-12-23 2016-06-23 Palo Alto Research Center Incorporated Method for roll-to-roll production of flexible, stretchy objects with integrated thermoelectric modules, electronics and heat dissipation
JP2019050239A (ja) * 2017-09-07 2019-03-28 株式会社村田製作所 半導体パッケージ
WO2021241635A1 (fr) * 2020-05-29 2021-12-02 リンテック株式会社 Module de conversion thermoélectrique et son procédé de fabrication
WO2022084884A1 (fr) * 2020-10-21 2022-04-28 3M Innovative Properties Company Dispositif thermoélectrique flexible comprenant une chambre à vapeur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160181504A1 (en) * 2014-12-23 2016-06-23 Palo Alto Research Center Incorporated Method for roll-to-roll production of flexible, stretchy objects with integrated thermoelectric modules, electronics and heat dissipation
JP2019050239A (ja) * 2017-09-07 2019-03-28 株式会社村田製作所 半導体パッケージ
WO2021241635A1 (fr) * 2020-05-29 2021-12-02 リンテック株式会社 Module de conversion thermoélectrique et son procédé de fabrication
WO2022084884A1 (fr) * 2020-10-21 2022-04-28 3M Innovative Properties Company Dispositif thermoélectrique flexible comprenant une chambre à vapeur

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