WO2023127923A1 - Feuille composite et son procédé de production, et élément de conversion thermoélectrique - Google Patents

Feuille composite et son procédé de production, et élément de conversion thermoélectrique Download PDF

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Publication number
WO2023127923A1
WO2023127923A1 PCT/JP2022/048403 JP2022048403W WO2023127923A1 WO 2023127923 A1 WO2023127923 A1 WO 2023127923A1 JP 2022048403 W JP2022048403 W JP 2022048403W WO 2023127923 A1 WO2023127923 A1 WO 2023127923A1
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Prior art keywords
composite sheet
sheet
base sheet
thermoelectric conversion
composite
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PCT/JP2022/048403
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English (en)
Japanese (ja)
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秀樹 内田
雅之 高尻
克真 三浦
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日本ゼオン株式会社
学校法人東海大学
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Priority to JP2023571079A priority Critical patent/JPWO2023127923A1/ja
Publication of WO2023127923A1 publication Critical patent/WO2023127923A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—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
    • 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
    • H10N10/856—Thermoelectric active materials comprising organic compositions

Definitions

  • the present invention relates to a composite sheet, a manufacturing method thereof, and a thermoelectric conversion element.
  • the present invention relates to a composite sheet containing carbon nanotubes, a method for producing the same, and a thermoelectric conversion element.
  • Patent Literature 1 proposes a sheet including a fibrous base material and single-walled carbon nanotubes attached to fibers that constitute the fibrous base material. Sheets containing nanocarbon materials are used in various applications by taking advantage of their advantageous properties.
  • Patent Documents 2 and 3 discuss a thermoelectric conversion element formed of a material containing a nanocarbon material such as a carbon nanotube.
  • thermoelectric conversion element creates a temperature difference between electrodes, and the temperature difference causes a potential difference to produce an electromotive force.
  • the conventionally proposed thermoelectric conversion elements have room for further expansion in terms of the temperature difference that can be generated.
  • structural films constituting thermoelectric conversion elements are required to have excellent structural strength from the viewpoint of durability.
  • the structural films that have been conventionally proposed have room for further improvement in terms of both increasing the temperature difference that can be formed and increasing the structural strength at a high level.
  • an object of the present invention is to provide a composite sheet that can create a large temperature difference when used to form a thermoelectric conversion element and has excellent structural strength, and a method for manufacturing the same.
  • the present inventors have conducted intensive studies with the aim of solving the above problems.
  • the present inventors have found that a composite sheet satisfying a predetermined structure, which is formed by adhering a nanocarbon material to a base sheet having a network structure, exhibits a high temperature when used to form a thermoelectric conversion element.
  • the inventors have found that it is possible to create a difference and have excellent structural strength, and have completed the present invention.
  • a composite sheet of the present invention comprises a base sheet having a network structure and a nanocarbon material
  • a composite sheet comprising a nanocarbon film portion formed by adhering to the composite sheet, the composite sheet having a plurality of through-holes penetrating in the thickness direction and being self-supporting.
  • Such a composite sheet has excellent structural strength and good heat dissipation, and can create a large temperature difference when used to form a thermoelectric conversion element.
  • self-standing refers to the ability to maintain its shape independently without being damaged even without the presence of a support.
  • the base sheet is self-supporting. If the base sheet is self-supporting, the structural strength of the composite sheet can be further increased.
  • the base sheet is preferably made of engineering plastic. If the base sheet is made of engineering plastic, the structural strength of the composite sheet can be further increased, and a greater temperature difference can be created when used to form a thermoelectric conversion element.
  • the base sheet has a mesh structure with an opening of 80 ⁇ m or more and 200 ⁇ m or less. If the base sheet has a network structure with an opening of 80 ⁇ m or more and 200 ⁇ m or less, the structural strength of the composite sheet can be further increased, and a greater temperature difference can be created when used to form a thermoelectric conversion element.
  • the nanocarbon material contains carbon nanotubes. If the nanocarbon film portion of the composite sheet contains carbon nanotubes, the structural strength of the composite sheet can be further increased, and a greater temperature difference can be created when used to form a thermoelectric conversion element.
  • the total opening area of the through holes on one side of the composite sheet is A1
  • the value of A1 / A2 x 100(%) is preferably 5% or more and 90% or less. If the value of A 1 /A 2 ⁇ 100 (%) satisfies the above range, it is possible to further increase the structural strength of the composite sheet and create a greater temperature difference when used to form a thermoelectric conversion element. be.
  • Various open area values can be measured according to the methods described in the examples of the present specification.
  • an object of the present invention is to advantageously solve the above problems, and a method for manufacturing a composite sheet according to the present invention is a composite sheet according to any one of [1] to [6] above.
  • the manufacturing method of (1) characterized by comprising a contacting step of contacting the base sheet with a dispersion liquid in which the nanocarbon material is dispersed in a dispersion medium.
  • the nanocarbon film portion is formed through the contact step of contacting the base sheet with the dispersion liquid in which the nanocarbon material is dispersed in the dispersion medium.
  • the composite sheet of the present invention can be produced satisfactorily.
  • the contacting step is repeated a plurality of times, and the total area of the through holes on one side of the composite sheet is A1 .
  • the value of A 1 /A 2 ⁇ 100 (%) is preferably 5% or more and 90% or less, where A 2 is the total open area of the mesh on one side.
  • thermoelectric conversion element of the present invention comprises the composite sheet according to any one of [1] to [6]. It is characterized by Such a thermoelectric conversion element is excellent in thermoelectric conversion performance.
  • thermoelectric conversion element it is possible to provide a composite sheet that can create a large temperature difference when used to form a thermoelectric conversion element and has excellent structural strength, and a method for manufacturing the same.
  • the composite sheet of the present invention can be produced satisfactorily according to the method for producing a composite sheet of the present invention. Moreover, the composite sheet of the present invention can be suitably used not only for thermoelectric conversion elements but also for other applications such as sensor elements.
  • the composite sheet of the present invention includes a base sheet having a network structure and a nanocarbon film portion formed by attaching a nanocarbon material to the base sheet. Furthermore, the composite sheet of the present invention is characterized by having a plurality of through-holes penetrating in the thickness direction and being self-supporting. The sheet of the present invention may optionally contain other components such as additives used in manufacturing the composite sheet.
  • the nanocarbon material is “adhered” to the base sheet simply means that a film made of the nanocarbon material is arranged adjacently on one or both sides of the base sheet having a network structure. It does not mean a state in which the nanocarbon film portion exists on the wall surfaces of the openings forming the network structure as a result of the nanocarbon material adhering to the wall surfaces.
  • FIG. 1 shows a microscopic image of a composite sheet according to one example of the present invention.
  • FIG. 1 is an enlarged observation image of a part of the composite sheet.
  • a nanocarbon material 2 is attached to a base sheet 1 having a network structure, and a plurality of through holes 3 are present that penetrate the composite sheet in the thickness direction.
  • the through holes 3 create a temperature difference within the sheet when, for example, one end of the composite sheet is heated and the other end is not heated. can contribute. This is because the presence of the through-holes 3 enhances air permeability, which improves heat dissipation and facilitates lowering the temperature of the unheated end.
  • the composite sheet has A 1 /
  • the value of A 2 ⁇ 100 (%) is preferably 5% or more, more preferably 20% or more, preferably 90% or less, and more preferably 78% or less. If the value of A 1 /A 2 ⁇ 100 (%) is equal to or greater than the above lower limit, it becomes possible to create a larger temperature difference when used to form a thermoelectric conversion element. If the value of A 1 /A 2 ⁇ 100 (%) is equal to or less than the above upper limit, the structural strength of the composite sheet can be further increased.
  • the value of A 1 /A 2 ⁇ 100 (%) corresponds to the ratio of the total open area of the composite sheet to the total open area of the base sheet before attaching the nanocarbon material. . Therefore, the value of A 1 /A 2 ⁇ 100 (%) can also be regarded as the pore area retention rate when the composite sheet is formed using the base sheet.
  • the base sheet having a network structure constituting the composite sheet of the present invention preferably has self-supporting properties. In other words, it is preferable that the base sheet be able to maintain its shape by itself without breaking even in the absence of a support.
  • the base sheet is preferably made of engineering plastic. Engineering plastics include polyphenylene sulfide, polycarbonate, polyamide resin (polyamide 6, polyamide 66), polyacetal, aromatic polyamide, liquid crystal polymer, polyether sulfone, polyether imide, polyether ether ketone, polyimide, fluorine resin, and more.
  • polyesters such as nylon, polyethylene, and polyethylene terephthalate, polypropylene, vinyl chloride, and acrylonitrile-butadiene-styrene (ABS) resins are also included.
  • ABS acrylonitrile-butadiene-styrene
  • polyphenylene sulfide and polyester are preferred, and polyphenylene sulfide is particularly preferred.
  • the constituent material of the base sheet preferably has a thermal conductivity of 0.50 W/mK or less, more preferably 0.30 W/mK or less.
  • the lower limit of thermal conductivity is not particularly limited, it can be, for example, 0.05 W/mK or more. If the thermal conductivity is equal to or less than the above upper limit, it becomes possible to create a larger temperature difference when used to form a thermoelectric conversion element.
  • the mesh structure of the base sheet preferably has an opening of 50 ⁇ m or more, more preferably 90 ⁇ m or more, preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less. If the opening is at least the above lower limit, it is possible to create a larger temperature difference when used to form a thermoelectric conversion element. Moreover, if the opening is equal to or less than the above upper limit, the structural strength of the composite sheet can be further increased.
  • the thread diameter of the threads forming the network structure of the base sheet is preferably 100 ⁇ m or less, more preferably 60 ⁇ m or less.
  • the lower limit of the thread diameter is not particularly limited, it can usually be 10 ⁇ m or more. If the yarn diameter is equal to or less than the above upper limit, it becomes possible to create a larger temperature difference when used to form a thermoelectric conversion element.
  • Carbon nanotubes (CNT), graphene, fullerene, and the like can be cited as the nanocarbon material contained in the nanocarbon film part constituting the composite sheet of the present invention.
  • CNT is included as the nanocarbon material.
  • CNTs include single-walled carbon nanotubes and multi-walled carbon nanotubes, but single-walled carbon nanotubes are more preferred.
  • thermoelectric conversion element it is more preferable to include single-walled carbon nanotubes because multi-walled carbon nanotubes have a low power generation capacity.
  • the nanocarbon film portion contains single-walled carbon nanotubes (single-walled CNTs) as a main component.
  • the ratio of single-walled CNTs in the nanocarbon film portion is preferably more than 50% by mass, preferably 90% by mass or more, more preferably 95% by mass or more, and 100% by mass.
  • the CNTs include multi-layered CNTs
  • the number of layers of the multi-layered CNTs is preferably three or less.
  • CNTs Preferred attributes of CNTs will be described below, and these attributes preferably apply to both CNTs as the material used in manufacturing the sheet of the present invention and CNTs contained in the composite sheet of the present invention. More specifically, at least the BET specific surface area, average diameter, etc. are, in principle, the BET ratio exhibited by the CNT as a material even after various treatments included in the manufacturing method of the composite sheet described later. No less than the surface area value.
  • CNTs can be produced using known CNT synthesis methods such as an arc discharge method, laser ablation method, and chemical vapor deposition method (CVD method), without being particularly limited.
  • CNTs are synthesized, for example, by supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for producing carbon nanotubes on its surface, and synthesizing CNTs by chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a method of dramatically improving the catalytic activity of the catalyst layer by allowing a trace amount of oxidizing agent (catalyst activating substance) to exist in the system (super-growth method; see International Publication No. 2006/011655). , can be efficiently manufactured.
  • the carbon nanotube obtained by the super growth method may be called "SGCNT.”
  • CNTs preferably show an upward convex shape in the t-plot obtained from the adsorption isotherm.
  • the growth of a nitrogen gas adsorption layer on a substance having pores on its surface is classified into the following processes (1) to (3). Then, the slope of the t-plot changes due to the following processes (1) to (3).
  • the t-plot showing an upwardly convex shape is located on a straight line passing through the origin in a region where the average thickness t of the nitrogen gas adsorption layer is small, whereas when t becomes large, the plot is on the straight line.
  • position shifted downward from A CNT having such a t-plot shape has a large ratio of internal specific surface area to the total specific surface area of the CNT, indicating that a large number of openings are formed in the CNT.
  • the inflection point of the t-plot of CNT is preferably in the range that satisfies 0.2 ⁇ t (nm) ⁇ 1.5, and is in the range of 0.45 ⁇ t (nm) ⁇ 1.5. is more preferable, and it is even more preferable to be in the range of 0.55 ⁇ t(nm) ⁇ 1.0.
  • CNTs having the inflection point of the t-plot within such a range are more difficult to agglomerate in the dispersion liquid when such CNTs are used to prepare the dispersion liquid. As a result, a more homogeneous composite sheet can be obtained.
  • the "position of the inflection point" is the intersection of the approximate straight line A in the process (1) described above and the approximate straight line B in the process (3) described above.
  • the CNT preferably has a ratio (S2/S1) of the internal specific surface area S2 to the total specific surface area S1 obtained from the t-plot of 0.05 or more and 0.30 or less. CNTs having a value of S2/S1 within such a range are more difficult to agglomerate in the dispersion liquid when such CNTs are used to prepare the dispersion liquid. As a result, a more homogeneous composite sheet can be obtained.
  • the total specific surface area S1 and internal specific surface area S2 of CNT can be obtained from the t-plot. Specifically, first, the total specific surface area S1 can be obtained from the slope of the approximate straight line in process (1), and the external specific surface area S3 can be obtained from the slope of the approximate straight line in process (3). By subtracting the external specific surface area S3 from the total specific surface area S1, the internal specific surface area S2 can be calculated.
  • the measurement of the adsorption isotherm of CNT, the creation of the t-plot, and the calculation of the total specific surface area S1 and the internal specific surface area S2 based on the analysis of the t-plot can be performed, for example, by a commercially available measurement device "BELSORP ( (registered trademark)-mini” (manufactured by Nippon Bell Co., Ltd.).
  • the CNT preferably has a BET specific surface area of 600 m 2 /g or more, more preferably 800 m 2 /g or more, preferably 2000 m 2 /g or less, and 1800 m 2 /g or less. It is more preferably 1600 m 2 /g or less. If the BET specific surface area is within the above range, it is possible to create a larger temperature difference when used to form a thermoelectric conversion element.
  • the average diameter of CNTs is preferably 1 nm or more, preferably 60 nm or less, more preferably 30 nm or less, and even more preferably 10 nm or less.
  • the average length of the CNTs is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, even more preferably 80 ⁇ m or more, preferably 600 ⁇ m or less, and preferably 500 ⁇ m or less. More preferably, it is 400 ⁇ m or less.
  • CNTs having an average diameter and/or average length within the above ranges are more difficult to agglomerate in the dispersion when such CNTs are used to prepare a dispersion, and a more homogeneous composite sheet can be obtained. can be done.
  • the average diameter and average length of CNTs can be calculated as the number average value of 100 CNTs measured by microscopic observation.
  • CNTs usually have an aspect ratio (length/diameter) of greater than 10.
  • the average diameter, average length and aspect ratio of CNTs can be obtained by measuring the diameter and length of 100 randomly selected CNTs using a scanning electron microscope or transmission electron microscope.
  • the sheet of the present invention preferably does not contain a binder.
  • a method for producing a composite sheet is characterized by including a contacting step of contacting a base sheet with a dispersion liquid in which a nanocarbon material is dispersed in a dispersion medium. Furthermore, the method of manufacturing the composite sheet preferably repeats the contacting step multiple times. Then, in the method for manufacturing the composite sheet, it is preferable to carry out the drying step after the completion of the contacting step. The drying step may be carried out after each contacting step is completed, or may be carried out once after repeating the contacting step a plurality of times.
  • the above-described composite sheet of the present invention can be manufactured satisfactorily.
  • a preparatory step it is preferable to perform a preparatory step to prepare a dispersion liquid in which the nanocarbon material is dispersed in the dispersion medium.
  • the nanocarbon material is dispersed in a dispersion medium to prepare a dispersion.
  • the nanocarbon material the nanocarbon material as described above can be used.
  • the dispersion medium is not particularly limited, and water, isopropanol, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylacetamide, toluene, tetrahydrofuran, ethyl acetate, acetonitrile, ethylene glycol, methyl isobutyl ketone and butyl Alcohol can be used.
  • a dispersant can be added as an additive to improve the dispersibility of the nanocarbon material when preparing the dispersion.
  • the dispersant is not particularly limited.
  • known surfactants such as sodium dodecylsulfonate, sodium deoxycholate, sodium cholate, sodium dodecylbenzenesulfonate, etc.
  • synthetic or natural polymers that can function as dispersants can be used.
  • the amount of dispersant added can be within a general range.
  • the nanocarbon material is added to the dispersion medium containing the surfactant as described above to obtain a coarse dispersion, and the resulting coarse dispersion is disclosed in International Publication No. 2014/115560.
  • a dispersing method that can obtain a cavitation effect and / or a dispersing method that can obtain a crushing effect, as disclosed in can be done.
  • the dispersing method is not limited to these two methods, and it is of course possible to apply a method of direct stirring using a stirrer.
  • the dispersion time in the preparation process can be, for example, 1 minute or more and 20 minutes or less.
  • the base sheet is brought into contact with a dispersion liquid in which the nanocarbon material is dispersed in a dispersion medium.
  • the contact method is not particularly limited as long as at least one side, preferably both sides, of the base sheet can be brought into contact with the nanocarbon material dispersion. Examples include a method of impregnating a material sheet and a method of applying a nanocarbon material dispersion onto a base sheet. Among them, the method of impregnating the substrate sheet with the nanocarbon material dispersion is preferred.
  • the contacting step is repeated several times to obtain the nanocarbon material attached to the base sheet. It is preferred to increase the amount of carbon material. In this way, it is preferable that the value of A 1 /A 2 ⁇ 100 (%) is 5% or more and 90% or less as a result of repeating the contacting step a plurality of times.
  • the drying step the composite sheet is dried to remove the dispersion medium and the like.
  • the drying method in the drying step is not particularly limited, and includes hot air drying, vacuum drying, hot roll drying, infrared irradiation, and the like.
  • the drying temperature is not particularly limited, but usually room temperature to 200° C.
  • the drying time is not particularly limited, but is usually from 1 hour to 48 hours.
  • the composite sheet of the present invention obtained as described above can create a large temperature difference when used to form a thermoelectric conversion element, and has excellent structural strength.
  • thermography Thermoshot F30, manufactured by NEC Avio Infrared Technologies.
  • thermography Thermoshot F30, manufactured by NEC Avio Infrared Technologies.
  • the difference between the temperature in the hottest measurement area adjacent to the hot plate surface and the temperature in the measurement area furthest in the vertical direction from the hot plate was obtained to evaluate the temperature difference.
  • a larger temperature difference detected in this test means that a larger temperature difference can be created when used to form a thermoelectric conversion element.
  • thermoelectric property evaluation device (“ZEM-3” manufactured by Advance Riko Co., Ltd.) was prepared, and the Seebeck coefficient of the composite material sheet when a temperature difference of 0 to 5 ° C. was applied at room temperature in an air atmosphere. S ( ⁇ V/K) was measured.
  • BET specific surface area The BET specific surface area of CNT as a nanocarbon material used in Examples and Comparative Examples was measured using a fully automatic specific surface area measuring device (manufactured by Mountec Co., Ltd., product name "Macsorb (registered trademark) HM model-1210"). It was measured.
  • Example 1 ⁇ Preparation process> According to the description of International Publication No. WO 2006/011655, by the super-growth method, CNT (SGCNT, ratio of single-walled CNT: 90%, average diameter: 3.5 nm, average length: 350 ⁇ m, BET specific surface area: 1200 m 2 /g ) was prepared. The obtained CNT was used as a nanocarbon material and added to distilled water as a dispersion medium at a concentration of 0.5% by mass. In addition, sodium dodecylbenzenesulfonate (SDBS) was added as a dispersant at a concentration of 1% by mass.
  • SDBS sodium dodecylbenzenesulfonate
  • Example 2 Various operations were performed in the same manner as in Example 1 except that a PPS sheet different from that in Example 1 (opening 100 ⁇ m, thread diameter 34 ⁇ m, number of meshes 180, thermal conductivity: 0.29 W/mK) was used as the base sheet. , measured and evaluated. Table 1 shows the results.
  • Example 1 Various operations, measurements, and evaluations were performed in the same manner as in Example 1, except that a polyester mesh sheet was used as the base sheet. Table 1 shows the results. The resulting composite sheet did not stand on its own, and neither the Seebeck coefficient nor the temperature could be measured.
  • Example 2 Various operations, measurements, and evaluations were performed in the same manner as in Example 1, except that a cotton cloth (open area ratio cannot be measured) was used as the base sheet. Table 1 shows the results. The resulting composite sheet was not self-supporting and unstable, and various attributes could not be measured.
  • Example 3 Various operations, measurements, and evaluations were performed in the same manner as in Example 1, except that a polypropylene nonwoven fabric was used as the base sheet. Table 1 shows the results. Film folding occurred after the second contacting step, and various attributes of the resulting composite sheet could not be measured.
  • Example 4 A CNT sheet (undried) was produced by dropping the 0.5% by mass nanocarbon material dispersion liquid prepared in Example 1 onto a membrane filter and filter paper, and suction-filtrating it. After that, the CNT sheet (undried) was dried in a dryer at 60° C. for 24 hours to obtain a CNT sheet. As in Example 1, the electrical conductivity, the Seebeck coefficient, and the temperature difference that can be created in the sheet were measured for the obtained CNT sheet. Table 1 shows the results.
  • PPS polyphenylene sulfide
  • PP polypropylene
  • thermoelectric conversion element it is possible to provide a composite sheet that can create a large temperature difference when used to form a thermoelectric conversion element and has excellent structural strength, and a method for manufacturing the same.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

Cette feuille composite comprend : une feuille de substrat ayant une structure maillée ; et une section de film de nanocarbone formée suite à l'adhérence d'un matériau de nanocarbone à la feuille de substrat. Cette feuille composite est autoportante et comporte de multiples trous traversants qui pénètrent dans la direction de l'épaisseur.
PCT/JP2022/048403 2021-12-28 2022-12-27 Feuille composite et son procédé de production, et élément de conversion thermoélectrique WO2023127923A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121133A1 (fr) * 2011-03-04 2012-09-13 独立行政法人産業技術総合研究所 Matériau de conversion thermoélectrique et dispositif de conversion thermoélectrique flexible mettant en œuvre ledit matériau
KR20130006133A (ko) * 2011-07-08 2013-01-16 (주)케이에이치 케미컬 발열, 보온 및 축열 기능을 갖는 섬유 및 직물의 제조 방법
WO2019065517A1 (fr) * 2017-09-28 2019-04-04 日本ゼオン株式会社 Feuille et procédé de fabrication de celle-ci
WO2019065910A1 (fr) * 2017-09-28 2019-04-04 日本ゼオン株式会社 Feuille de carbone
WO2019171987A1 (fr) * 2018-03-07 2019-09-12 日本ゼオン株式会社 Structure conductrice, corps composite, procédé de production de structure conductrice, et procédé de production de corps composite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012121133A1 (fr) * 2011-03-04 2012-09-13 独立行政法人産業技術総合研究所 Matériau de conversion thermoélectrique et dispositif de conversion thermoélectrique flexible mettant en œuvre ledit matériau
KR20130006133A (ko) * 2011-07-08 2013-01-16 (주)케이에이치 케미컬 발열, 보온 및 축열 기능을 갖는 섬유 및 직물의 제조 방법
WO2019065517A1 (fr) * 2017-09-28 2019-04-04 日本ゼオン株式会社 Feuille et procédé de fabrication de celle-ci
WO2019065910A1 (fr) * 2017-09-28 2019-04-04 日本ゼオン株式会社 Feuille de carbone
WO2019171987A1 (fr) * 2018-03-07 2019-09-12 日本ゼオン株式会社 Structure conductrice, corps composite, procédé de production de structure conductrice, et procédé de production de corps composite

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