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WO2021112268A1 - Procédé de production d'un matériau thermoélectrique poreux et élément thermoélectrique comprenant un matériau thermoélectrique poreux - Google Patents

Procédé de production d'un matériau thermoélectrique poreux et élément thermoélectrique comprenant un matériau thermoélectrique poreux Download PDF

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Publication number
WO2021112268A1
WO2021112268A1 PCT/KR2019/016865 KR2019016865W WO2021112268A1 WO 2021112268 A1 WO2021112268 A1 WO 2021112268A1 KR 2019016865 W KR2019016865 W KR 2019016865W WO 2021112268 A1 WO2021112268 A1 WO 2021112268A1
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Prior art keywords
thermoelectric
thermoelectric material
porous
electrode
polymer
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Korean (ko)
Inventor
양승진
박주현
양승호
황병진
연병훈
손경현
박정구
장봉중
이태희
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LT Metal Co Ltd
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LT Metal Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or 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
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
    • 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
    • H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
    • 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 porous thermoelectric material including micropores, a manufacturing method thereof, and a thermoelectric device having improved thermoelectric performance including the porous thermoelectric material.
  • Thermoelectric technology is generally a technology that directly converts thermal energy into electrical energy and electrical energy into thermal energy in a solid state, and is applied in thermoelectric power generation that converts thermal energy into electrical energy and thermoelectric cooling that converts electrical energy into thermal energy.
  • the thermoelectric material used for such thermoelectric power generation and thermoelectric cooling improves the performance of the thermoelectric element as the thermoelectric characteristics increase.
  • the dimensionless figure of merit (ZT) is an important factor in determining the thermoelectric conversion energy efficiency.
  • thermoelectric materials are generally manufactured by dissolving and solidifying raw materials constituting the thermoelectric material to prepare a master alloy, then press-molding and sintering the same. These thermoelectric materials have only some differences in manufacturing methods and conditions, and it is difficult to secure desired levels of Seebeck coefficient, electrical conductivity, thermal conductivity, and the like.
  • the present invention has been devised to solve the above-described problems, and a novel manufacturing method of a thermoelectric material capable of simultaneously realizing performance improvement and reduced usage by reducing thermal conductivity while maintaining electrical conductivity by securing porosity in the thermoelectric material, and the method It is a technical task to provide a porous thermoelectric material manufactured by
  • thermoelectric device including the aforementioned porous thermoelectric material.
  • the present invention comprises the steps of (i) dissolving and solidifying a raw material for a thermoelectric material to form a master alloy; (ii) rapidly cooling the mother alloy to form a metal ribbon; (iii) mixing the metal ribbon with a polymer that is thermally decomposed at a predetermined temperature or higher and pulverizing it in an inert atmosphere; and (iv) sintering the pulverized product of step (iii) at a temperature higher than the thermal decomposition temperature of the polymer.
  • the thermally decomposable polymer may be pyrolyzed by sintering to form a plurality of pores and removed.
  • the thermally decomposable polymer may be selected from the group consisting of a thermoplastic polymer having a thermal decomposition temperature of 200 to 500 °C, a natural polymer, and a water-soluble polymer.
  • the thermally decomposable polymer may have a residual carbon content of 5.0% or less after thermal decomposition.
  • the thermally decomposable polymer is polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), polybromonietide biphenyl (PBB), polyvinyl alcohol (PVA), And it may be at least one selected from the group consisting of ethyl cellulose (EC).
  • PMMA polymethyl methacrylate
  • PBMA polybutyl methacrylate
  • PBB polybromonietide biphenyl
  • PVA polyvinyl alcohol
  • EC ethyl cellulose
  • the thermally decomposable polymer may be a spherical particle having an average particle diameter (D 50 ) of 5 to 50 ⁇ m.
  • the thermally decomposable polymer may be added in an amount of 0.1 to 2 parts by weight based on the total weight of the metal ribbon.
  • step (iv) the pulverized product of step (iii) may be put into a molding mold and sintered by hot pressing.
  • the thermoelectric material may be at least one of a Bi-Te-based thermoelectric material and a Skuttrudite-based thermoelectric material.
  • the porous thermoelectric material may have a porosity of 0.1 to 10%, a pore size of 5 to 50 ⁇ m, and a density of 90 to 99.9%.
  • the present invention provides a porous thermoelectric material manufactured by the above-described method.
  • the present invention is a first substrate; a second substrate facing the first substrate; a first electrode and a second electrode respectively disposed between the first substrate and the second substrate; a plurality of thermoelectric legs interposed between the first electrode and the second electrode; and a bonding material disposed between at least one of the first electrode and the thermoelectric leg and between the thermoelectric leg and the second electrode, wherein at least one of the plurality of thermoelectric legs includes the aforementioned porous thermoelectric material.
  • the bonding material is Sn-based solder; Alternatively, it may have a composition including the Sn-based solder and a metal dendrite having an average branch length of 5 to 50 ⁇ m.
  • thermoelectric element may be applied to at least one of cooling, power generation, and a thin film sensor.
  • a porous thermoelectric material uniformly containing micropore size and workability can be easily manufactured by using a pyrolyzable polymer as a pore former by a sintering process when manufacturing a thermoelectric material.
  • thermoelectric material used it is economical by reducing the amount of thermoelectric material used compared to non-porous thermoelectric materials, and the thermal conductivity is reduced without significantly lowering the electrical conductivity and Seebeck coefficient due to the regular pores contained in the thermoelectric material. performance can be improved.
  • the effect according to the present invention is not limited by the contents exemplified above, and more various effects are included in the present specification.
  • FIG. 1 is a process flowchart of a manufacturing method according to an embodiment of the present invention.
  • thermoelectric material 2 is a schematic diagram of a thermoelectric material according to the manufacturing method of the present invention.
  • thermoelectric element 4 is a perspective view illustrating a thermoelectric element according to an embodiment of the present invention.
  • thermoelectric device 5 is a cross-sectional view of a thermoelectric device according to an embodiment of the present invention.
  • thermoelectric device 7 is a power factor graph using the thermoelectric devices of Examples 1 to 12 and Comparative Example 1.
  • FIG. 7 is a power factor graph using the thermoelectric devices of Examples 1 to 12 and Comparative Example 1.
  • thermoelectric figure of merit graph using the thermoelectric devices of Examples 1 to 12 and Comparative Example 1.
  • FIG. 8 is a thermoelectric figure of merit graph using the thermoelectric devices of Examples 1 to 12 and Comparative Example 1.
  • planar when referred to as “planar”, it means when the target part is viewed from above, and “in cross-section” means when viewed from the side when the cross-section of the target part is vertically cut.
  • thermoelectric element when manufacturing a thermoelectric element, a pore former having a high thermal decomposition rate and easy particle size control is mixed with a thermoelectric material to improve thermoelectric properties using a thermoelectric material porous with a predetermined pore size and porosity. do.
  • thermoelectric performance index (ZT) value when some pores are included in the thermoelectric material, it does not significantly affect the electrical conductivity, but may induce a decrease in thermal conductivity, thereby improving the thermoelectric performance index (ZT) value. Accordingly, it is possible to manufacture a superior thermoelectric element, and to reduce the amount of thermoelectric material used, thereby reducing costs.
  • a thermally decomposable polymer of an organic component that is thermally decomposed in the application temperature range of the sintering process is used as a pore former instead of the conventional complex pore former containing inorganic and organic components.
  • a thermally decomposable polymer is mixed with a thermoelectric material powder (eg, a metal ribbon) and pulverized by a ball mill, and then the pulverized product is sintered through a hot press (HP).
  • the thermally decomposable polymer is an organic component having a high thermal decomposition rate, the diameter, porosity, etc. of the pores after sintering can be easily controlled by adjusting the particle diameter, content, shape, etc.
  • thermoelectric element due to the residue and improved thermoelectric performance.
  • thermoelectric material a porous thermoelectric material according to an embodiment of the present invention
  • it is not limited only by the following manufacturing method, and the steps of each process may be modified or selectively mixed as needed.
  • the present invention is to porousize a conventional thermoelectric material used as a thermoelectric material for thermoelectric power generation and cooling.
  • the raw material for a thermoelectric material is subjected to rapid solidification (RSP) to form a metal ribbon and then pulverized (e.g., ball mill method) and sintering (eg, hot press), but using a polymer that can be thermally decomposed within the application temperature range of the sintering process as a pore former to prepare a porous thermoelectric material.
  • RSP rapid solidification
  • pulverized e.g., ball mill method
  • sintering e.g, hot press
  • step' dissolving and solidifying a raw material for a thermoelectric material to form a master alloy
  • step'S10 step' dissolving and solidifying a raw material for a thermoelectric material to form a master alloy
  • step'S20 step' forming a metal ribbon by rapidly cooling the master alloy
  • step'S30 step' mixing the metal ribbon and the thermally decomposable polymer and pulverizing them in an inert atmosphere
  • step (iii) sintering the pulverized product of step (iii) at a temperature higher than the thermal decomposition temperature of the polymer ('S40 step').
  • FIG. 1 is a conceptual diagram illustrating a method of manufacturing a porous thermoelectric material according to the present invention in each step.
  • the manufacturing method is divided into each process step and described as follows.
  • This step is a step of mixing, dissolving and solidifying the raw materials of the thermoelectric material according to the stoichiometric ratio constituting the porous thermoelectric material to form a master alloy.
  • thermoelectric material As the thermoelectric material according to the present invention, a conventional thermoelectric material known in the art may be used, and the thermoelectric material is not particularly limited.
  • Non-limiting examples of usable thermoelectric materials include Bi-Te-based, Co-Sb-based, Pb-Te-based, Ge-Tb-based, Si-Ge-based, Sb-Te-based, Sm-Co-based, and transition metal silicide-based materials. , Skuttrudite, Silicide, Half heusler, or a combination thereof.
  • it may be a Bi-Te-based or Skuttrudite-based thermoelectric material.
  • Bi, Te, Sb and Se may be used as raw materials for the thermoelectric material in step S10, which may be different depending on the composition for cooling/power generation.
  • Bi and Te are the main components, and depending on the n-type and the p-type, each may have a composition additionally including a Se or Sb component.
  • the Bi and Te raw material is, may be mixed in a ratio according to the stoichiometric composition of Bi 2 Te 3 Wh 0.2, and preferably be a Bi 2 Te 3 Wh 0.15.
  • the raw material for a thermoelectric material may include (i) at least one first element selected from the group consisting of Bi and Sb; and a raw material having a composition including one or more second elements selected from the group consisting of Te and Se. More specifically, when the raw material for the n-type thermoelectric material has a Bi-Te-Se-based alloy composition, 50 to 55 wt% of Bi, 40 to 45 wt% of Te, and 3 to 4 wt% of Se based on 100 wt% of the total It may be a composition comprising.
  • the raw material for the p-type thermoelectric material is a Bi-Sb-Te alloy composition
  • the composition may include 10 to 15 wt% of Bi, 25 to 30 wt% of Sb, and 55 to 60 wt% of Te based on 100 wt% of the total. have.
  • a doping element powder may be added to the composition of the thermoelectric material to be manufactured.
  • the dopant is introduced to allow the Bi-Te-based thermoelectric material to have n-type or p-type characteristics
  • conventional components in the art that can be used for the n-type or p-type thermoelectric material may be used without limitation.
  • it may be one or more metals selected from the group consisting of Al, Sn, Mn, Ag, Cu, and Ga.
  • the content of the at least one metal to be doped is not particularly limited, and may be, for example, in the range of 0.001 to 1% by weight based on the total weight.
  • the size and shape of the thermoelectric material is not particularly limited, but may be in the form of a mass of about 2 to 5 mm in size.
  • the purity of the thermoelectric material is preferably 5N or more high purity.
  • step S10 after the above-described raw material for thermoelectric material is charged into a quartz tube, a quartz tube in a vacuum state is charged into a furnace at a temperature of 600 to 1000° C. for 1-10 hours for 10 hours. Stir and dissolve at a rate of ⁇ 15 times/min to form the master alloy.
  • the master alloy In order to manufacture a ribbon using the rapid solidification method (RSP), it is necessary to prepare a master alloy of a uniform thermoelectric material (eg, Bi 2 -Te 3 system). Accordingly, the master alloy may be manufactured in a size of ⁇ 30 * 100 mm or approximately ⁇ 20 ⁇ 30 * 100 ⁇ 150 mm. It may be a Bi-Te-based alloy or a Skuttrudite-based alloy having a high purity of 5N or higher manufactured through the step S10.
  • a uniform thermoelectric material eg, Bi 2 -Te 3 system
  • the master alloy may be manufactured in a size of ⁇ 30 * 100 mm or approximately ⁇ 20 ⁇ 30 * 100 ⁇ 150 mm. It may be a Bi-Te-based alloy or a Skuttrudite-based alloy having a high purity of 5N or higher manufactured through the step S10.
  • a metal ribbon eg, Bi-Te-based
  • R.S.P rapid solidification method
  • step S20 after charging the master alloy ingot into a nozzle installed in the melt spinning equipment, it is completely dissolved using a heating element that can supply heat and continuously maintain it to form a melt, and then to the melt By pressurizing and spraying an inert gas, the melt is brought into contact with the surface of a rotating high-speed rotating wheel to rapidly cool it. Through this, a metal ribbon of a thermoelectric material (eg, Bi-Te-based) is formed.
  • a thermoelectric material eg, Bi-Te-based
  • the heating element is not particularly limited as long as it can continuously supply and maintain heat, and a conventional resistance heating element known in the art may be used.
  • a resistance heating element that generates heat by receiving a current may be used.
  • the temperature may be controlled by an electric furnace type heater, for example, a graphite heater.
  • the temperature range at which the resistance heating element generates heat is not particularly limited as long as it is a range capable of completely dissolving the master alloy of the thermoelectric material (Bi-Te type), for example, 500 to 800°C, preferably 600 to 700°C. will become
  • the type or pressurization range of the inert gas is also not particularly limited, and for example, it is preferable to pressurize the inert gas in the range of 0.1 to 0.5 MPa using argon gas or the like.
  • the high-speed rotating wheel in contact with the melt may use a conventional wheel known in the art, for example, a copper wheel (Cu wheel).
  • the rotation speed of the high-speed rotating wheel is not particularly limited, and for example, the linear speed of the wheel may be in the range of 5 to 50 m/s.
  • the alloy ribbon of the thermoelectric material having a thin thickness and a microstructure may be formed while the melt in contact with the surface of the wheel is rapidly cooled.
  • the cooling rate of the dissolved master alloy by controlling the cooling rate of the dissolved master alloy, uniform particle size control is possible, and when the cooling rate is generally slow, nano-sized amorphous powder can be prepared, or fine particle powder can be prepared. .
  • the concentration and type of the raw material it can be manufactured under different manufacturing conditions.
  • the master alloy that has undergone the above-described process does not become crystalline through a rapid cooling (RSP) process, but is solidified in a state in which an amorphous structure and a crystalline structure are mixed.
  • RSP rapid cooling
  • the rapid cooling rate is very fast, it is manufactured in the form of a ribbon, but if the cooling rate is adjusted, powder having a size of several hundred nanometers can be prepared in the form of a half-ribbon simply connected.
  • thermoelectric material eg, Bi-Te-based
  • the length of the prepared metal ribbon is 5 to 15 mm
  • the width is 0.5 to 5 mm
  • the thickness may be 10 ⁇ m or less.
  • a predetermined thermally decomposable polymer is added to form a nano-sized amorphous fine powder having a fine particle size and shape and thermal decomposition A pulverized product in which the polymer is uniformly mixed is prepared.
  • a pyrolytic polymer that is thermally decomposed at a predetermined temperature together with the above-described metal ribbon is added as a pore former and pulverized.
  • a conventional pore former uses a complex component including both an organic component and an inorganic component. Since the organic component is removed from the pore former after heat treatment to form a pore structure, while the inorganic component remains in the final thermoelectric material, the performance of the thermoelectric material may be deteriorated due to unwanted metal residues. In addition, since the conventional pore former contains inorganic components, it is difficult to control the desired pore size or pore size.
  • the thermally decomposable polymer employed in the present invention is an organic component that is thermally decomposed by forming and sintering processes to be described later without performing a separate heat treatment process to form a plurality of pores and removed at the same time.
  • This thermally decomposable polymer is a pore former that forms a predetermined pore size and pore size in the thermoelectric material, and since the content of residual carbon after sintering is minimized, degradation of the performance of the thermoelectric material due to the residue can be fundamentally prevented. have.
  • the thermally decomposable polymer is an organic component that is 100% thermally decomposed during thermal decomposition, the size, shape and porosity of the pores after sintering can be easily controlled by adjusting the average particle diameter, content, shape, etc. of the polymer used.
  • the thermally decomposable polymer is a material that is thermally decomposed and carbonized and removed by the application temperature of the sintering process to be described later, its components, content, shape, etc. are not particularly limited, and conventional polymers, copolymers, resins, etc. known in the art Can be used. In addition, the use of a monomolecular compound also falls within the scope of the present invention.
  • the thermally decomposable polymer may be selected from the group consisting of a thermoplastic polymer having a thermal decomposition temperature of 200 to 500°C, a natural polymer, and a water-soluble polymer.
  • the thermally decomposable polymer may have a residual carbon content of 5.0% or less after thermal decomposition by sintering, specifically 0 to 1.0% or less, more specifically 0 to 0.5% or less based on 100% of the total of the thermally decomposable polymer. .
  • thermally degradable polymers that can be used include polymethyl methacrylate (PMMA), polybutyl methacrylate (PBMA), polybromonietide biphenyl (PBB), polyvinyl alcohol (PVA), ethyl cellulose. (EC), or a mixture thereof.
  • PMMA polymethyl methacrylate
  • PBMA polybutyl methacrylate
  • PBB polybromonietide biphenyl
  • PVA polyvinyl alcohol
  • EC ethyl cellulose.
  • polyethylene, polypropylene, glucose, fructose, sucrose, xylose, starch, cellulose, etc. can also be used.
  • PMMA, PBMA, or a mixture thereof having a relatively low decomposition temperature and no residual carbon is preferred.
  • PMMA, PBMA, etc. are 100% pyrolyzed at about 400 °C, so almost no residue is generated.
  • the pore diameter, porosity, pore shape, etc. formed after sintering can be easily adjusted according to the particle diameter, shape, and content thereof of the thermally decomposable polymer used.
  • the size of the thermally decomposable polymer is not particularly limited, and may be appropriately adjusted in consideration of the porosity and pore size to be formed.
  • the average particle diameter (D 50 ) of the thermally decomposable polymer may be 5 to 50 ⁇ m, specifically 5 to 30 ⁇ m.
  • the shape of the thermally decomposable polymer is not particularly limited, and may be, for example, a spherical shape, a triangular or more polygonal shape, a needle shape, a plate shape, or an amorphous shape. It is preferably a spherical particle, and more preferably a spherical particle having excellent sphericity.
  • the amount of the thermally decomposable polymer is not particularly limited, and may be added in an amount of 0.1 to 2 parts by weight based on the total weight of the pulverized metal ribbon, for example.
  • the pulverization process of step S30 may be performed without limitation, and may be pulverized using a ball mill method, for example, a conventional pulverization/pulverization process known in the art.
  • the particle size of the pulverized powder is not particularly limited, and may be appropriately adjusted within a range known in the art.
  • the average particle diameter of the pulverized product in which the thermoelectric material (eg, Bi-Te-based) and the thermally decomposable polymer are mixed may be adjusted to 100 ⁇ m or less, preferably in the range of 10 to 100 ⁇ m.
  • the above-described crushing/grinding process is performed in an inert atmosphere.
  • the type or pressure range of the inert gas is not particularly limited, and for example, nitrogen gas, argon gas, or a mixture thereof may be used.
  • the oxygen content in the pulverized powder may be reduced to control the oxidation degree to be low.
  • the pulverized product according to the present invention can reduce the oxygen content by about 30% or more, specifically 30 to 45%, compared to the pulverized product carried out under atmospheric conditions containing oxygen, preferably the The oxygen content in the pulverized product may be controlled to 0.03% or less, preferably in the range of 0.02 to 0.03%.
  • a preform is manufactured by extruding a mixture of the pulverized material of the metal ribbon obtained in the above step and a thermally decomposable polymer, and then, a high-density thermoelectric material is manufactured through pressure sintering.
  • a molded body having a predetermined shape is manufactured to ensure high density in the pressure sintering process.
  • the compression process may use a conventional method known in the art, for example, it is preferable to use a cold press or a compressor.
  • the compression conditions are not particularly limited, and may be appropriately adjusted under conventional compression conditions known in the art.
  • thermoelectric material having high density and porosity.
  • the pressure sintering method that can be used in the present invention, there is a hot press (HP) or the like.
  • the pressure sintering conditions are not particularly limited, and for example, sintering can be carried out using a Hot Press device under a pressure of 20 to 80 MPa, specifically, a pressure of 40 to 70 MPa, at a temperature of 200 to 500° C. for 40 to 80 minutes. have. If it is smaller than the above-mentioned conditions, it is impossible to have the desired pore size and porosity, and if it exceeds the above-mentioned conditions, the vapor pressure of Te is high and volatilized, making it unsuitable for the intended composition. high.
  • FIG. 2 is a schematic diagram showing the structural change of a thermoelectric material including a thermally decomposable polymer according to the molding and sintering steps.
  • FIG. 2(a) is a preform manufactured to a predetermined standard through an extrusion process, wherein the preform has a predetermined particle size and shape in a matrix made of a thermoelectric material. It shows a structure in which the polymer is randomly distributed.
  • the volume of the polymer is decreased as the thermally decomposable polymer is gradually thermally decomposed and/or carbonized as the temperature rises (see Fig. 2(b)), As a result, when the thermal decomposition of the polymer is completed, a porous structure having a plurality of pores is formed at the location where the polymer is removed (see FIG. 2(c)).
  • the plurality of pores may be regularly distributed or randomly formed, and may have a closed type that is not connected to each other or an open pore structure that is three-dimensionally connected to each other.
  • the porous thermoelectric material of the present invention prepared through the above-described manufacturing method may have a micropore size and uniform porosity.
  • the porosity of the porous thermoelectric material may be 0.1 to 10%, specifically 0.5 to 5%.
  • the pore size included in the porous thermoelectric material can be easily adjusted according to the average particle diameter of the thermally decomposable polymer used. As an example, the pore size may be 5 to 50 ⁇ m.
  • the porous thermoelectric material may have a relative density of 90 to 99.9%, specifically 92% to 99.9%.
  • the degree of oxidation is controlled, so that the oxygen content in the thermoelectric material can be controlled to a predetermined range or less.
  • thermoelectric element of the present invention is provided with the above-described porous thermoelectric material, and includes all elements for thermoelectric power generation and/or cooling.
  • thermoelectric element includes two substrates facing each other; conductive electrodes and a plurality of thermoelectric materials (thermoelectric legs) respectively disposed on upper and lower portions of the two substrates; and a bonding layer disposed between the thermoelectric material and the conductive electrode, wherein at least one of the plurality of thermoelectric legs includes the aforementioned porous thermoelectric material.
  • thermoelectric element according to the present invention.
  • the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.
  • thermoelectric element 100 is a perspective view schematically showing the structure of the thermoelectric element 100 according to an embodiment of the present invention
  • FIG. 5 is a cross-sectional view of the thermoelectric element 100 .
  • the thermoelectric element 100 includes: a first substrate 11; a second substrate 11 facing the first substrate 11; a first electrode 20a and a second electrode 20b respectively disposed between the first substrate 11 and the second substrate 11; a plurality of thermoelectric legs 30 interposed between the first electrode 20a and the second electrode 20b; and a bonding material 40 disposed between the first electrode 20a and the thermoelectric leg 30 and between the thermoelectric leg 30 and the second electrode 20b.
  • thermoelectric element As in this specification, each configuration of the thermoelectric element will be described in detail as follows.
  • the first substrate 11 and the second substrate 11 each generate an exothermic or endothermic reaction when power is applied to the thermoelectric element 100 , and may be made of a conventional electrically insulating material known in the art.
  • each of the first substrate 11 and the second substrate 11 may be a ceramic substrate composed of one or more compositions of Al 2 O 3 , AlN, SiC, and ZrO 2 .
  • it may be composed of a high heat-resistance insulating resin or engineering plastic.
  • first substrate 11 and the second substrate 11 may be a metal substrate made of a conventional conductive metal material known in the art.
  • the first substrate 11 and the second substrate 11 may be formed of at least one metal among aluminum (Al), zinc (Zn), copper (Cu), nickel (Ni), and cobalt (Co), respectively. may include.
  • a first insulating layer (not shown) is formed on one surface of the first substrate 11 on which the first electrode 20a is disposed, and the second substrate 11 on which the second electrode 20b is disposed.
  • a second insulating layer (not shown) is formed on one surface, and the first insulating layer and the second insulating layer are disposed to face each other.
  • the first insulating layer and the second insulating layer may be the same as or different from each other, and an electrically insulating material that is easy to form a film may be used.
  • the insulating resin may be used alone or a mixture of the insulating resin and the ceramic filler (powder) may be included.
  • each of the first insulating layer and the second insulating layer may be an epoxy resin layer including a ceramic filler.
  • Each of the first substrate 11 and the second substrate 11 may have a flat plate shape, and the size or thickness thereof is not particularly limited.
  • the thickness of each of the first substrate 11 and the second substrate 11 may be 0.5 to 2 mm, preferably 0.5 to 1.5 mm, more preferably 0.6 to 0.8 mm.
  • the positions of the heat absorption and heat generation of the substrate can be changed according to the direction of the current.
  • One of the two substrates is a cold side substrate on which an endothermic reaction occurs, and a heat dissipation pad may be applied to this substrate.
  • the heat dissipation pad may be formed of a silicone polymer or an acrylic polymer, and has a thermal conductivity in the range of 0.5 to 5.0 W/mk, thereby maximizing heat transfer efficiency. It can also act as an insulator.
  • the other one of the two substrates may be a heating part substrate (hot side).
  • a first electrode 20a and a second electrode 20b are respectively disposed on the first substrate 11 and the second substrate 11 disposed to face each other. That is, the second electrode 20b is disposed at a position opposite to the first electrode 20a.
  • the material of the first electrode 20a and the second electrode 20b is not particularly limited, and a material used as an electrode in the art may be used without limitation.
  • the first electrode 20a and the second electrode 20b are the same as or different from each other, and each independently aluminum (Al), zinc (Zn), copper (Cu), nickel (Ni), and cobalt. At least one metal of (Co) can be used.
  • nickel, gold, silver, titanium, etc. may be further included. Its size can also be adjusted in various ways.
  • it may be a copper (Cu) electrode.
  • the first electrode 20a and the second electrode 20b may be patterned in a predetermined shape, and the shape is not particularly limited.
  • a method for patterning the first electrode 20a and the second electrode 20b a conventionally known patterning method may be used without limitation. For example, a lift-off semiconductor process, a deposition method, a photolithography method, etc. may be used.
  • thermoelectric legs 30 are interposed between the first electrode 20a and the second electrode 20b.
  • the thermoelectric leg 30 includes a plurality of P-type thermoelectric legs 30a and N-type thermoelectric legs 30b, respectively, which are alternately disposed in one direction. As described above, the P-type thermoelectric leg 30a and the N-type thermoelectric leg 30b adjacent in one direction are electrically connected in series with the first electrode 20a and the second electrode 20b, respectively. Each of these thermoelectric legs 30a and 30b includes a thermoelectric semiconductor substrate.
  • thermoelectric semiconductor included in the thermoelectric leg 30 may be formed of a conventional thermoelectric material in the art that generates electricity when a temperature difference occurs at both ends when electricity is applied, or when a temperature difference occurs at both ends, and the thermoelectric As long as the material has a regular pore size and porosity having a porosity, it is not particularly limited to a component thereof.
  • thermoelectric semiconductors including at least one element selected from the group consisting of a transition metal, a rare earth element, a group 13 element, a group 14 element, a group 15 element, and a group 16 element may be used.
  • examples of rare earth elements include Y, Ce, La, and the like
  • examples of transition metals include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu
  • It may be one or more of Zn, Ag, and Re
  • examples of the group 13 element may include at least one of B, Al, Ga, and In
  • examples of the group 14 element include C, Si, Ge, Sn, and Pb.
  • examples of the group 15 elements may be at least one of P, As, Sb, and Bi
  • examples of the group 16 elements may include one or more of S, Se, and Te.
  • thermoelectric semiconductors include bismuth (Bi), telerium (Te), cobalt (Co), samarium (Sb), indium (In), and cerium (Ce) having a composition containing at least two or more of cerium (Ce). and, non-limiting examples thereof include Bi-Te-based, Co-Sb-based, Pb-Te-based, Ge-Tb-based, Si-Ge-based, Sb-Te-based, Sm-Co-based, transition metal silicide-based, and Suku. Terdite (Skuttrudite)-based, silicide (Silicide)-based, half whistler (Half heusler), or a combination thereof, and the like.
  • thermoelectric semiconductor a (Bi,Sb) 2 (Te, Se) 3 thermoelectric semiconductor in which Sb and Se are used as dopants may be exemplified, and as the Co-Sb-based thermoelectric semiconductor, CoSb may be exemplified.
  • Three -type thermoelectric semiconductor can be exemplified, and AgSbTe 2 and CuSbTe 2 can be exemplified as the Sb-Te-based thermoelectric semiconductor, and PbTe, (PbTe)mAgSbTe 2 and the like can be exemplified as the Pb-Te-based thermoelectric semiconductor.
  • it may be composed of a Bi-Te-based or CoSb-based thermoelectric material.
  • thermoelectric leg 30 including the P-type thermoelectric leg 30a and the N-type thermoelectric leg 30b may be formed in a predetermined shape, for example, a rectangular parallelepiped shape by a method such as cutting, and applied to a thermoelectric element.
  • thermoelectric element 100 includes: between the first electrode 20a and the thermoelectric leg 30 ; and a bonding material 40 disposed between at least one, preferably both, of the thermoelectric leg 30 and the second electrode 20b.
  • bonding material 40 conventional bonding material components known in the art may be used without limitation, and Sn-based solder may be used as an example.
  • the bonding material 40 may include Sn; A first Sn-based solder composition comprising at least one of Pb, Al, and Zn as a first metal;
  • the first solder may be formed of a Sn-based second solder composition including a second metal of at least one of Ni, Co, and Ag.
  • the bonding material 40 may include a metal powder having a dendrite shape in a conventional Sn-based solder known in the art.
  • Such a metal dendrite is a conductive metal particle having a single main axis and having a shape in which a plurality of branched phases branch vertically or obliquely from the main axis and grow two-dimensionally or three-dimensionally.
  • shaft represents the rod-shaped part used as the base from which several branches branch.
  • the average branched length of these metal dendrites is not particularly limited, and may be, for example, 5 to 50 ⁇ m, preferably 5 to 30 ⁇ m.
  • the length of the major axis of the main axis means the total length of the main axis, and may be 5 to 50 ⁇ m, specifically 5 to 30 ⁇ m.
  • the longest branching length among the plurality of branched phases may be 5 to 30 ⁇ m, and specifically, 10 to 25 ⁇ m.
  • the number of branches (number of branches/long diameter) with respect to the major axis of the main axis may be 0.5 to 10 pieces/ ⁇ m, specifically 1 to 8 pieces/ ⁇ m.
  • the average particle diameter (D 50 ) of the metal dendrites refers to a two-dimensional size including the major axis length of the dendrites, and may be, for example, 5 to 50 ⁇ m, specifically 5 to 30 ⁇ m.
  • the main axis thickness of the dendrite may be 0.3 to 5.0 ⁇ m.
  • the metal dendrite has a higher specific surface area than the spherical metal particles as it has the above-described structural characteristics.
  • the metal dendrite may have a specific surface area measured by BET measurement of 0.4 to 3.0 m 2 /g, specifically 0.5 to 2.0 m 2 /g.
  • the apparent density of the metal dendrite may be 0.5 to 1.5 g/cm 3 , and an oxygen content of 0.35% or less is suitable.
  • the metal dendrite is not particularly limited to the metal material to be used as long as the above-described structural characteristics and physical properties are satisfied.
  • copper dendrite (Cu dendrite), silver (Ag) coated copper dendrite (Ag coated Cu dendrite), or a mixture thereof may be used.
  • copper (Cu) is preferable because it is economical as well as similar in electrical conductivity to silver (Ag).
  • the content of the metal dendrite is not particularly limited, and may be included, for example, in an amount of 1 to 40% by weight, preferably 5 to 30% by weight, based on the total weight of the bonding material.
  • the content of such copper dendrite is 1 to 40 weight based on the total weight of the bonding material. %, preferably 5 to 30% by weight.
  • metal dendrites can be used alone as a bonding material component, and in addition, metal powders having various materials, particle sizes, and/or shapes are further included and mixed as a bonding material component also falls within the scope of the present invention.
  • metal powders such as the above-described metal dendrite and spherical shape, needle shape, flake shape, and amorphous shape may be mixed.
  • Sn-based solder mixed with the above-described metal dendrite may use a conventional Sn-based solder component known in the art.
  • the Sn-based solder is Sn; It may have a composition including at least one metal among Pb, Al, and Zn. .
  • thermoelectric element 100 of the present invention may be disposed between the first electrode 20a and the thermoelectric leg 30; and a diffusion barrier layer (not shown) disposed between the thermoelectric leg 30 and the second electrode 20b.
  • a diffusion barrier layer can be used without limitation, a conventional component known in the art, for example, tantalum (Ta), tungsten (W), molybdenum (Mo), and includes at least one selected from the group consisting of titanium (Ti) can do.
  • the first electrode 20a and the second electrode 20b may be electrically connected to a power supply source.
  • a DC voltage When a DC voltage is applied from the outside, the holes of the p-type thermoelectric leg 30a and the electrons of the n-type thermoelectric leg 30b move, thereby generating heat and endothermic heat at both ends of the thermoelectric leg.
  • thermoelectric element 100 in the thermoelectric element 100 according to another embodiment of the present invention, at least one of the first electrode 20a and the second electrode 20b may be exposed to a heat source. When heat is supplied by an external heat source, electrons and holes move and current flows in the thermoelectric element to generate electricity.
  • thermoelectric element may be manufactured according to a method known in the art.
  • a manufacturing method For an embodiment of such a manufacturing method, (a) preparing two insulating substrates; (b) forming a first electrode and a second electrode on one surface of the two insulating substrates, respectively; and (c) disposing the first electrode and the second electrode to face each other, arranging a plurality of porous thermoelectric legs between them, and bonding them using the bonding material.
  • the manufacturing method is not limited only by the following method or sequence, and steps of each process may be modified or selectively mixed as needed.
  • thermoelectric leg using a thermoelectric material As an example of a method of manufacturing a thermoelectric leg using a thermoelectric material in the manufacturing method, a Bi-Te or Skuttrudite-based thermoelectric material is melted using RSP, then a metal ribbon is manufactured, and the metal The ribbon and the thermally decomposable polymer are mixed in a predetermined range and then pulverized, and the pulverized product is molded and hot press sintered to form a porous sintered body. Then, slicing is performed according to the target thickness, and lapping is performed according to the final thickness to adjust the height of the material to within 1/100. After surface coating of Co, Ni, Cr, and W is performed on the surface of the thermoelectric material whose step is controlled, dicing is finally performed according to the size of the material to manufacture the thermoelectric leg.
  • a ceramic substrate or a metal substrate is used as the substrate, and a Cu electrode pattern is formed on one surface of the substrate, and then is fixed by heat treatment.
  • an insulating resin or a mixture of the insulating resin and a ceramic filler (powder) is applied on one surface of the metal substrate on which the electrode is disposed to prevent conduction.
  • thermoelectric legs are disposed and bonded between the first electrode and the second electrode using the thermoelectric legs and the substrate prepared as described above.
  • a bonding material include Sn-based solder; Alternatively, a Sn-based solder paste including the Sn solder and metal dendrite in a predetermined mixing ratio is applied.
  • a bonding material paste is applied to a predetermined thickness according to the pattern of the first electrode 20a, and n-type and p-type thermoelectric legs are arranged thereon.
  • the final configuration is completed by placing the previously manufactured n-type and p-type thermoelectric legs in an arrangement in a state where only the bonding material is applied. Then, after heat treatment at 300 to 500 °C final bonding, the wire is connected to complete the manufacture of the thermoelectric element.
  • thermoelectric leg and/or a thermoelectric element including the same may be provided in a thermoelectric cooling system, a thermoelectric power generation system, and/or a thin-film sensor, and may be applied to at least one of cooling, power generation, and thin-film sensor.
  • thermoelectric power generation system refers to a conventional system that generates power using a temperature difference, and for example, a waste heat furnace, a vehicle thermoelectric power generation system, a solar thermoelectric power generation system, and the like.
  • thermoelectric cooling system may include, but is not limited to, a micro cooling system, a general-purpose cooling device, an air conditioner, a waste heat power generation system, and the like.
  • the thin-film sensor includes all sensor fields using micro-power, such as a thin-film thermoelectric element.
  • thermoelectric power generation system the thermoelectric cooling system, and/or the thin film type sensor
  • thermoelectric cooling system the thermoelectric cooling system
  • thin film type sensor the thermoelectric cooling system
  • thermoelectric cooling system the thermoelectric cooling system
  • thin film type sensor the thermoelectric cooling system
  • the thin film type sensor the thermoelectric cooling system
  • thermoelectric material containing Bi, Te, Sb, and Se having a high purity of 4N or higher was prepared in the form of a mass of about 2-5 mm. In the case of p-type, it was made to have a ternary system such as Bi, Te, and Sb.
  • a ⁇ 30 * 100 mm master alloy ingot was prepared by charging the thermoelectric material with a quartz tube (Quartz) into the locking furnace, stirring and dissolving at 650 to 750 ° C for 2 to 4 hours at a rate of 10 times/min. After that, the master alloy ingot is charged into a nozzle installed in the melt spinning equipment and completely melted at a temperature of about 700 ° C.
  • a Bi-Te-based metal ribbon was formed as it was rapidly cooled in contact with the surface of a rotating copper wheel (Cu wheel). At this time, the rotational speed of the copper wheel proceeded to 1000 rpm. Thereafter, the formed metal ribbon and a thermally decomposable polymer [polymethyl methacrylate (PMMA) having an average particle diameter of 5 ⁇ m] were mixed and pulverized to an average particle diameter of 100 ⁇ m or less using a ball mill method in an argon (Ar) atmosphere. The pulverized product was heated to about 525° C.
  • PMMA polymethyl methacrylate
  • thermoelectric material having a high density of 99% or more was manufactured.
  • thermoelectric material was prepared.
  • Example 1 pyrolytic polymer Addition amount (parts by weight) Average particle size ( ⁇ m) Comparative Example 1 0.00 - Example 1 0.10 5.00
  • Example 2 20.00
  • Example 3 50.00
  • Example 4 0.50
  • Example 5 20.00
  • Example 6 50.00
  • Example 7 1.00 5.00
  • Example 8 20.00
  • Example 9 50.00
  • Example 10 2.00 5.00
  • Example 11 20.00
  • Example 12 50.00
  • thermoelectric material containing Bi, Te, Sb, and Se having a high purity of 4N or higher was prepared in the form of a mass of about 2-5 mm. In the case of p-type, it was made to have a ternary system such as Bi, Te, and Sb.
  • a ⁇ 30 * 100 mm master alloy ingot was prepared by charging the thermoelectric material with a quartz tube (Quartz) into a locking furnace, and then stirring and dissolving at 650 to 750 ° C for 2 to 4 hours at a rate of 10 times/min. After that, the master alloy ingot is charged into a nozzle installed in the melt spinning equipment and completely melted at a temperature of about 700 ° C.
  • a resistance heating element a structure that surrounds the nozzle as a graphite heater
  • a Bi-Te-based metal ribbon was formed as it was rapidly cooled in contact with the surface of a rotating copper wheel (Cu wheel). At this time, the rotational speed of the copper wheel proceeded to 1000rpm.
  • the formed metal ribbon was pulverized to have an average particle diameter of 100 ⁇ m or less by using a ball mill method in an argon (Ar) atmosphere.
  • FIG. 3 is an electron micrograph of the thermally decomposable polymer used in Examples 3, 6, 9, and 12 of the present application. It was confirmed that the average particle diameter was about 50 ⁇ m class spherical particles.
  • thermoelectric material prepared in Examples 1 to 12 and Comparative Example 1 were measured by Archimedes' method, respectively, and the results are shown in Table 2.
  • Example 1 pyrolytic polymer Density after sintering (g/cm 3 ) Relative density (%) Addition amount (parts by weight) Average particle size ( ⁇ m) Comparative Example 1 0.00 - 6.84 - Example 1 0.10 5.00 6.82 99.71 Example 2 20.00 6.81 99.56 Example 3 50.00 6.81 99.56 Example 4 0.50 5.00 6.79 99.27 Example 5 20.00 6.78 99.12 Example 6 50.00 6.76 98.83 Example 7 1.00 5.00 6.77 98.98 Example 8 20.00 6.76 98.83 Example 9 50.00 6.72 98.25 Example 10 2.00 5.00 6.50 95.03 Example 11 20.00 6.47 94.59 Example 12 50.00 6.31 92.25
  • thermoelectric materials prepared in Examples 1 to 12 and Comparative Example 1 were measured as follows, and the results are shown in Table 3 and FIGS. 7 to 8, respectively.
  • thermoelectric figure of merit The thermoelectric figure of merit ZT values were compared, and the results are shown in FIG. 8 below. The measured value was compared with the value of 150°C where the power factor and ZT value had the highest value.
  • thermoelectric element of the present invention including the porous thermoelectric material reduces the thermal conductivity without significantly lowering the electrical conductivity and Seebeck coefficient due to the regular pore structure contained in the thermoelectric material, thereby improving the thermoelectric performance. It was found that further improvement was possible. Specifically, the decrease in electrical resistance and Seebeck coefficient was not significant until the addition amount of the thermally decomposable polymer was 1 part by weight, whereas the decrease in thermal conductivity was relatively large, so that the thermoelectric performance index (ZT) value was 1 The maximum value was shown when adding parts by weight. In addition, it was found that when particles having an average particle diameter of about 50 ⁇ m were used as the thermally decomposable polymer, the maximum value of the thermoelectric performance index compared to the same amount added was shown.

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Abstract

La présente invention concerne un matériau thermoélectrique poreux comprenant des pores fins, un procédé de production associé et un élément thermoélectrique comprenant le matériau thermoélectrique poreux et présentant ainsi une performance thermoélectrique améliorée. La présente invention permet de réguler facilement la taille de pores inclus dans un matériau thermoélectrique et la porosité de ce dernier et, du fait des pores réguliers inclus dans le matériau thermoélectrique produit, ne réduit pas de manière significative la conductivité électrique et le coefficient Seebeck et réduit pourtant de manière significative la conductivité thermique, et peut ainsi améliorer une performance thermoélectrique.
PCT/KR2019/016865 2019-12-02 2019-12-02 Procédé de production d'un matériau thermoélectrique poreux et élément thermoélectrique comprenant un matériau thermoélectrique poreux Ceased WO2021112268A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004225118A (ja) * 2003-01-23 2004-08-12 Yamaha Corp 熱電材料インゴット、その製造方法及び熱電モジュールの製造方法
KR101090868B1 (ko) * 2004-12-24 2011-12-08 재단법인 포항산업과학연구원 다공성 열전소자의 제조방법
JP2015053466A (ja) * 2013-08-07 2015-03-19 株式会社Ｎｔｔファシリティーズ 熱電材料、熱電材料の製造方法及び熱電変換装置
KR20180016717A (ko) * 2016-08-05 2018-02-19 한국전자통신연구원 열전소자의 제조방법
KR20190013468A (ko) * 2017-07-31 2019-02-11 삼성전자주식회사 열전재료 잉크, 이를 이용하여 제조된 열전소자 및 열전장치, 및 상기 열전장치의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004225118A (ja) * 2003-01-23 2004-08-12 Yamaha Corp 熱電材料インゴット、その製造方法及び熱電モジュールの製造方法
KR101090868B1 (ko) * 2004-12-24 2011-12-08 재단법인 포항산업과학연구원 다공성 열전소자의 제조방법
JP2015053466A (ja) * 2013-08-07 2015-03-19 株式会社Ｎｔｔファシリティーズ 熱電材料、熱電材料の製造方法及び熱電変換装置
KR20180016717A (ko) * 2016-08-05 2018-02-19 한국전자통신연구원 열전소자의 제조방법
KR20190013468A (ko) * 2017-07-31 2019-02-11 삼성전자주식회사 열전재료 잉크, 이를 이용하여 제조된 열전소자 및 열전장치, 및 상기 열전장치의 제조방법

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