[go: up one dir, main page]

WO2018110794A1 - Élément thermoélectrique retenu par oxydation et volatilisation et son procédé de fabrication - Google Patents

Élément thermoélectrique retenu par oxydation et volatilisation et son procédé de fabrication Download PDF

Info

Publication number
WO2018110794A1
WO2018110794A1 PCT/KR2017/009122 KR2017009122W WO2018110794A1 WO 2018110794 A1 WO2018110794 A1 WO 2018110794A1 KR 2017009122 W KR2017009122 W KR 2017009122W WO 2018110794 A1 WO2018110794 A1 WO 2018110794A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide film
thermoelectric
temperature
group
thermoelectric material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2017/009122
Other languages
English (en)
Korean (ko)
Inventor
이순일
서원선
맹은지
두 응웬반
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Korea Institute of Ceramic Engineering and Technology KICET
Original Assignee
Korea Institute of Ceramic Engineering and Technology KICET
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Institute of Ceramic Engineering and Technology KICET filed Critical Korea Institute of Ceramic Engineering and Technology KICET
Publication of WO2018110794A1 publication Critical patent/WO2018110794A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

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

Definitions

  • the present invention relates to a thermoelectric element for preventing oxidation and volatilization of a thermoelectric material used in the medium and high temperature regions, and more particularly, to the thermoelectric material used at high temperature, due to oxidation and volatilization of some elements. Its performance is reduced and its reliability is lowered. Unlike a conventional method of manufacturing an oxidation / volatile volatilization film using surface coating technology, a small amount of oxygen active element is used to maintain the thermoelectric performance of the thermoelectric material while maintaining a self-protection barrier on the surface. It relates to a thermoelectric element and a manufacturing method which can prevent oxidation and volatilization at high temperature as well as medium temperature.
  • Thermoelectric phenomena were first discovered by German physicist TJSeebeck, and in a circuit containing two different conductors, a current or voltage is generated by applying different temperatures to the contacts between the conductors. The heat flow from place to cold creates current. This phenomenon is called the Seebeck Effect.
  • thermoelectric phenomenon which is that when direct current flows through a circuit consisting of different conductors, One side is heated while the other is cooled. This is called the Peltier Effect.
  • thermoelectric coolers which are called by various names such as thermoelectric modules, Peltier elements, thermoelectric coolers (TEC), and thermoelectric modules (TEM), are small heat pumps (heat pumps). Absorbs and heats high temperature heat source).
  • TEC thermoelectric coolers
  • TEM thermoelectric modules
  • thermoelectric power generation technology having advantages such as thermoelectric power generation using thermoelectric elements and recycling of waste thermal energy using thermoelectric elements has emerged as a new field of interest.
  • thermoelectric devices exhibit low utilization compared to their potential due to low thermoelectric material properties, oxidation and volatilization of thermoelectric materials used in the medium and high temperature ranges, and therefore, research on new thermoelectric devices is required.
  • most of the thermoelectric materials used at medium and high temperatures are degraded due to oxidation and volatilization of some elements, their performance is reduced and reliability is low.
  • the problem to be solved by the present invention is a protective film (self-protection barrier) that can suppress oxidation and volatilization not only in the medium temperature region (for example 200 to 450 °C) but also in the high temperature region (for example 400 to 1000 °C)
  • a protective film self-protection barrier
  • a protective film capable of suppressing oxidation and volatilization not only in the medium temperature region (for example, 200 to 450 ° C) but also in the high temperature region (for example, 400 to 1000 ° C).
  • a protective film capable of suppressing oxidation and volatilization not only in the medium temperature region (for example, 200 to 450 ° C) but also in the high temperature region (for example, 400 to 1000 ° C).
  • the present invention includes a thermoelectric material and a protective film formed on the thermoelectric material, wherein the protective film includes a first oxide film formed on the thermoelectric material and a second oxide film formed on the first oxide film,
  • the first oxide film is an oxide film containing at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg and Y provides a thermoelectric element.
  • thermoelectric material may also include at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y.
  • the oxygen active element contained in the first oxide film and the thermoelectric material is preferably contained in the thermoelectric element 0.01 to 2.0wt%.
  • thermoelectric material may be a skutterudite-based, chalcogenide-based, silicide-based, half-heusler-based, clasrate-based, zintl-based, and the like. It may include one or more thermoelectric materials selected from the group consisting of oxides.
  • the first oxide film may include an M x (A, B) y O z- based oxide film, wherein M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y, wherein x Is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 3, x and z vary depending on the valence of the oxygen active element, and A is Bi, Sb, Fe, Ni , Zn, Na, Ca and Pb may be at least one material selected from the group consisting of, B may be at least one material selected from the group consisting of Co, Te and Se.
  • M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y
  • x Is in the range of 1 to 3 y is in the range of 0 to 1
  • z is in the range of 1 to 3
  • x and z vary depending on the valence of the oxygen active element
  • A is
  • the first oxide film may include a first oxide layer having 0 ⁇ y ⁇ 0.2 and a second oxide layer having 0.2 ⁇ y ⁇ 1.
  • the second oxide film may include an A x B y O z based oxide film
  • A may be at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb
  • B may be at least one material selected from the group consisting of Co, Te, and Se, wherein x is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 6, and z May vary depending on the valence of A and B.
  • thermoelectric material powder thermoelectric material powder
  • oxygen active element powder is one or more oxygen actives selected from the group consisting of Al, Hf, Ce, Mg and Y
  • the protective film includes a first oxide film formed on the thermoelectric material and a second oxide film formed on the first oxide film, wherein the first oxide film is formed of Al, Hf, Ce, Mg, and Y.
  • the oxygen active element powder is preferably contained in the mixed powder 0.01 to 2.0wt%.
  • thermoelectric material powder In the forming of the mixed powder, it is preferable to use a dry powder mixing method while minimizing air contact in a glove box when mixing the thermoelectric material powder and the oxygen active element powder.
  • the sintering may use at least one method selected from the group consisting of Spark Plasma Sintering and Hot Press, and the sintering is preferably performed in a vacuum atmosphere at a temperature of 400 to 1100 ° C. Do.
  • the first oxide film may include an M x (A, B) y O z- based oxide film, wherein M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y, wherein x Is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 3, x and z vary depending on the valence of the oxygen active element, and A is Bi, Sb, Fe, Ni , Zn, Na, Ca and Pb may be at least one material selected from the group consisting of, B may be at least one material selected from the group consisting of Co, Te and Se.
  • M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y
  • x Is in the range of 1 to 3 y is in the range of 0 to 1
  • z is in the range of 1 to 3
  • x and z vary depending on the valence of the oxygen active element
  • A is
  • the first oxide film may include a first oxide layer having 0 ⁇ y ⁇ 0.2 and a second oxide layer having 0.2 ⁇ y ⁇ 1.
  • the second oxide film may include an A x B y O z based oxide film
  • A may be at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb
  • B may be at least one material selected from the group consisting of Co, Te, and Se, wherein x is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 6, and z May vary depending on the valence of A and B.
  • the heat treatment is a step of heating up to a second temperature of 500 to 650 °C at a temperature lower than the first temperature of 400 to 450 °C oxidized the element A and the B element and maintaining the heat treatment at the second temperature It may include.
  • the heat treatment is a step of heating up to a first temperature of 400 ⁇ 450 °C oxidizing the element A and the B element, maintaining the heat treatment at the first temperature and 500 to 650 °C higher than the first temperature It may include the step of raising the temperature up to a second temperature and the heat treatment by maintaining at the second temperature.
  • the heat treatment is a step of heating up at a first temperature increase rate up to a first temperature of 400 ⁇ 450 °C oxidized A and B elements, and the second temperature of 500 to 650 °C higher than the first temperature It may include the step of heating up at a second temperature increase rate slower than the first temperature increase rate and the heat treatment by maintaining at the second temperature.
  • thermoelectric material powder is Skutterudite-based, Chalcogenide-based, Silicide-based, Half-Heusler-based, Clasrate-based, Zintl-based And at least one thermoelectric material selected from the group consisting of oxides.
  • thermoelectric element of the present invention can suppress oxidation and volatilization not only in the middle temperature region (eg, 200 to 450 ° C) but also in the high temperature region (eg, 400 to 1000 ° C).
  • thermoelectric materials used at high temperature are oxidized and volatilization of some elements, and their performance is reduced and reliability is low. Unlike the conventional method of manufacturing an oxidation / volatile volatilization film using surface coating technology, they have excellent durability and a small amount of oxygen.
  • the active element is used to form a protective film (self-protection barrier) on the surface while maintaining the thermoelectric performance of the thermoelectric material to prevent oxidation and volatilization at high temperature as well as medium temperature.
  • a protective film (self-protection barrier) capable of suppressing oxidation and volatilization can be formed on the surface of the thermoelectric material not only in the medium temperature region (for example, 200 to 450 ° C) but also in the high temperature region (for example, 400 to 1000 ° C).
  • the protective film can be formed by a simple process without a complicated coating process. Since the first oxide film and the second oxide film are formed in duplicate on the thermoelectric material as a protective film, oxidation and volatilization can be suppressed not only at medium temperature (eg, 200 to 450 ° C.) but also at high temperature (eg, 400 to 1000 ° C.). .
  • thermoelectric module The formation of a protective film (self-protection barrier) using an oxygen active element can form a very uniform and dense protective film without additional processes such as dip coating or spray coating. ⁇ It can prevent high temperature oxidation and volatilization, which is the limit of application of high temperature thermoelectric element, and enormous ripple effect is expected to commercialize thermoelectric element.
  • the protective film by the conventional coating method it is impossible to completely coat the high-temperature exposed portion of the thermoelectric material, but in the case of the self-protection barrier according to the present invention, it is possible to sufficiently suppress oxidation and volatilization, and thus high temperature reliability. In addition, it can provide more diversity in terms of the design of thermoelectric modules.
  • thermoelectric device of the present invention given a temperature difference between both ends of a thermoelectric element, a thermoelectric power generation using a voltage is generated by a Seebeck effect, and one side generates heat when a DC current is applied between both ends of a material. And it can be applied to thermoelectric cooling (Peltier) effect using the Peltier effect (other side endotherm).
  • thermoelectric element thermoelectric element
  • FIG. 2 is a view illustrating a heat treatment process according to a first example.
  • FIG 3 is a view illustrating a heat treatment process according to a second example.
  • FIG. 4 is a diagram illustrating a heat treatment process according to a third example.
  • thermoelectric device 5 to 10 are diagrams for showing the change in surface oxidation with the heat treatment time for the thermoelectric device manufactured without the addition of the oxygen active element according to Experimental Example 1.
  • FIG. 11 is a view showing a change in the thickness of the surface oxide film according to the heat treatment time for a thermoelectric device manufactured without adding an oxygen active element according to Experimental Example 1.
  • FIG. 11 is a view showing a change in the thickness of the surface oxide film according to the heat treatment time for a thermoelectric device manufactured without adding an oxygen active element according to Experimental Example 1.
  • FIG. 12 is a view showing an oxide film form when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C. for 10 hours.
  • FIG. 13 is a view showing an oxide film form when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C. for 50 hours.
  • FIG. 14 is a view showing an oxide film form when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C. for 80 hours.
  • FIG. 15 is a view showing an oxide film form when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C. for 100 hours.
  • FIG. 16 shows SEM and EDS analysis results of the oxide film formed on the thermoelectric device when the thermoelectric device manufactured by adding 1 wt% of Al as an oxygen active element was exposed to air at 600 ° C. for 50 hours according to Experimental Example 2.
  • FIG. 17 is a view showing a change in oxide film thickness with exposure time when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C.
  • FIG. 17 is a view showing a change in oxide film thickness with exposure time when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C.
  • thermoelectric material 100: thermoelectric material
  • thermoelectric device includes a thermoelectric material and a protective film formed on the thermoelectric material, wherein the protective film is formed on the first oxide film and the first oxide film on the thermoelectric material. And a second oxide film formed, wherein the first oxide film is an oxide film including at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y.
  • a method of manufacturing a thermoelectric device includes preparing a thermoelectric material powder, mixing the thermoelectric material powder and an oxygen active element powder to form a mixed powder, and Sintering the mixed powder and heat-treating the sintered body formed by the sintering in an oxidizing atmosphere to form a protective film on the thermoelectric material, wherein the oxygen-active element powder is Al, Hf, Ce, Mg, and Y.
  • At least one oxygen-active element selected from the group consisting of: wherein the protective film comprises a first oxide film formed on the thermoelectric material, and a second oxide film formed on the first oxide film, wherein the first oxide film is Al, Hf It is characterized in that the oxide film containing at least one oxygen active element selected from the group consisting of, Ce, Mg and Y.
  • thermoelectric materials are problematic due to oxidation and volatilization.
  • most of thermoelectric materials (medium and high temperature thermoelectric materials) used at medium and high temperatures are degraded due to oxidation and volatilization of some elements. And since the reliability is low, there is a need to solve this problem.
  • the present invention provides a thermoelectric element including a protective film (self-protection barrier) capable of suppressing oxidation and volatilization in a high temperature region (for example, 400 to 1000 ° C) as well as a medium temperature region (for example, 200 to 450 ° C).
  • a protective film self-protection barrier
  • a medium temperature region for example, 200 to 450 ° C.
  • thermoelectric element used in the medium and high temperature region.
  • the present invention provides a thermoelectric material for a protective film (self-protection barrier) capable of suppressing oxidation and volatilization not only in the medium temperature region (for example, 200 to 450 ° C) but also in the high temperature region (for example, 400 to 1000 ° C).
  • a method for manufacturing a thermoelectric element which can be formed on a surface and can form the protective film in a simple process without a complicated coating process.
  • thermoelectric element' is used to mean a thermoelectric material and a protective film (self-protection barrier) formed thereon.
  • thermoelectric device includes a thermoelectric material and a protective film formed on the thermoelectric material, wherein the protective film is formed on the first oxide film and the first oxide film on the thermoelectric material. And a second oxide film formed, wherein the first oxide film is an oxide film including at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y.
  • thermoelectric material may also include at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y.
  • the oxygen active element contained in the first oxide film and the thermoelectric material is preferably contained in the thermoelectric element 0.01 to 2.0wt%.
  • thermoelectric material may be a skutterudite-based, chalcogenide-based, silicide-based, half-heusler-based, clasrate-based, zintl-based, and the like. It may include one or more thermoelectric materials selected from the group consisting of oxides.
  • the first oxide film may include an M x (A, B) y O z- based oxide film, wherein M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y, wherein x Is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 3, x and z vary depending on the valence of the oxygen active element, and A is Bi, Sb, Fe, Ni , Zn, Na, Ca and Pb may be at least one material selected from the group consisting of, B may be at least one material selected from the group consisting of Co, Te and Se.
  • M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y
  • x Is in the range of 1 to 3 y is in the range of 0 to 1
  • z is in the range of 1 to 3
  • x and z vary depending on the valence of the oxygen active element
  • A is
  • the first oxide film may include a first oxide layer having 0 ⁇ y ⁇ 0.2 and a second oxide layer having 0.2 ⁇ y ⁇ 1.
  • the second oxide film may include an A x B y O z based oxide film
  • A may be at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb
  • B may be at least one material selected from the group consisting of Co, Te, and Se, wherein x is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 6, and z May vary depending on the valence of A and B.
  • a method of manufacturing a thermoelectric device includes preparing a thermoelectric material powder, mixing the thermoelectric material powder and an oxygen active element powder to form a mixed powder, and Sintering the mixed powder and heat-treating the sintered body formed by the sintering in an oxidizing atmosphere to form a protective film on the thermoelectric material, wherein the oxygen-active element powder is Al, Hf, Ce, Mg, and Y.
  • At least one oxygen-active element selected from the group consisting of: wherein the protective film comprises a first oxide film formed on the thermoelectric material, and a second oxide film formed on the first oxide film, wherein the first oxide film is Al, Hf It is characterized in that the oxide film containing at least one oxygen active element selected from the group consisting of, Ce, Mg and Y.
  • the oxygen active element powder is preferably contained in the mixed powder 0.01 to 2.0wt%.
  • thermoelectric material powder In the forming of the mixed powder, it is preferable to use a dry powder mixing method while minimizing air contact in a glove box when mixing the thermoelectric material powder and the oxygen active element powder.
  • the sintering may use at least one method selected from the group consisting of Spark Plasma Sintering and Hot Press, and the sintering is preferably performed in a vacuum atmosphere at a temperature of 400 to 1100 ° C. Do.
  • the first oxide film may include an M x (A, B) y O z- based oxide film, wherein M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y, wherein x Is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 3, x and z vary depending on the valence of the oxygen active element, and A is Bi, Sb, Fe, Ni , Zn, Na, Ca and Pb may be at least one material selected from the group consisting of, B may be at least one material selected from the group consisting of Co, Te and Se.
  • M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y
  • x Is in the range of 1 to 3 y is in the range of 0 to 1
  • z is in the range of 1 to 3
  • x and z vary depending on the valence of the oxygen active element
  • A is
  • the first oxide film may include a first oxide layer having 0 ⁇ y ⁇ 0.2 and a second oxide layer having 0.2 ⁇ y ⁇ 1.
  • the second oxide film may include an A x B y O z based oxide film
  • A may be at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb
  • B may be at least one material selected from the group consisting of Co, Te, and Se, wherein x is in the range of 1 to 3, y is in the range of 0 to 1, z is in the range of 1 to 6, and z May vary depending on the valence of A and B.
  • the heat treatment is a step of heating up to a second temperature of 500 to 650 °C at a temperature lower than the first temperature of 400 to 450 °C oxidized the element A and the B element and maintaining the heat treatment at the second temperature It may include.
  • the heat treatment is a step of heating up to a first temperature of 400 ⁇ 450 °C oxidizing the element A and the B element, maintaining the heat treatment at the first temperature and 500 to 650 °C higher than the first temperature It may include the step of raising the temperature up to a second temperature and the heat treatment by maintaining at the second temperature.
  • the heat treatment is a step of heating up at a first temperature increase rate up to a first temperature of 400 ⁇ 450 °C oxidized A and B elements, and the second temperature of 500 to 650 °C higher than the first temperature It may include the step of heating up at a second temperature increase rate slower than the first temperature increase rate and the heat treatment by maintaining at the second temperature.
  • thermoelectric material powder is Skutterudite-based, Chalcogenide-based, Silicide-based, Half-Heusler-based, Clasrate-based, Zintl-based And at least one thermoelectric material selected from the group consisting of oxides.
  • thermoelectric device according to a preferred embodiment of the present invention will be described in more detail.
  • thermoelectric element thermoelectric element
  • thermoelectric element may include a thermoelectric material 100 and a protective film (self-protection) formed on the thermoelectric material 100. barrier)) 200.
  • the thermoelectric material 100 is a skutterudite-based, chalcogenide-based, silicide-based, half-heusler-based, clasrate-based, zintl, etc. It may include at least one thermoelectric material selected from the group consisting of) and oxide-based.
  • the skutterudite-based thermoelectric material may be a material having an AB 3 -based composition (Co, Ni, Fe, Ir) (Sb, P, As) 3 and the like.
  • A may be at least one material selected from the group consisting of Co, Ni, Ir, and Fe
  • B may be at least one material selected from the group consisting of Sb, P, and As.
  • CoSb 3 may be used as an example of the skutterudite thermoelectric material.
  • the chalcogenide-based thermoelectric material is a (Bi, Sb) 2 (Te, Se) 3- based thermoelectric material, M (Bi, Sb) (Te, Se) 2 (where M is Ag, Cu, etc.) thermoelectric material, Pb-Te system thermoelectric material etc. are mentioned as an example.
  • the (Bi, Sb) 2 (Te, Se) 3- based thermoelectric material is Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 Se 3 , Sb 2 Se 3 , Bi x Sb 2 - xTe 3 (where X is greater than 2 Small real numbers), Bi 2 Se x Te 3 -X (where X is a real number less than 3), and Sb 2 Se x Te 3-X (where X is a real number less than 3).
  • thermoelectric materials examples include AgSbTe 2 , CuSbTe 2 , and the like.
  • Examples of the Pb-Te-based thermoelectric material may include PbTe.
  • the silicide-based thermoelectric material may be SiGe or the like.
  • Zintl-based thermoelectric material examples include Ca x Yb 1-x Zn 2 Sb 2 .
  • oxide-based thermoelectric material examples include ZnO, NaCo 2 O 4 , Ca 3 Co 4 O 9 , and the like.
  • the passivation layer 200 includes a first oxide layer 210 formed on the thermoelectric material 100 and a second oxide layer 220 formed on the first oxide layer 210.
  • the first oxide film 210 is an oxide film including at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y.
  • the first oxide film may have a thickness of 0.2 to 1 ⁇ m.
  • the first oxide film 210 is an oxide film including an oxygen active element and a component of a thermoelectric material.
  • the first oxide film may include an M x (A, B) y O z based oxide film.
  • M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg and Y, x is in the range of 1 to 3, y is in the range of 0 to 1, and z is in the range of 1 to 3 X and z vary according to the valence of the oxygen active element, and A may be at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb, wherein B is It may be one or more materials selected from the group consisting of Co, Te and Se.
  • the first oxide film 210 may be mixed with an amorphous phase and a crystalline phase, and may include a first oxide layer 210a having 0 ⁇ y ⁇ 0.2 and a second oxide layer 210b having 0.2 ⁇ y ⁇ 1. .
  • the first oxide film 210 is an oxide film formed by oxidizing an oxygen active element.
  • the first oxide layer 210a is an Al 2 - y Sb y O 3 (0 ⁇ y ⁇ 0.2) oxide film, in which amorphous and crystalline are mixed.
  • the second oxide layer 210b may be an Al 2 -y Sb y O 3 (0.2 ⁇ y ⁇ 1) oxide film and a layer in which crystalline and amorphous materials are mixed.
  • the first oxide layer may have a thickness of 5 to 100 nm.
  • the thermoelectric material 100 may include one or more oxygen active elements selected from the group consisting of Al, Hf, Ce, Mg, and Y, and are contained in the first oxide film 210 and the thermoelectric material 100.
  • the oxygen-active element thus contained is preferably contained in the thermoelectric element 0.01 to 2.0wt%.
  • the second oxide film 220 may have a thickness of about 5 to 30 ⁇ m.
  • the second oxide film may include an A x B y O z based oxide film, wherein A is at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb.
  • B may be at least one material selected from the group consisting of Co, Te, and Se, wherein x is in the range of 1 to 3, y is in the range of 0 to 1, and z is in the range of 1 to 6 Z may vary depending on the valence of A and B.
  • the second oxide film 220 is an oxide film formed by oxidizing a volatile element of the thermoelectric material 100.
  • thermoelectric device According to a preferred embodiment of the present invention, a method of manufacturing a thermoelectric device according to a preferred embodiment of the present invention will be described in more detail.
  • Thermoelectric materials powder is prepared.
  • thermoelectric material powder is Skutterudite-based, Chalcogenide-based, Silicide-based, Half-Heusler-based, Clasrate-based, Zintl-based And at least one thermoelectric material selected from the group consisting of oxides.
  • the skutterudite-based thermoelectric material may be a material having an AB 3 -based composition (Co, Ni, Fe, Ir) (Sb, P, As) 3 and the like.
  • A may be at least one material selected from the group consisting of Co, Ni, Ir, and Fe
  • B may be at least one material selected from the group consisting of Sb, P, and As.
  • CoSb 3 may be used as an example of the skutterudite thermoelectric material.
  • the chalcogenide-based thermoelectric material is a (Bi, Sb) 2 (Te, Se) 3- based thermoelectric material, M (Bi, Sb) (Te, Se) 2 (where M is Ag, Cu, etc.) thermoelectric material, Pb-Te system thermoelectric material etc. are mentioned as an example.
  • the (Bi, Sb) 2 (Te, Se) 3- based thermoelectric material is Bi 2 Te 3 , Sb 2 Te 3 , Bi 2 Se 3 , Sb 2 Se 3 , Bi x Sb 2 - xTe 3 (where X is greater than 2 Small real numbers), Bi 2 Se x Te 3 -X (where X is a real number less than 3), and Sb 2 Se x Te 3-X (where X is a real number less than 3).
  • thermoelectric materials examples include AgSbTe 2 , CuSbTe 2 , and the like.
  • Examples of the Pb-Te-based thermoelectric material may include PbTe.
  • the silicide-based thermoelectric material may be SiGe or the like.
  • Zintl-based thermoelectric material examples include Ca x Yb 1-x Zn 2 Sb 2 .
  • oxide-based thermoelectric material examples include ZnO, NaCo 2 O 4 , Ca 3 Co 4 O 9 , and the like.
  • the thermoelectric material powder and the oxygen active element powder are mixed to form a mixed powder.
  • the oxygen active element powder includes at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y as an oxidizing material.
  • the oxygen active element powder is preferably contained in the mixed powder 0.01 to 2.0wt%. In mixing the thermoelectric material powder and the oxygen active element powder, it is preferable to use a dry powder mixing method while minimizing air contact in a glove box.
  • the mixed powder is sintered.
  • the sintering may use one or more methods selected from the group consisting of Spark Plasma Sintering and Hot Press.
  • the sintering is preferably carried out in a vacuum atmosphere at a temperature of 400 ⁇ 1100 °C.
  • the sintering is preferably carried out for 1 to 120 minutes.
  • a step of cutting the sintered body into a desired size may be added.
  • the sintered body formed by the sintering is heat-treated in an oxidizing atmosphere to form a protective film on the thermoelectric material.
  • the protective film is formed on the thermoelectric material by the heat treatment, and the protective film includes a first oxide film formed on the thermoelectric material and a second oxide film formed on the first oxide film.
  • the oxidizing atmosphere is an atmosphere such as air, oxygen (O 2 ), or the like.
  • the protective film includes a first oxide film formed on the thermoelectric material and a second oxide film formed on the first oxide film.
  • the first oxide film 210 is an oxide film including at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg, and Y.
  • the first oxide film may have a thickness of 0.2 to 1 ⁇ m.
  • the first oxide film 210 is an oxide film including an oxygen active element and a component of a thermoelectric material.
  • the first oxide film may include an M x (A, B) y O z based oxide film.
  • M is at least one oxygen active element selected from the group consisting of Al, Hf, Ce, Mg and Y, x is in the range of 1 to 3, y is in the range of 0 to 1, and z is in the range of 1 to 3 X and z vary according to the valence of the oxygen active element, and A may be at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb, wherein B is It may be one or more materials selected from the group consisting of Co, Te and Se.
  • the first oxide film 210 may be mixed with an amorphous phase and a crystalline phase, and may include a first oxide layer 210a having 0 ⁇ y ⁇ 0.2 and a second oxide layer 210b having 0.2 ⁇ y ⁇ 1. .
  • the first oxide film 210 is an oxide film formed by oxidizing an oxygen active element.
  • the first oxide layer 210a is an Al 2 - y Sb y O 3 (0 ⁇ y ⁇ 0.2) oxide film, in which amorphous and crystalline are mixed.
  • the second oxide layer 210b may be an Al 2 -y Sb y O 3 (0.2 ⁇ y ⁇ 1) oxide film and a layer in which crystalline and amorphous materials are mixed.
  • the first oxide layer may have a thickness of 5 to 100 nm.
  • the second oxide film 220 may have a thickness of about 5 to 30 ⁇ m.
  • the second oxide film may include an A x B y O z based oxide film, wherein A is at least one material selected from the group consisting of Bi, Sb, Fe, Ni, Zn, Na, Ca, and Pb.
  • B may be at least one material selected from the group consisting of Co, Te, and Se, wherein x is in the range of 1 to 3, y is in the range of 0 to 1, and z is in the range of 1 to 6 Z may vary depending on the valence of A and B.
  • the second oxide film 220 is an oxide film formed by oxidizing a volatile element of the thermoelectric material 100.
  • FIG. 2 is a view illustrating a heat treatment process according to a first example.
  • the heat treatment is a second temperature (T2) of 500 to 650 °C at a temperature lower than the first temperature (T1) of 400 to 450 °C volatile A and B elements are oxidized It may include the step of increasing the temperature and the heat treatment by maintaining at the second temperature (T2). At least one oxygen-active element selected from the group consisting of Al, Hf, Ce, Mg, and Y is oxidized at a second temperature T2 of 500 to 650 ° C. during the heat treatment to form a first oxide film. It is determined that the second oxide film is formed by heat treatment at a first temperature T1 and is formed until the first oxide film is formed.
  • the holding time in the said 2nd temperature T2 is about 10 minutes-about 12 hours. If the holding time at the second temperature T2 is short, the thickness of the first oxide film may become thin and may not play a sufficient role as a protective film. Even if the holding time at the second temperature T2 is too long, the thickness of the first oxide film is too long. May not increase compared to the holding time and is uneconomical in terms of time and cost.
  • the temperature increase rate to the said 2nd temperature T2 is 1-50 degreeC / min, More preferably, it is about 2-20 degreeC / min.
  • FIG 3 is a view illustrating a heat treatment process according to a second example.
  • the heat treatment may be performed by heating up to a first temperature T1 of 400 to 450 ° C. at which the volatile A and B elements are oxidized, and at the first temperature T1. Maintaining and heat-treating, heating to a second temperature T2 of 500 to 650 ° C. higher than the first temperature T1, and maintaining and heat-treating at the second temperature T2. .
  • the holding time in the said 2nd temperature T2 is about 10 minutes-about 12 hours. If the holding time at the first temperature T1 is long, the thickness of the second oxide film may be thickened, and the thickness of the second oxide film may be controlled by adjusting the holding time at the first temperature T1. have.
  • the holding time at said 1st temperature T1 is about 1 second-about 30 minutes.
  • the temperature increase rate to the said 1st temperature T1 is 1-50 degreeC / min, More preferably, it is about 2-20 degreeC / min.
  • the temperature increase rate from the first temperature T1 to the second temperature T2 is preferably 1 to 50 ° C / min, more preferably about 2 to 20 ° C / min.
  • FIG. 4 is a diagram illustrating a heat treatment process according to a third example.
  • the heat treatment is a step of raising the temperature at a first temperature increase rate to a first temperature T1 of 400 to 450 ° C. at which the volatile A and B elements are oxidized. And heating to a second temperature increase rate slower than the first temperature increase rate to a second temperature T2 of 500 to 650 ° C. higher than the temperature, and maintaining and heat-processing at the second temperature T2.
  • the holding time in the said 2nd temperature T2 is about 10 minutes-about 12 hours.
  • the temperature increase rate to the said 1st temperature T1 is 2-50 degreeC / min
  • the temperature increase rate to the said 2nd temperature is about 1-20 degreeC / min.
  • a second oxide film is formed. At least one oxygen-active element selected from the group consisting of Al, Hf, Ce, Mg, and Y is oxidized at the second temperature T2 to form a first oxide film.
  • the first oxide film and the second oxide film are formed in a double layer as a protective film on the thermoelectric material, oxidation and volatilization can be suppressed not only at medium temperature (eg, 200 to 450 ° C) but also at high temperature (eg, 400 to 1000 ° C). There are advantages to it.
  • a protective film (self-protection barrier) using an oxygen active element can form a very uniform and dense protective film without additional processes such as dip coating or spray coating.
  • ⁇ Designed as a limitation of high temperature thermoelectric device application It can prevent oxidation and volatilization, and it is expected to have enormous ripple effect on commercialization of thermoelectric device.
  • the protective film by the conventional coating method it is impossible to completely coat the high-temperature exposed portion of the thermoelectric material, but in the case of the protective film (self-protection barrier) according to the present invention, oxidation and volatilization can be sufficiently suppressed. This provides greater diversity in terms of design of thermoelectric modules as well as high temperature reliability.
  • thermoelectric material powder was prepared.
  • the thermoelectric material powder is a CoSb 3 powder as a skutterudite thermoelectric material.
  • the average particle diameter of the said thermoelectric material powder was about 40-45 micrometers.
  • thermoelectric material powder was sintered.
  • the sintering was performed using a Spark Plasma Sintering method, which was performed in a vacuum atmosphere at a temperature of 630 ° C. At this time, the degree of vacuum was about 10 ⁇ 2 torr.
  • the sintered body formed by the sintering was heat-treated in an air atmosphere to form a protective film on the thermoelectric material.
  • the heat treatment was carried out at 600 °C, the temperature increase rate up to 600 °C was about 10 °C / min, and the change of the protective film according to the heat treatment time was observed.
  • thermoelectric material powder was prepared.
  • the thermoelectric material powder is a CoSb 3 powder as a skutterudite thermoelectric material.
  • the average particle diameter of the said thermoelectric material powder was about 40-45 micrometers.
  • thermoelectric material powder 99 wt% of the thermoelectric material powder and 1 wt% of Al powder, which is an oxygen active element powder, were mixed to form a mixed powder.
  • a dry powder mixing method was used while minimizing air contact in a glove box.
  • the average particle diameter of the said Al powder was about 3 micrometers.
  • the mixed powder was sintered.
  • the sintering was performed using a Spark Plasma Sintering method, which was performed for 10 minutes in a vacuum atmosphere at a temperature of 630 ° C. At this time, the degree of vacuum was about 10 ⁇ 2 torr.
  • the sintered body formed by the sintering was heat-treated in an air atmosphere to form a protective film on the thermoelectric material.
  • the heat treatment was carried out at 600 °C, the temperature increase rate up to 600 °C was about 10 °C / min, and the change of the protective film according to the heat treatment time was observed.
  • FIG. 5 to 10 are diagrams for showing the change in surface oxidation with heat treatment time for a thermoelectric device manufactured without adding an oxygen active element according to Experimental Example 1, and is oxidized in air at 600 ° C. Shows the case.
  • FIG. 5 is a view showing the results of scanning electron microscope (SEM) and Energy Dispersive Spectrometry (EDS) analysis when oxidized for 1 hour in an air at 600 ° C.
  • FIG. 7 shows SEM and EDS analysis results when oxidized for 5 hours in the air, and FIG. 7 shows SEM and EDS analysis results when oxidized for 10 hours in the air at 600 ° C.
  • FIG. 9 shows SEM and EDS analysis results when oxidized for 20 hours in the air, and FIG. 9 shows SEM and EDS analysis results when oxidized for 50 hours in the air at 600 ° C. SEM and EDS analysis results when oxidized for 100 hours in the air.
  • FIG. 11 is a view showing a change in the surface oxide film thickness with respect to the heat treatment time for a thermoelectric device manufactured without adding an oxygen active element according to Experimental Example 1, and shows a case where it is oxidized in an air at 600 ° C.
  • FIG. 11 is a view showing a change in the surface oxide film thickness with respect to the heat treatment time for a thermoelectric device manufactured without adding an oxygen active element according to Experimental Example 1, and shows a case where it is oxidized in an air at 600 ° C.
  • FIG. 12 is a view showing SEM analysis results of an oxide film formed when a thermoelectric element manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 was exposed to air at 600 ° C. for 10 hours.
  • FIG. 13 is a view showing SEM analysis results of oxide films formed when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 was exposed to air at 600 ° C. for 50 hours.
  • FIG. 14 is a view showing SEM analysis results of an oxide film formed when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 was exposed to air at 600 ° C. for 80 hours.
  • FIG. 15 is a view showing SEM analysis results of an oxide film formed when a thermoelectric element manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 was exposed to air at 600 ° C. for 100 hours.
  • FIG. 16 shows SEM and EDS analysis results of the oxide film formed on the thermoelectric device when the thermoelectric device manufactured by adding 1 wt% of Al as an oxygen active element was exposed to air at 600 ° C. for 50 hours according to Experimental Example 2.
  • FIG. 17 is a view showing a change in oxide film thickness with exposure time when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C.
  • FIG. 17 is a view showing a change in oxide film thickness with exposure time when a thermoelectric device manufactured by adding 1 wt% of an oxygen active element Al according to Experimental Example 2 is exposed to air at 600 ° C.
  • thermoelectric element of the present invention can suppress oxidation and volatilization not only in the middle temperature region (for example, 200 to 450 ° C) but also in the high temperature region (for example, 400 to 1000 ° C), and there is industrial applicability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention se rapporte à un élément thermoélectrique comprenant des matériaux thermoélectriques et un film de protection formé sur les matériaux thermoélectriques, le film de protection comprenant un premier film d'oxyde formé sur les matériaux thermoélectriques et un second film d'oxyde formé sur le premier film d'oxyde, le premier film d'oxyde comprenant au moins un élément à base d'oxygène actif choisi dans le groupe constitué par l'aluminium (Al), le hafnium (Hf), le cérium (Ce), le magnésium (Mg), et l'yttrium (Y), et à son procédé de fabrication. Selon la présente invention, un film de protection (une barrière d'auto-protection) capable de limiter l'oxydation et la volatilisation dans une plage de température élevée (par exemple, comprise entre 400 et 1000 °C) ainsi qu'une plage de température moyenne (par exemple, comprise entre 200 et 450 °C) peut être formé sur des matériaux thermoélectriques selon un processus simple sans processus de revêtement compliqués, ce qui permet la fabrication d'un élément thermoélectrique présentant une propriété thermique supérieure.
PCT/KR2017/009122 2016-12-13 2017-08-22 Élément thermoélectrique retenu par oxydation et volatilisation et son procédé de fabrication Ceased WO2018110794A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0169134 2016-12-13
KR1020160169134A KR101772392B1 (ko) 2016-12-13 2016-12-13 산화 및 휘발이 억제되는 열전소자 및 그 제조방법

Publications (1)

Publication Number Publication Date
WO2018110794A1 true WO2018110794A1 (fr) 2018-06-21

Family

ID=59760005

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/009122 Ceased WO2018110794A1 (fr) 2016-12-13 2017-08-22 Élément thermoélectrique retenu par oxydation et volatilisation et son procédé de fabrication

Country Status (2)

Country Link
KR (1) KR101772392B1 (fr)
WO (1) WO2018110794A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110265540A (zh) * 2019-05-31 2019-09-20 上海大学 钡铜碲基p型热电材料及其制备方法
JP2020107650A (ja) * 2018-12-26 2020-07-09 三菱マテリアル株式会社 熱電変換材料、熱電変換素子、及び、熱電変換モジュール

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102198213B1 (ko) 2017-10-31 2021-01-04 한국전기연구원 확산방지층과 산화방지막, 산화막이 형성된 열전레그가 구비된 열전모듈 제조방법 및 그에 의한 열전모듈
KR102158328B1 (ko) 2018-06-11 2020-09-21 주식회사 엘지화학 열전 재료 및 이를 포함하는 열전 소자
KR102100048B1 (ko) * 2018-09-18 2020-04-10 김대희 열전발전을 이용한 폐기물 소각장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10256611A (ja) * 1997-03-14 1998-09-25 Toshiba Corp 熱電変換材料およびその製造方法
JP2000252526A (ja) * 1998-06-30 2000-09-14 Matsushita Electric Ind Co Ltd スカッテルダイト系熱電材料及び熱電カップル並びにその製造方法
JP2002359406A (ja) * 2001-05-31 2002-12-13 Komatsu Ltd 熱電素子とその製造方法
JP2011249442A (ja) * 2010-05-25 2011-12-08 Showa Denko Kk 熱電素子およびその製造方法、ならびに熱電モジュール
JP2014204080A (ja) * 2013-04-09 2014-10-27 宮川化成工業株式会社 熱電材料およびその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5671985B2 (ja) 2010-12-03 2015-02-18 株式会社豊田中央研究所 複合熱電材料及びその製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10256611A (ja) * 1997-03-14 1998-09-25 Toshiba Corp 熱電変換材料およびその製造方法
JP2000252526A (ja) * 1998-06-30 2000-09-14 Matsushita Electric Ind Co Ltd スカッテルダイト系熱電材料及び熱電カップル並びにその製造方法
JP2002359406A (ja) * 2001-05-31 2002-12-13 Komatsu Ltd 熱電素子とその製造方法
JP2011249442A (ja) * 2010-05-25 2011-12-08 Showa Denko Kk 熱電素子およびその製造方法、ならびに熱電モジュール
JP2014204080A (ja) * 2013-04-09 2014-10-27 宮川化成工業株式会社 熱電材料およびその製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020107650A (ja) * 2018-12-26 2020-07-09 三菱マテリアル株式会社 熱電変換材料、熱電変換素子、及び、熱電変換モジュール
CN113272977A (zh) * 2018-12-26 2021-08-17 三菱综合材料株式会社 热电转换材料、热电转换元件及热电转换模块
JP7159854B2 (ja) 2018-12-26 2022-10-25 三菱マテリアル株式会社 熱電変換材料、熱電変換素子、及び、熱電変換モジュール
CN113272977B (zh) * 2018-12-26 2024-10-15 三菱综合材料株式会社 热电转换材料、热电转换元件及热电转换模块
CN110265540A (zh) * 2019-05-31 2019-09-20 上海大学 钡铜碲基p型热电材料及其制备方法
CN110265540B (zh) * 2019-05-31 2022-07-08 上海大学 钡铜碲基p型热电材料及其制备方法

Also Published As

Publication number Publication date
KR101772392B1 (ko) 2017-08-29

Similar Documents

Publication Publication Date Title
WO2018110794A1 (fr) Élément thermoélectrique retenu par oxydation et volatilisation et son procédé de fabrication
WO2015050420A1 (fr) Nouveau semi-conducteur composé et son utilisation
JP5600732B2 (ja) 保護層でコーティングされている熱電材料
WO2011122888A2 (fr) Matériau thermoélectrique, module et dispositif thermoélectriques comprenant le matériau thermoélectrique
Kim et al. Thermoelectric properties of P-type Sb2Te3 thick film processed by a screen-printing technique and a subsequent annealing process
WO2016167525A1 (fr) Matériaux thermoélectriques, élément thermoélectrique et module thermoélectrique les comprenant
WO2013070049A1 (fr) Pâte conductrice, et dispositif électronique et photopile comprenant une électrode formée au moyen de la pâte conductrice
WO2012157916A1 (fr) Nouveau semi-conducteur composé et son utilisation
WO2015080527A1 (fr) Nouveau composé semi-conducteur et utilisation de celui-ci
US7435896B2 (en) Thermoelectric conversion material, thermoelectric conversion element using the material, cooling device and electric apparatus using the element, and electric power generation method and cooling method using the element
WO2020085681A1 (fr) Élément thermoélectrique et son procédé de fabrication
JP2002100814A (ja) 高いゼーベック係数と高い電気伝導度を有する複合酸化物
WO2018038477A1 (fr) Matériau thermoélectrique à super-réseau et dispositif thermoélectrique l'utilisant
WO2020149464A1 (fr) Matériau thermoélectrique et son procédé de préparation
WO2015046810A1 (fr) Composé semi-conducteur d'un nouveau type et son utilisation
WO2016099155A1 (fr) Poudre thermoélectrique et matériaux thermoélectriques fabriqués au moyen de celle-ci
WO2020149465A1 (fr) Procédé de fabrication de matériau thermoélectrique
WO2022025325A1 (fr) Matériau thermoélectrique comprenant une couche barrière de diffusion multicouche, et élément thermoélectrique pourvu de celui-ci
KR101357172B1 (ko) 안티몬―텔루륨계 페이스트 합성법과 페이스트를 이용한 ｐ형 열전물질의 형성 방법
WO2015034318A1 (fr) Matériau thermoélectrique
WO2016052948A1 (fr) Semi-conducteur composé et son procédé de fabrication
WO2022131395A1 (fr) Module de conversion thermoélectrique
WO2019117559A1 (fr) Film mince de métal de transition-dichalcogénure et son procédé de fabrication
WO2015034321A1 (fr) Procédé pour fabriquer un matériau thermoélectrique
CN108091756A (zh) 热电转换元件及其制造方法

Legal Events

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

Ref document number: 17881308

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17881308

Country of ref document: EP

Kind code of ref document: A1