WO2013048186A1 - Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure - Google Patents
Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure Download PDFInfo
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- WO2013048186A1 WO2013048186A1 PCT/KR2012/007928 KR2012007928W WO2013048186A1 WO 2013048186 A1 WO2013048186 A1 WO 2013048186A1 KR 2012007928 W KR2012007928 W KR 2012007928W WO 2013048186 A1 WO2013048186 A1 WO 2013048186A1
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- 239000000843 powder Substances 0.000 title claims abstract description 47
- 239000011258 core-shell material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 37
- 238000002360 preparation method Methods 0.000 title description 3
- 239000011858 nanopowder Substances 0.000 claims abstract description 44
- 239000011247 coating layer Substances 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 12
- 238000000231 atomic layer deposition Methods 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 4
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 claims description 4
- RVIXKDRPFPUUOO-UHFFFAOYSA-N Dimethyl selenide Natural products C[Se]C RVIXKDRPFPUUOO-UHFFFAOYSA-N 0.000 claims description 2
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- SWAKCLHCWHYEOW-UHFFFAOYSA-N chloro selenohypochlorite Chemical compound Cl[Se]Cl SWAKCLHCWHYEOW-UHFFFAOYSA-N 0.000 claims description 2
- YMUZFVVKDBZHGP-UHFFFAOYSA-N dimethyl telluride Chemical compound C[Te]C YMUZFVVKDBZHGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000002490 spark plasma sintering Methods 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H10N10/857—Thermoelectric active materials comprising compositions changing continuously or discontinuously inside the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
Definitions
- the present disclosure relates to nano thermoelectric powder with a core-shell structure capable of enhancing thermoelectric efficiency, and thermoelectric elements using the same.
- thermoelectric material is an energy conversion material that produces electrical energy when giving temperature difference between both ends of the material, but produces temperature difference between both ends of the material when giving electrical energy to the material.
- thermoelectric material The efficiency of the thermoelectric material may be defined by the following equation that represents the dimensionless ZT value. (S: seeback coefficient, : electrical conductivity, ⁇ : thermal conductivity)
- the ZT value is proportional to the electrical conductivity and the seeback coefficient, and is inversely proportional to the thermal conductivity.
- the thermal conductivity includes the thermal conductivity of electron and lattice, it is hard to control the thermal conductivity of electron due to the intrinsic properties of the material.
- the thermal conductivity of lattice is a function affected by specific heat, mobility of phonon, and an average free path of phonon, the specific heat, the mobility of phonon, and the average free path of phonon are controlled to reduce the thermal conductivity.
- the type in which the simple nano structure is inserted into the bulk-type thermoelectric element also affects the reduction of the electrical conductivity , which is not enough to efficiently increase the ZT value.
- thermoelectric material Therefore, researches for reducing the thermal conductivity of the thermoelectric material are urgently required without reducing the electrical conductivity of the thermoelectric material.
- the present invention provides nano thermoelectric powder with a core-shell structure, including coating layers on a surface of the nano powder.
- the present invention provides the thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure.
- thermoelectric module including top and bottom insulating substrates formed with metal electrodes and facing each other, and a plurality of thermoelectric elements between the top and bottom insulating substrates, wherein the thermoelectric elements are the thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure and are connected in series via the metal electrode formed by the media of the top and bottom insulating substrates.
- a method for manufacturing the nano thermoelectric powder with the core-shell structure of the present invention includes (a) manufacturing an ingot by inputting, melting and cooling basic materials into a furnace; (b) preparing nano powder by crushing and grinding the ingot; and (c) forming coating layers on a surface of the nano powder.
- thermoelectric element of the present invention includes (a) manufacturing an ingot by inputting, melting and cooling basic materials into a furnace; (b) preparing the nano powder by crushing and grinding the ingot; (c) forming coating layers on a surface of the nano powder, and (d) sintering the nano thermoelectric powder with the core-shell structure manufactured in the forming of the coating layers.
- thermoelectric module of the present invention may be manufactured using the method alternately arranging and electrically connecting the thermoelectric elements on the top and bottom insulating substrates formed with the metal electrode, but is not limited thereto.
- the present invention provides thermoelectric elements with the enhanced thermoelectric efficiency by forming a coating layer thinner than average free path of the phonon on the surface of the nano powder prior to sintering of the nano powder.
- the coating layer having the nano-scale is formed on the surface of the nano powder.
- the coating layer with the nano-scale formed on the surface of the nano powder does not affect the mobility of electron related to electrical conductivity, and increases only the scattering of the phonon, thereby providing the thermoelectric element having the reduced thermal conductivity without reducing the electrical conductivity.
- FIG.1 schematically shows a process of manufacturing thermoelectric elements according to the related art.
- FIG.2 schematically shows a process of manufacturing the thermoelectric elements of the present invention.
- FIG. 3 schematically shows a process of manufacturing the thermoelectric elements by sintering nano thermoelectric powder with a core-shell structure synthesized according to an exemplary embodiment of the present invention.
- the present invention provides nano thermoelectric powder with a core-shell structure including coating layers on a surface of the nano powder, and may provide the thermoelectric elements having enhanced thermoelectric efficiency by the preparation of the nano thermoelectric powder with the core-shell structure.
- thermoelectric elements may be defined as the following equation that represents the dimensionless ZT value. (S: seeback coefficient, : electrical conductivity, ⁇ : thermal conductivity)
- the ZT value is proportional to the electrical conductivity and the seeback coefficient, and is inversely proportional to the thermal conductivity.
- thermoelectric powder with the core-shell structure of the present invention may provide the thermoelectric elements having enhanced thermoelectric efficiency.
- the nano powder when manufacturing the thermoelectric elements by powder metallurgy, is powder having a nano size obtained by crushing and grinding an ingot, and the nano powder is sintered to provide the thermoelectric elements .
- the present invention forms the coating layer on the surface of the nano powder by the sintering preprocessing process of the nano powder to provide the nano thermoelectric powder with the core-shell structure, and may provide the thermoelectric elements having reduced thermal conductivity and enhanced thermoelectric efficiency even without affecting the electrical conductivity due to the formed coating layer.
- the thickness of the coating layer formed on the surface of the nano powder has to be formed thinner than that of the average free path of the phonon, thereby allowing the scattering of the phonon to increase, lowering the thermal conductivity by the phonon and therefore, lowering the whole thermal conductivity ⁇ .
- the present invention relates to the nano thermoelectric powder with the core-shell structure.
- the average free path of the phonon which is the unique value of the material, depends on the material of the nano powder.
- the material of the nano powder may use at least two types selected from the group composed of, for example, Bi, Te, Sb and Se, the average free path of the phonon of Bi2Te3 as an embodiment among them is roughly about 3nm, and therefore, the thickness of the coating layer formed on the surface of the nano powder is preferably between 1 and 3.5 nm.
- the coating layer with the nano-scale formed on the surface of the nano powder does not affect the mobility of the electron related to the electrical conductivity, and allows the scattering only of the phonon to increase, thereby providing the thermoelectric elements having reduced thermal conductivity even without reducing the electrical conductivity.
- An average grain size of the nano powder of a core among the nano thermoelectric powder with the core-shell structure may be between 30 and 50 ⁇ m, but is not limited thereto.
- the coating layer that is, a shell among the nano thermoelectric powder with the core-shell structure consists of the same material as material composing the nano powder, or may be composed of other material.
- the coating layer may be composed of at least one types selected from the group composed of Na, K, Rb, Bi, Te, Sb and Se, but is not limited thereto.
- thermoelectric elements having enhanced thermoelectric performance obtained by sintering the nano thermoelectric powder with the core-shell structure.
- thermoelectric module including the thermoelectric elements.
- thermoelectric module including the thermoelectric elements may be implemented depending on the method adopting typically in the industry, but as non-restrictive example, includes top and bottom insulating substrates formed with the metal electrode and facing each other, and a plurality of thermoelectric elements s between the top and bottom insulating substrates wherein the thermoelectric elements are the thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure of the present invention, and may be structure connected in serial by the media of the metal electrode of the top and bottom insulating substrates.
- the method manufacturing the nano thermoelectric powder with the core-shell structure of the present invention includes (a) manufacturing an ingot by inputting, melting, and cooling the basic materials into a furnace; (b) preparing the nano powder by crushing and grinding the ingot; and (c) forming coating layers on the surface of the nano powder.
- the manufacturing the ingot may be performed depending on the ordinary method in the art.
- the manufacturing the ingot may be manufactured by inputting, melting, and cooling the basic materials into the furnace.
- the base material may use at least two selected from the group composed of Bi, Te, Sb and Se, but is not limited thereto.
- the preparing the nano powder crushes and grinds the ingot manufactured in the manufacturing of the ingot into the nano powder depending on the ordinary method in the art.
- the forming of coating layers forms the coating layer B on the surface of the nano powder A, wherein the coating layers may be formed by an Atomic Layer Deposition (ALD) method or a Hydrothermal Deposition method and is not limited thereto.
- ALD Atomic Layer Deposition
- Hydrothermal Deposition a Hydrothermal Deposition method
- At least one precursor selected from the group composed of BiMe3, TeMe2, SbMe3, SeMe2, BiCl3, TeCl2, SbCl3, SeCl2, [Bi(SiMe3)3], [Te(SiMe3)2], [Sb(SiMe3)3] and [Se(SiMe3)2] may be used.
- At least one precursor selected from the group composed of NaOH, KOH, RbOH, NaBH4, KBH4 and RbBH4 may be used.
- the nano thermoelectric powder with the core-shell structure of the present invention may form the coating layer thinner than the average free path of phonon on the surface of the nano powder by the Atomic Layer Deposition (ALD) method or the Hydrothermal Deposition method, and the like.
- ALD Atomic Layer Deposition
- Hydrothermal Deposition method and the like.
- thermoelectric powder with the core-shell structure of the present invention is manufactured through the following (a) to (c) processes, and the thermoelectric elements may be manufactured through the following (d) process.
- the sintering of the nano thermoelectric powder sinters the nano thermoelectric powder C with the core-shell structure in which the coating layer B is formed on the surface of the nano powder A of the present invention to produce a pellet-type thermoelectric element D, and the sintering is performed depending on the method on the ordinary method in the art, for example, a Hot Press method and a Spark Plasma Sintering method.
- the coating layer that is, shells of the nano thermoelectric powder with the core-shell structure does not affect the mobility of electron related to the electrical conductivity, and increases only the scattering of phonon, thereby reducing the thermal conductivity while maintaining the electrical conductivity and therefore, enhancing the thermoelectric performance.
- the present invention provides the thermoelectric module including the thermoelectric elements with very enhanced thermoelectric performance.
- thermoelectric module may be manufactured depending on the ordinary method in the art.
- the thermocouple module may be manufactured by alternately arranging and electrically connecting the thermoelectric elements of the present invention on the top and bottom insulating substrates on which the metal electrodes are formed.
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Abstract
Provided is nano thermoelectric powder with a core-shell structure. Specifically, the nano thermoelectric powder of the core-shell structure of the present invention forms coating layer on the surface of nano powder prior to sintering of the nano powder. An advantage of some aspects of the present invention is that it provides thermoelectric elements having reduced thermal conductivity and enhanced thermoelectric efficiency without affecting electrical conductivity using the nano thermoelectric powder with the core-shell structure.
Description
The present disclosure relates to nano thermoelectric powder with a core-shell structure capable of enhancing thermoelectric efficiency, and thermoelectric elements using the same.
In general, the thermoelectric material is an energy conversion material that produces electrical energy when giving temperature difference between both ends of the material, but produces temperature difference between both ends of the material when giving electrical energy to the material.
The efficiency of the thermoelectric material may be defined by the following equation that represents the dimensionless ZT value. (S: seeback coefficient, : electrical conductivity, κ: thermal conductivity)
The ZT value is proportional to the electrical conductivity and the seeback coefficient, and is inversely proportional to the thermal conductivity.
Recently, to enhance the ZT value, many attempts to reduce the thermal conductivity have been performed.
The thermal conductivityκinclude the thermal conductivity of electron and lattice, it is hard to control the thermal conductivity of electron due to the intrinsic properties of the material. However, since the thermal conductivity of lattice is a function affected by specific heat, mobility of phonon, and an average free path of phonon, the specific heat, the mobility of phonon, and the average free path of phonon are controlled to reduce the thermal conductivity.
Many groups adopts a type in which a simple nano structure is inserted into a bulk-type thermoelectric element and as a result, have focused only the increase in the scattering of the phonon affecting the thermal conductivity κ.
However, the type in which the simple nano structure is inserted into the bulk-type thermoelectric element also affects the reduction of the electrical conductivity , which is not enough to efficiently increase the ZT value.
The present invention provides nano thermoelectric powder with a core-shell structure, including coating layers on a surface of the nano powder.
The present invention provides the thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure.
According to an embodiment of the present invention, there is provided a thermoelectric module including top and bottom insulating substrates formed with metal electrodes and facing each other, and a plurality of thermoelectric elements between the top and bottom insulating substrates, wherein the thermoelectric elements are the thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure and are connected in series via the metal electrode formed by the media of the top and bottom insulating substrates.
According to another embodiment of the present invention, there is provided a method for manufacturing the nano thermoelectric powder with the core-shell structure of the present invention includes (a) manufacturing an ingot by inputting, melting and cooling basic materials into a furnace; (b) preparing nano powder by crushing and grinding the ingot; and (c) forming coating layers on a surface of the nano powder.
According to another embodiment of the present invention, there is provided a method for manufacturing the thermoelectric element of the present invention includes (a) manufacturing an ingot by inputting, melting and cooling basic materials into a furnace; (b) preparing the nano powder by crushing and grinding the ingot; (c) forming coating layers on a surface of the nano powder, and (d) sintering the nano thermoelectric powder with the core-shell structure manufactured in the forming of the coating layers.
The thermoelectric module of the present invention may be manufactured using the method alternately arranging and electrically connecting the thermoelectric elements on the top and bottom insulating substrates formed with the metal electrode, but is not limited thereto.
The present invention provides thermoelectric elements with the enhanced thermoelectric efficiency by forming a coating layer thinner than average free path of the phonon on the surface of the nano powder prior to sintering of the nano powder.
Since the average free path of the phonon has nano-scale, the coating layer having the nano-scale is formed on the surface of the nano powder.
The coating layer with the nano-scale formed on the surface of the nano powder does not affect the mobility of electron related to electrical conductivity, and increases only the scattering of the phonon, thereby providing the thermoelectric element having the reduced thermal conductivity without reducing the electrical conductivity.
The above and other aspects, features and advantages of certain exemplary embodiments of the present invention will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG.1 schematically shows a process of manufacturing thermoelectric elements according to the related art.
FIG.2 schematically shows a process of manufacturing the thermoelectric elements of the present invention.
FIG. 3 schematically shows a process of manufacturing the thermoelectric elements by sintering nano thermoelectric powder with a core-shell structure synthesized according to an exemplary embodiment of the present invention.
<Reference Numerals>
A. : nano powder
B. : coating layer
C. : nano thermoelectric powder with a core-shell structure
D. : pellet-type thermoelectric element
Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. Wherever possible, the same reference numerals will be used to refer to the same elements throughout the specification, and a duplicated description thereof will be omitted. It will be understood that although the terms "first", "second", etc. are used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element.
The present invention provides nano thermoelectric powder with a core-shell structure including coating layers on a surface of the nano powder, and may provide the thermoelectric elements having enhanced thermoelectric efficiency by the preparation of the nano thermoelectric powder with the core-shell structure.
The efficiency of the thermoelectric elements may be defined as the following equation that represents the dimensionless ZT value. (S: seeback coefficient, : electrical conductivity, κ: thermal conductivity)
The ZT value is proportional to the electrical conductivity and the seeback coefficient, and is inversely proportional to the thermal conductivity.
Hereinafter, it is described in detail how the nano thermoelectric powder with the core-shell structure of the present invention may provide the thermoelectric elements having enhanced thermoelectric efficiency.
In FIG. 2, when manufacturing the thermoelectric elements by powder metallurgy, the nano powder is powder having a nano size obtained by crushing and grinding an ingot, and the nano powder is sintered to provide the thermoelectric elements .
Unlike the process manufacturing prior thermoelectric elements of FIG. 1, as shown in FIG. 2, the present invention forms the coating layer on the surface of the nano powder by the sintering preprocessing process of the nano powder to provide the nano thermoelectric powder with the core-shell structure, and may provide the thermoelectric elements having reduced thermal conductivity and enhanced thermoelectric efficiency even without affecting the electrical conductivity due to the formed coating layer.
Specifically, to provide the thermoelectric elements having reduced thermal conductivity without affecting the electrical conductivity , the thickness of the coating layer formed on the surface of the nano powder has to be formed thinner than that of the average free path of the phonon, thereby allowing the scattering of the phonon to increase, lowering the thermal conductivity by the phonon and therefore, lowering the whole thermal conductivity κ. The present invention relates to the nano thermoelectric powder with the core-shell structure.
Here, the average free path of the phonon, which is the unique value of the material, depends on the material of the nano powder.
The material of the nano powder may use at least two types selected from the group composed of, for example, Bi, Te, Sb and Se, the average free path of the phonon of Bi2Te3 as an embodiment among them is roughly about 3㎚, and therefore, the thickness of the coating layer formed on the surface of the nano powder is preferably between 1 and 3.5 ㎚.
The coating layer with the nano-scale formed on the surface of the nano powder does not affect the mobility of the electron related to the electrical conductivity, and allows the scattering only of the phonon to increase, thereby providing the thermoelectric elements having reduced thermal conductivity even without reducing the electrical conductivity.
An average grain size of the nano powder of a core among the nano thermoelectric powder with the core-shell structure may be between 30 and 50 ㎛, but is not limited thereto.
The coating layer, that is, a shell among the nano thermoelectric powder with the core-shell structure consists of the same material as material composing the nano powder, or may be composed of other material.
The coating layer may be composed of at least one types selected from the group composed of Na, K, Rb, Bi, Te, Sb and Se, but is not limited thereto.
The present invention provides the thermoelectric elements having enhanced thermoelectric performance obtained by sintering the nano thermoelectric powder with the core-shell structure.
Further, the present invention provides the thermoelectric module including the thermoelectric elements.
The thermoelectric module including the thermoelectric elements may be implemented depending on the method adopting typically in the industry, but as non-restrictive example, includes top and bottom insulating substrates formed with the metal electrode and facing each other, and a plurality of thermoelectric elements s between the top and bottom insulating substrates wherein the thermoelectric elements are the thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure of the present invention, and may be structure connected in serial by the media of the metal electrode of the top and bottom insulating substrates.
The method manufacturing the nano thermoelectric powder with the core-shell structure of the present invention includes (a) manufacturing an ingot by inputting, melting, and cooling the basic materials into a furnace; (b) preparing the nano powder by crushing and grinding the ingot; and (c) forming coating layers on the surface of the nano powder.
The manufacturing the ingot may be performed depending on the ordinary method in the art. For example, The manufacturing the ingot may be manufactured by inputting, melting, and cooling the basic materials into the furnace.
The base material may use at least two selected from the group composed of Bi, Te, Sb and Se, but is not limited thereto.
The preparing the nano powder crushes and grinds the ingot manufactured in the manufacturing of the ingot into the nano powder depending on the ordinary method in the art.
In FIG. 3, the forming of coating layers forms the coating layer B on the surface of the nano powder A, wherein the coating layers may be formed by an Atomic Layer Deposition (ALD) method or a Hydrothermal Deposition method and is not limited thereto.
When forming the coating layer on the surface of the nano powder by the Atomic Layer Deposition (ALD) method, at least one precursor selected from the group composed of BiMe3, TeMe2, SbMe3, SeMe2, BiCl3, TeCl2, SbCl3, SeCl2, [Bi(SiMe3)3], [Te(SiMe3)2], [Sb(SiMe3)3] and [Se(SiMe3)2] may be used.
Further, when forming the coating layer on the surface of the nano powder by the Hydrothermal Deposition method, at least one precursor selected from the group composed of NaOH, KOH, RbOH, NaBH4, KBH4 and RbBH4 may be used.
The nano thermoelectric powder with the core-shell structure of the present invention may form the coating layer thinner than the average free path of phonon on the surface of the nano powder by the Atomic Layer Deposition (ALD) method or the Hydrothermal Deposition method, and the like.
The nano thermoelectric powder with the core-shell structure of the present invention is manufactured through the following (a) to (c) processes, and the thermoelectric elements may be manufactured through the following (d) process.
(a) manufacturing an ingot by inputting, melting, and cooling basic materials into a furnacel; (b) preparing the nano powder by crushing and grinding the ingot; (c) forming coating layers on the surface of the nano powder, and (d) sintering the nano thermoelectric powder with the core-shell structure manufactured in the forming of the coating layer.
In FIG. 3, the sintering of the nano thermoelectric powder sinters the nano thermoelectric powder C with the core-shell structure in which the coating layer B is formed on the surface of the nano powder A of the present invention to produce a pellet-type thermoelectric element D, and the sintering is performed depending on the method on the ordinary method in the art, for example, a Hot Press method and a Spark Plasma Sintering method.
In the thermoelectric elements manufactured through the (a) to (d) processes, the coating layer, that is, shells of the nano thermoelectric powder with the core-shell structure does not affect the mobility of electron related to the electrical conductivity, and increases only the scattering of phonon, thereby reducing the thermal conductivity while maintaining the electrical conductivity and therefore, enhancing the thermoelectric performance.
The present invention provides the thermoelectric module including the thermoelectric elements with very enhanced thermoelectric performance.
The thermoelectric module may be manufactured depending on the ordinary method in the art. For example, the thermocouple module may be manufactured by alternately arranging and electrically connecting the thermoelectric elements of the present invention on the top and bottom insulating substrates on which the metal electrodes are formed.
While the invention has been shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the scope of the invention is defined not by the detailed description of the invention but by the appended claims, and all differences within the scope will be construed as being included in the present invention.
Claims (18)
- A nano thermoelectric powder with a core-shell structure comprising a coating layer on a surface of the nano powder.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein a thickness of the coating layer is thinner than that of a average free path of phonon.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein the thickness of the coating layer is between 1 and 3.5 ㎚.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein the nano powder is at least two powders selected from the group composed of Bi, Te, Sb and Se.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein an average grain size of the nano powder is between 30 and 50 ㎛.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein the coating layer consists of the same material as a material composing the nano powder.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein the coating layer consists of a material different from the material composing the nano powder.
- The nano thermoelectric powder with the core-shell structure of claim 1, wherein the coating layer is composed of at least one or two selected from the group composed of Na, K, Rb, Bi, Te, Sb and Se.
- Thermoelectric elements obtained by sintering the nano thermoelectric powder with the core-shell structure of any one of claims 1 to 8.
- A thermoelectric module, comprising top and bottom insulating substrates formed with metal electrodes and facing each other, and a plurality of thermoelectric elements between the top and bottom insulating substrates, wherein the thermoelectric elements are the thermoelectric elements of claim 9, and the thermoelectric elements s are connected in series via the metal electrode formed on the media of the top and bottom insulating substrates.
- The method manufacturing nano thermoelectric powder with a core-shell structure, comprising (a) manufacturing an ingot by inputting, melting and cooling basic materials into a furnace; (b) preparing the nano powder by crushing and grinding the ingot; and (c) forming coating layers on the surface of the nano powder.
- The method manufacturing the nano thermoelectric powder with the core-shell structure of claim 11, wherein the basic materials in the manufacturing of an ingot uses at least two selected from the group consisted of Bi, Te, Sb and Se.
- The method manufacturing the nano thermoelectric powder with a core-shell structure of claim 11, wherein the coating layer in the forming of coating layers is formed by ALD(Atomic Layer Deposition) method; or Hydrothermal Deposition method.
- The method manufacturing the nano thermoelectric powder with the core-shell structure of claim 13, wherein the coating layer in the forming of coating layers is formed by the ALD(Atomic Layer Deposition) method using at least one precursor selected from the group composed of BiMe3, TeMe2, SbMe3, SeMe2, BiCl3, TeCl2, SbCl3, SeCl2, [Bi(SiMe3)3], [Te(SiMe3)2], [Sb(SiMe3)3] and [Se(SiMe3)2].
- The method manufacturing the nano thermoelectric powder with the core-shell structure of claim 13, wherein the coating layer in the forming of coating layers is formed by Hydrothermal Deposition method using at least one precursor selected from the group consisted of NaOH, KOH, RbOH, NaBH4, KBH4 and RbBH4.
- The method manufacturing the thermoelectric elements, comprising (a) manufacturing an ingot by inputing, melting and cooling the basic materials into the furnace; (b) preparing the nano powder by crushing and grinding the ingot; (c) forming coating layers on the surface of the nano powder, and (d) sintering the nano thermoelectric powder with the core-shell structure manufactured in the forming of coating layers.
- The method manufacturing the thermoelectric elements of claim 16, wherein the sintering of the nano thermoelectric powder is performed by a Hot Press method and a Spark Plasma Sintering method.
- The method manufacturing the thermoelectric module alternately arranging and electrically connecting thermoelectric elements manufactured of claim 16 on the top and bottom insulating substrates formed with the metal electrode.
Priority Applications (3)
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CN201280058111.7A CN103959494A (en) | 2011-09-29 | 2012-09-28 | Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure |
EP12837323.0A EP2761681A4 (en) | 2011-09-29 | 2012-09-28 | Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure |
US14/348,691 US20140246065A1 (en) | 2011-09-29 | 2012-09-28 | Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure |
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KR10-2011-0099210 | 2011-09-29 | ||
KR1020110099210A KR101950370B1 (en) | 2011-09-29 | 2011-09-29 | Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure |
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PCT/KR2012/007928 WO2013048186A1 (en) | 2011-09-29 | 2012-09-28 | Method for enhancement of thermoelectric efficiency by the preparation of nano thermoelectric powder with core-shell structure |
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US (1) | US20140246065A1 (en) |
EP (1) | EP2761681A4 (en) |
KR (1) | KR101950370B1 (en) |
CN (1) | CN103959494A (en) |
WO (1) | WO2013048186A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2698373A3 (en) * | 2012-08-13 | 2014-04-09 | Air Products And Chemicals, Inc. | Precursors for gst films in ald/cvd processes |
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JP6001578B2 (en) * | 2014-01-31 | 2016-10-05 | トヨタ自動車株式会社 | Method for producing core / shell type nanoparticles and method for producing sintered body using the method |
WO2018200474A1 (en) * | 2017-04-24 | 2018-11-01 | The Regents Of The University Of Michigan | Heating and cooling device |
CN111834516B (en) * | 2020-07-27 | 2023-06-30 | 厦门理工学院 | In-situ generated core-shell structure thermoelectric material and preparation method thereof |
KR102560139B1 (en) * | 2021-08-27 | 2023-07-26 | 공주대학교 산학협력단 | Plated Bi-Sb-Te alloy-sintered body and its manufacturing method |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004071870A (en) * | 2002-08-07 | 2004-03-04 | Kitagawa Ind Co Ltd | Thermoelectric material molding and manufacturing method of thermoelectric material molding |
JP2007158197A (en) * | 2005-12-07 | 2007-06-21 | National Institute For Materials Science | Self formation method of environmental resistance coated film in semiconductor-based thermoelectric material |
KR20100088903A (en) * | 2009-02-02 | 2010-08-11 | 삼성전자주식회사 | Thermoelectric device and method of manufacturing the same |
KR20110064702A (en) * | 2009-12-08 | 2011-06-15 | 삼성전자주식회사 | Core-shell nanowire with uneven structure and thermoelectric device using the same |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8044292B2 (en) * | 2006-10-13 | 2011-10-25 | Toyota Motor Engineering & Manufacturing North America, Inc. | Homogeneous thermoelectric nanocomposite using core-shell nanoparticles |
CN100546063C (en) * | 2008-02-26 | 2009-09-30 | 杭州电子科技大学 | A kind of preparation method of core-shell structure nano pyroelectric material |
KR101580575B1 (en) * | 2008-04-25 | 2015-12-28 | 에이에스엠 인터내셔널 엔.브이. | Synthesis and use of precursors for ALD of tellurium and selenium thin films |
US20110100408A1 (en) * | 2008-07-29 | 2011-05-05 | Hi-Z Technology Inc | Quantum well module with low K crystalline covered substrates |
KR101530376B1 (en) * | 2008-10-23 | 2015-06-26 | 한국교통대학교산학협력단 | Bulk thermoelectric material and thermoelectric device comprising same |
US9718043B2 (en) * | 2009-02-24 | 2017-08-01 | Toyota Motor Engineering & Manufacturing North America, Inc. | Core-shell nanoparticles and process for producing the same |
GB2482311A (en) * | 2010-07-28 | 2012-02-01 | Sharp Kk | II-III-N and II-N semiconductor nanoparticles, comprising the Group II elements Zinc (Zn) or Magensium (Mg) |
-
2011
- 2011-09-29 KR KR1020110099210A patent/KR101950370B1/en active IP Right Grant
-
2012
- 2012-09-28 WO PCT/KR2012/007928 patent/WO2013048186A1/en active Application Filing
- 2012-09-28 CN CN201280058111.7A patent/CN103959494A/en active Pending
- 2012-09-28 US US14/348,691 patent/US20140246065A1/en not_active Abandoned
- 2012-09-28 EP EP12837323.0A patent/EP2761681A4/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004071870A (en) * | 2002-08-07 | 2004-03-04 | Kitagawa Ind Co Ltd | Thermoelectric material molding and manufacturing method of thermoelectric material molding |
JP2007158197A (en) * | 2005-12-07 | 2007-06-21 | National Institute For Materials Science | Self formation method of environmental resistance coated film in semiconductor-based thermoelectric material |
KR20100088903A (en) * | 2009-02-02 | 2010-08-11 | 삼성전자주식회사 | Thermoelectric device and method of manufacturing the same |
KR20110064702A (en) * | 2009-12-08 | 2011-06-15 | 삼성전자주식회사 | Core-shell nanowire with uneven structure and thermoelectric device using the same |
Non-Patent Citations (1)
Title |
---|
See also references of EP2761681A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2698373A3 (en) * | 2012-08-13 | 2014-04-09 | Air Products And Chemicals, Inc. | Precursors for gst films in ald/cvd processes |
EP3293193A3 (en) * | 2012-08-13 | 2018-05-16 | Versum Materials US, LLC | Precursors for gst films in ald/cvd processes |
Also Published As
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US20140246065A1 (en) | 2014-09-04 |
KR101950370B1 (en) | 2019-02-20 |
KR20130035010A (en) | 2013-04-08 |
EP2761681A4 (en) | 2016-01-06 |
EP2761681A1 (en) | 2014-08-06 |
CN103959494A (en) | 2014-07-30 |
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