WO2015057018A1 - 열전 재료 및 그 제조 방법 - Google Patents
열전 재료 및 그 제조 방법 Download PDFInfo
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- WO2015057018A1 WO2015057018A1 PCT/KR2014/009795 KR2014009795W WO2015057018A1 WO 2015057018 A1 WO2015057018 A1 WO 2015057018A1 KR 2014009795 W KR2014009795 W KR 2014009795W WO 2015057018 A1 WO2015057018 A1 WO 2015057018A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
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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
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
Definitions
- the present invention relates to a thermoelectric conversion technology, and more particularly, to a thermoelectric conversion material having excellent thermoelectric conversion characteristics, a method of manufacturing the same, and a use thereof.
- Compound A semiconductor is a compound which acts as a semiconductor by combining two or more elements rather than a single element such as silicon or germanium.
- Various kinds of such compound semiconductors are currently developed and used in various fields.
- a compound semiconductor may be used in a thermoelectric conversion element using a Peltier effect, a light emitting element such as a light emitting diode or a laser diode using the photoelectric conversion effect, and a solar cell.
- thermoelectric conversion element may be applied to thermoelectric power generation, thermoelectric conversion cooling, or the like, and is generally configured in such a manner that an N-type thermoelectric semiconductor and a P-type thermoelectric semiconductor are electrically connected in series and thermally in parallel.
- thermoelectric conversion power generation is a form of power generation that converts thermal energy into electrical energy by using thermoelectric power generated by providing a temperature difference to a thermoelectric conversion element.
- thermoelectric conversion cooling is a form of cooling which converts electrical energy into thermal energy by taking advantage of the effect that a temperature difference occurs at both ends when a direct current flows through both ends of the thermoelectric conversion element.
- thermoelectric conversion element The energy conversion efficiency of such a thermoelectric conversion element is largely dependent on ZT which is a figure of merit of a thermoelectric conversion material.
- ZT may be determined according to Seebeck coefficient, electrical conductivity, thermal conductivity, and the like, and the higher the ZT value, the better the thermoelectric conversion material.
- thermoelectric conversion materials Although many thermoelectric conversion materials have been proposed so far, there is no situation that sufficient thermoelectric conversion materials having high thermoelectric conversion performance are provided. In particular, in recent years, the field of application for thermoelectric conversion materials is gradually expanding, and the temperature conditions may vary depending on the application field. However, since thermoelectric conversion performance may vary depending on temperature, each thermoelectric conversion material needs to be optimized for thermoelectric conversion performance in a field in which the thermoelectric conversion material is applied. However, it is not yet seen that thermoelectric conversion materials with optimized performance over a wide and wide temperature range are well prepared.
- an object of the present invention is to provide a thermoelectric material having excellent thermoelectric conversion performance in a wide temperature range, a method of manufacturing the same, and an apparatus using the same.
- thermoelectric material represented by the following Chemical Formula 1 after repeated studies on the thermoelectric material, and confirmed that the novel thermoelectric conversion material may have excellent thermoelectric conversion performance.
- the present invention was completed.
- X is at least one or more selected from the group consisting of F, Cl, Br, and I, and 2 ⁇ x ⁇ 2.6 and 0 ⁇ y ⁇ 1.
- x in Chemical Formula 1 may be x ⁇ 2.2.
- x in Chemical Formula 1 may be x ⁇ 2.1.
- x in Chemical Formula 1 may be 2.025 ⁇ x.
- y in Formula 1 may be y ⁇ 0.1.
- y in Formula 1 may be y ⁇ 0.05.
- the method of manufacturing a thermoelectric material according to the present invention may further include a step of sintering the composite after the composite forming step.
- the pressure sintering step may be performed by a hot press method or a discharge plasma sintering method.
- thermoelectric conversion element according to the present invention for achieving the above object includes the thermoelectric material according to the present invention.
- thermoelectric generator according to the present invention for achieving the above object includes the thermoelectric material according to the present invention.
- thermoelectric material excellent in thermoelectric conversion performance can be provided.
- the lattice thermal conductivity may be lowered by adjusting the addition amount of Cu element, and the electrical conductivity may be increased by optimizing the carrier concentration through substitution of the halogen element with Se element.
- thermoelectric material according to the present invention can be used as another material in place of or in addition to the conventional thermoelectric material.
- thermoelectric material according to the present invention when used in a thermoelectric device for power generation or the like, stable thermoelectric conversion performance can be ensured even when a material is exposed to a relatively low temperature.
- thermoelectric material according to the present invention may be used in solar cells, infrared windows (IR windows), infrared sensors, magnetic elements, memories, and the like.
- thermoelectric material 1 is a flowchart schematically showing a method of manufacturing a thermoelectric material according to an aspect of the present invention.
- thermoelectric material according to the Examples and Comparative Examples of the present invention.
- thermoelectric material according to an aspect of the present invention may be represented by the following Chemical Formula 1.
- X is at least one or more selected from the group consisting of F, Cl, Br, and I, and 2 ⁇ x ⁇ 2.6 and 0 ⁇ y ⁇ 1.
- thermoelectric material according to the present invention is a Cu-Se-based thermoelectric material containing Cu and Se, and is composed of a form in which a part of Se is substituted with a halogen element. That is, the thermoelectric material according to the present invention may be configured in a form in which a part of Se site is deficient and F, Cl, Br and / or I are substituted in such deficient site.
- thermoelectric material according to the present invention the thermoelectric conversion performance can be further improved compared to the conventional Cu-Se-based thermoelectric material.
- thermoelectric material according to the present invention can be improved in electrical properties by substituting Se with a halogen element.
- the electrical conductivity can be remarkably improved by replacing X at the Se site to increase the hole concentration, that is, the carrier concentration. Therefore, the thermoelectric material according to the present invention is optimized in electrical properties compared to the conventional Cu-Se-based thermoelectric material, it is possible to implement a higher level of thermoelectric performance index.
- thermoelectric material according to the present invention contains a relatively large amount of Cu as compared to a conventional Cu-Se-based thermoelectric material.
- thermoelectric material according to the present invention is configured such that when the total content of Se and X is 1, the content of Cu in comparison thereto is greater than 2. According to this configuration of the present invention, the thermal conductivity of the thermoelectric material, particularly the lattice thermal conductivity, can be lowered, and the thermoelectric conversion performance can be improved.
- x in Chemical Formula 1 may satisfy the condition of x ⁇ 2.2.
- thermoelectric material according to the present invention may satisfy the condition of x ⁇ 2.15.
- thermoelectric material according to the present invention may satisfy the condition of x ⁇ 2.1.
- Chemical Formula 1 may satisfy a condition of 2.01 ⁇ x.
- x in Chemical Formula 1 may be configured to satisfy a condition of 2.025 ⁇ x.
- y in Formula 1 may be y ⁇ 0.1.
- y in Formula 1 may be 0.001 ⁇ y.
- y in Formula 1 may be y ⁇ 0.05.
- thermoelectric conversion performance of the thermoelectric material according to the present invention can be further improved.
- thermoelectric material represented by the formula (1) may include a part of the secondary phase, the amount may vary depending on the heat treatment conditions.
- thermoelectric material according to the present invention when the content of Se is 1 with respect to the Cu-Se-based thermoelectric material, the content of Cu is more than 2, a part of Se is formed to be replaced with a halogen element Can be. Therefore, the thermoelectric material according to the present invention, due to such a constitutional feature, compared with the conventional Cu-Se-based thermoelectric material, the electrical conductivity is increased, the thermal conductivity is reduced, the ZT value is increased, the thermoelectric conversion performance can be improved. have.
- thermoelectric material 1 is a flowchart schematically showing a method of manufacturing a thermoelectric material according to an aspect of the present invention.
- the method of manufacturing a thermoelectric material according to the present disclosure may include a mixture forming step S110 and a compound forming step S120.
- the mixture forming step (S110) to correspond to the formula (1), in addition to Cu and Se as a raw material may be mixed by mixing CuX (halogen compound containing copper) to form a mixture.
- CuX halogen compound containing copper
- each raw material may be mixed in powder form.
- the mixing between each raw material is made better, the reactivity between each raw material can be improved, the compound synthesis can be made well in step S120.
- the mixing of each raw material may be performed in the manner of hand milling (ball milling), ball milling (planetary ball mill), etc. using mortar (mortar)
- the present invention is not limited by this specific mixing method.
- the compound forming step (S120) is a step of forming a compound according to Chemical Formula 1 by heat-treating the mixture formed in step S110, that is, Cu x Se 1-y X y (X is F, Cl, Br and I At least one, 2 ⁇ x ⁇ 2.6, 0 ⁇ y ⁇ 1).
- the mixture produced in step S110 may be put into a furnace and heated at a predetermined temperature for a predetermined time to allow the compound of Formula 1 to be synthesized.
- step S120 may be performed by a solid phase reaction method.
- the raw material that is, the mixture used in the synthesis, does not change into a completely liquid state in the synthesis process, and the reaction may occur in the solid state.
- the step S120 may be performed for 1 hour to 24 hours in the temperature range of 200 °C to 650 °C. Since this temperature range is lower than the melting point of Cu, when heated in this temperature range, Cu x Se 1-y X y may be synthesized in a state where Cu is not dissolved. For example, the step S120 may be performed for 15 hours under a temperature condition of 450 ° C.
- step S120 for the synthesis of Cu x Se 1-y X y , a mixture of Cu, Se and X is put into a cemented carbide mold to make pellets, and the mixture of pellets is fused silica tube (fused are loaded in a silica tube) it can be sealed vacuum.
- the vacuum-sealed first mixture may be charged into a furnace and heat treated.
- thermoelectric material manufacturing method according to the present invention after the compound forming step (S120), may further comprise a step (S130) of pressure sintering the compound.
- step S130 may be performed by a hot press (Hot Press) method or a discharge plasma sintering (Spark Plasma Sintering) method.
- Hot Press Hot Press
- spark Plasma Sintering spark Plasma Sintering
- thermoelectric material according to the present invention when sintered by the pressure sintering method, it is easy to obtain a high sintered density and an effect of improving thermoelectric performance.
- the pressure sintering step may be performed under a pressure condition of 30MPa to 200MPa.
- the pressure sintering step may be performed under a temperature condition of 300 °C to 800 °C.
- the pressure sintering step may be performed for 1 minute to 12 hours under the pressure and temperature conditions.
- the step S130 may be performed while flowing a gas, such as Ar, He, N 2 , which contains a part of hydrogen or does not contain hydrogen in a vacuum state.
- a gas such as Ar, He, N 2 , which contains a part of hydrogen or does not contain hydrogen in a vacuum state.
- the step S130 may be performed by pulverizing the composite formed in the step S120 into a powder form, followed by pressure sintering. In this case, while improving convenience in the sintering and measuring process, the sintered density can be further increased.
- thermoelectric conversion element according to the present invention may include the above-mentioned thermoelectric material.
- thermoelectric material according to the present invention can effectively improve the ZT value in a wide temperature range compared to conventional thermoelectric materials, especially Cu-Se-based thermoelectric materials. Therefore, the thermoelectric material according to the present invention can be usefully used in thermoelectric conversion elements in place of or in addition to conventional thermoelectric conversion materials.
- thermoelectric material according to the present invention can be used in a thermoelectric power generation device that performs thermoelectric power generation using a waste heat source or the like. That is, the thermoelectric generator according to the present invention includes the thermoelectric material according to the present invention described above. In the case of the thermoelectric material according to the present invention, since it exhibits high conductivity values in a wide temperature range, such as a temperature range of 50 ° C. to 500 ° C., the thermoelectric material may be more usefully applied to thermoelectric power generation.
- thermoelectric material according to the present invention may be manufactured in the form of a bulk type thermoelectric material.
- Example 2 This composite was then sintered in the same manner as in Example 1 to obtain a sample of Example 2.
- Example 3 The amount of addition of Se and Br was different from that of Example 1, and a mixture of Cu 2.025 Se 0.95 Br 0.05 was obtained through mixing and synthesis in the same manner. This composite was then sintered in the same manner as in Example 1 to obtain a sample of Example 3.
- Examples 1-5 samples and Comparative Example samples electrical conductivity was measured at room temperature (RT) using ZEM-3 (Ulvac-Riko, Inc). And about the electrical conductivity measurement result, in Examples 1-3, it shows in FIG. 2 with a comparative example.
- the x-axis represents y of Chemical Formula 1.
- the x-axis represents a substitution element of Se, that is, a kind of X.
- Example 1 whose y is 0.001 is 542.9 S / cm, which is about 59.3% higher than that of the comparative example 340.8 S / cm.
- the electrical conductivity of Example 2 with y of 0.003 is 875.3 S / cm, which is about 157% higher than that of the comparative example.
- the electrical conductivity of Example 3 having y of 0.05 is 1333.6 S / cm, which is about 291% higher than that of the comparative example.
- thermoelectric conversion performance can be greatly improved due to the improved electrical conductivity.
- the substitution amount of Br increases, the electrical conductivity gradually improves.
- Example 4 the electrical conductivity of Example 4 in which a part of Se is substituted with Cl is 394.2 S / cm, which shows an increase in electrical conductivity of approximately 15.7% compared to the comparative example.
- the electrical conductivity of Example 5 in which a part of Se is substituted with I is 446.4 S / cm, which shows an increase in electrical conductivity of approximately 31% than that of the comparative example.
- thermoelectric conversion performance can be greatly improved.
Abstract
Description
Claims (11)
- 하기 화학식 1로 표시되는 열전 재료.<화학식 1>CuxSe1-yXy상기 화학식 1에서, X는 F, Cl, Br 및 I로 이루어진 군으로부터 선택된 적어도 어느 하나 이상이고, 2<x≤2.6 및 0<y<1이다.
- 제1항에 있어서,상기 화학식 1의 x는, x≤2.2인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 x는, x≤2.1인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 x는, 2.025≤x인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 y는, y<0.1인 것을 특징으로 하는 열전 재료.
- 제1항에 있어서,상기 화학식 1의 y는, y≤0.05인 것을 특징으로 하는 열전 재료.
- 제1항의 화학식 1에 대응되도록 Cu, Se 및 X를 칭량하여 혼합함으로써 혼합물을 형성하는 단계; 및상기 혼합물을 열처리하여 상기 화학식 1로 표시되는 화합물을 합성하는 단계를 포함하는 것을 특징으로 하는 제1항의 열전 재료 제조 방법.
- 제7항에 있어서,상기 합성물 형성 단계 후, 상기 합성물을 가압 소결하는 단계를 더 포함하는 것을 특징으로 하는 열전 재료 제조 방법.
- 제8항에 있어서,상기 가압 소결 단계는, 핫 프레스 방식 또는 방전 플라즈마 소결 방식에 의해 수행되는 것을 특징으로 하는 열전 재료 제조 방법.
- 제1항 내지 제6항 중 어느 한 항에 따른 열전 재료를 포함하는 열전 변환 소자.
- 제1항 내지 제6항 중 어느 한 항에 따른 열전 재료를 포함하는 열전 발전 장치.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CN201480048447.4A CN105518891A (zh) | 2013-10-17 | 2014-10-17 | 热电材料及其制造方法 |
JP2016518734A JP6358449B2 (ja) | 2013-10-17 | 2014-10-17 | 熱電材料及びその製造方法 |
EP14854063.6A EP3026720B1 (en) | 2013-10-17 | 2014-10-17 | Thermoelectric materials and their manufacturing method |
US14/914,582 US9960334B2 (en) | 2013-10-17 | 2014-10-17 | Thermoelectric materials and their manufacturing method |
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KR20130124040 | 2013-10-17 | ||
KR10-2013-0124040 | 2013-10-17 | ||
KR1020140133390A KR101635638B1 (ko) | 2013-10-17 | 2014-10-02 | 열전 재료 및 그 제조 방법 |
KR10-2014-0133390 | 2014-10-02 |
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WO2015057018A1 true WO2015057018A1 (ko) | 2015-04-23 |
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US (1) | US9960334B2 (ko) |
EP (1) | EP3026720B1 (ko) |
JP (1) | JP6358449B2 (ko) |
KR (1) | KR101635638B1 (ko) |
CN (1) | CN105518891A (ko) |
TW (1) | TWI546258B (ko) |
WO (1) | WO2015057018A1 (ko) |
Cited By (1)
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CN106981565A (zh) * | 2017-02-23 | 2017-07-25 | 深圳前海华兆新能源有限公司 | 高稳定性Cu2‑xSe复合热电材料及其制备方法 |
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WO2019171915A1 (ja) * | 2018-03-08 | 2019-09-12 | 住友電気工業株式会社 | 熱電材料素子、発電装置、光センサおよび熱電材料の製造方法 |
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US6091014A (en) * | 1999-03-16 | 2000-07-18 | University Of Kentucky Research Foundation | Thermoelectric materials based on intercalated layered metallic systems |
US20030057512A1 (en) * | 2001-08-31 | 2003-03-27 | Hans-Josef Sterzel | Thermoelectrically active materials and generators and peltier arrangements containing them |
US20100307556A1 (en) * | 2007-10-18 | 2010-12-09 | Lg Chem, Ltd | Process for preparation of compound containing 6a group element using reductant |
US20120055526A1 (en) * | 2010-08-26 | 2012-03-08 | Samsung Electronics Co., Ltd. | Thermoelectric material, and thermoelectric module and thermoelectric device comprising the thermoelectric material |
US20130032188A1 (en) * | 2010-02-22 | 2013-02-07 | Takeshi Kajihara | Thermoelectric power module |
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KR101452795B1 (ko) * | 2006-12-01 | 2014-10-21 | 메사추세츠 인스티튜트 오브 테크놀로지 | 나노 구조의 열전 재료에서의 높은 성능 지수를 위한 방법 |
JP2009253301A (ja) * | 2008-04-04 | 2009-10-29 | Samsung Electronics Co Ltd | ジカルコゲナイド熱電材料 |
WO2011094635A2 (en) * | 2010-01-29 | 2011-08-04 | Califoria Institute Of Technology | Nanocomposites with high thermoelectric performance and methods |
CN102674270A (zh) * | 2012-05-25 | 2012-09-19 | 武汉理工大学 | 一种低温固相反应制备Cu2Se热电材料的方法 |
CN104211024B (zh) * | 2013-06-04 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | P型可逆相变高性能热电材料及其制备方法 |
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2014
- 2014-10-02 KR KR1020140133390A patent/KR101635638B1/ko active IP Right Grant
- 2014-10-17 WO PCT/KR2014/009795 patent/WO2015057018A1/ko active Application Filing
- 2014-10-17 CN CN201480048447.4A patent/CN105518891A/zh active Pending
- 2014-10-17 EP EP14854063.6A patent/EP3026720B1/en active Active
- 2014-10-17 TW TW103135977A patent/TWI546258B/zh active
- 2014-10-17 JP JP2016518734A patent/JP6358449B2/ja active Active
- 2014-10-17 US US14/914,582 patent/US9960334B2/en active Active
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US6091014A (en) * | 1999-03-16 | 2000-07-18 | University Of Kentucky Research Foundation | Thermoelectric materials based on intercalated layered metallic systems |
US20030057512A1 (en) * | 2001-08-31 | 2003-03-27 | Hans-Josef Sterzel | Thermoelectrically active materials and generators and peltier arrangements containing them |
US20100307556A1 (en) * | 2007-10-18 | 2010-12-09 | Lg Chem, Ltd | Process for preparation of compound containing 6a group element using reductant |
US20130032188A1 (en) * | 2010-02-22 | 2013-02-07 | Takeshi Kajihara | Thermoelectric power module |
US20120055526A1 (en) * | 2010-08-26 | 2012-03-08 | Samsung Electronics Co., Ltd. | Thermoelectric material, and thermoelectric module and thermoelectric device comprising the thermoelectric material |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN106981565A (zh) * | 2017-02-23 | 2017-07-25 | 深圳前海华兆新能源有限公司 | 高稳定性Cu2‑xSe复合热电材料及其制备方法 |
Also Published As
Publication number | Publication date |
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EP3026720A4 (en) | 2017-01-04 |
KR20150044808A (ko) | 2015-04-27 |
JP2016537806A (ja) | 2016-12-01 |
EP3026720B1 (en) | 2018-12-05 |
JP6358449B2 (ja) | 2018-07-18 |
TWI546258B (zh) | 2016-08-21 |
US20160225970A1 (en) | 2016-08-04 |
CN105518891A (zh) | 2016-04-20 |
US9960334B2 (en) | 2018-05-01 |
EP3026720A1 (en) | 2016-06-01 |
TW201532969A (zh) | 2015-09-01 |
KR101635638B1 (ko) | 2016-07-01 |
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