KR20230149898A - N-type Thermoelectric materials of Cu doped Bi-Te-Se based solid solution and method for preparing the same - Google Patents
N-type Thermoelectric materials of Cu doped Bi-Te-Se based solid solution and method for preparing the same Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 239000006104 solid solution Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 9
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000011978 dissolution method Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 239000004615 ingredient Substances 0.000 claims 1
- 239000011669 selenium Substances 0.000 description 41
- 230000003247 decreasing effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052969 tetrahedrite Inorganic materials 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
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
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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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Abstract
본 발명은 n형 열전재료 및 그의 제조방법에 관한 것으로, 더욱 구체적으로는 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체에 구리(Cu)를 도핑하여 n형 열전재료를 제조함으로써, 열전도도는 감소하고 제벡계수 및 전기전도도의 증가로 인한 출력인자 값의 향상으로 인해 열전소자의 성능지수(dimensionless figure of merit, ZT)값은 상승하는 효과를 나타낼 수 있다.The present invention relates to an n-type thermoelectric material and a method for manufacturing the same. More specifically, the present invention relates to a solid solution of copper (Cu) in a bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3- based) solid solution. By manufacturing an n-type thermoelectric material by doping, the thermal conductivity is reduced and the output factor value is improved due to an increase in the Seebeck coefficient and electrical conductivity, thereby increasing the dimensionless figure of merit (ZT) value of the thermoelectric element. It can be expressed.
Description
본 발명은 n형 열전재료 및 그의 제조방법에 관한 것으로, 더욱 구체적으로는 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체에 구리(Cu)를 도핑함으로써 열전성능 및 열전효율이 향상된 n형 열전재료 및 그의 제조방법에 관한 것이다.The present invention relates to an n-type thermoelectric material and a method for manufacturing the same. More specifically, the present invention relates to a method for producing copper (Cu) in a solid solution of bismuth telluride (Bi 2 Te 3 based) and bismuth selenide (Bi 2 Se 3 based). It relates to an n-type thermoelectric material with improved thermoelectric performance and thermoelectric efficiency by doping and a method of manufacturing the same.
열전 소재의 에너지 변환 효율은 무차원 성능지수(dimensionless figureofmerit, ZT)로 평가되며, 재료마다 최대의 성능을 나타내는 온도가 다르다. 커테루다이트, 클라스레이트, 실리사이드 등이 중/고온 영역에서의 우수한 열전재료로서 알려져 있으며, 상온 부근의 저온 영역에서는 Bi2Te3계 재료가 우수한 성능을 나타낸다. Bi2Te3계 재료는 이미 냉각용 재료로서 상당한 시장을 형성하고 있으나, 발전용 재료로서는 보다 더 높은 성능지수가 요구되고 있어 여전히 활발한 연구가 진행되고 있다.The energy conversion efficiency of thermoelectric materials is evaluated by the dimensionless figure of merit (ZT), and the temperature at which each material achieves maximum performance is different. Caterudite, clathrate, silicide, etc. are known as excellent thermoelectric materials in the mid/high temperature range, and Bi 2 Te 3 based materials show excellent performance in the low temperature range around room temperature. Bi 2 Te 3 based materials have already formed a significant market as cooling materials, but as materials for power generation, a higher performance index is required, so active research is still underway.
Bi2Te3계는 일반적으로 같은 결정구조를 갖는 Sb2Te3계 및 Bi2Se3계와 고용체를 형성시켜 각각 p형(Bi, Sb)2Te3와 n형 Bi2(Te, Se)3로 쓰이는데, n형 재료는 p형 재료에 비해 낮은 성능지수를 나타내고 있으며, 열전특성이 조성과 운반자 농도에 매우 민감하게 변한다. 따라서 열전 소자의 제작에는 p형 및 n형 재료가 모두 필요하기 때문에, n형 Bi2Te3계 재료의 조성 및 운반자 농도 최적화를 통한 성능지수의 향상에 대한 연구가 필요하다.The Bi 2 Te 3 system generally forms a solid solution with the Sb 2 Te 3 system and the Bi 2 Se 3 system, which have the same crystal structure, to form p-type (Bi, Sb) 2 Te 3 and n-type Bi 2 (Te, Se) systems, respectively. It is used as 3 , and n-type materials show a lower performance index than p-type materials, and thermoelectric properties vary very sensitively to composition and carrier concentration. Therefore, since both p-type and n-type materials are required for the production of thermoelectric devices, research is needed on improving the performance index through optimizing the composition and carrier concentration of n-type Bi 2 Te 3 -based materials.
n형 Bi2Te3계 재료는 p형 재료에 비해 낮은 성능지수를 나타내고, 열전특성이 조성과 운반자 농도에 민감하게 변하기 때문에, n형 재료의 조성 및 운반자 농도 최적화를 통한 성능지수 향상에 대한 연구가 필요하다.Since n-type Bi 2 Te 3 based materials show a lower figure of merit compared to p-type materials and thermoelectric properties vary sensitively to composition and carrier concentration, research on improving the figure of merit through optimizing the composition and carrier concentration of n-type materials is needed.
이에 본 발명자들은 종래의 문제점을 해결하기 위해, Bi2Te3와 Bi2Se3의 고용체 형성을 통한 열전도도의 저감과 도핑을 통한 운반자 농도 최적화로 n형 Bi2Te3계 재료의 열전성능을 향상시킬 수 있는 기술을 개발하고 본 발명을 완성하였다.Accordingly, in order to solve the conventional problem, the present inventors improved the thermoelectric performance of the n-type Bi 2 Te 3 -based material by reducing thermal conductivity through the formation of a solid solution of Bi 2 Te 3 and Bi 2 Se 3 and optimizing the carrier concentration through doping. An improved technology was developed and the present invention was completed.
상기한 배경기술로서 설명된 사항들은 본 발명의 배경에 대한 이해증진을 위한 것일 뿐, 이 기술분야에서 통상의 지식을 가진 자에게 이미 알려진 종래기술에 해당함을 인정하는 것으로 받아들여져서는 안 될 것이다.The matters described above as background technology are only for the purpose of improving understanding of the background of the present invention, and should not be taken as admission that they correspond to prior art already known to those skilled in the art.
상기한 종래 기술의 문제점을 해결하기 위하여, 본 발명은 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체에 구리(Cu)를 도핑한 n형 열전재료를 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art described above, the present invention is an n-type thermoelectric doped with copper (Cu) in a solid solution of bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3- based) The purpose is to provide materials.
또한, 본 발명은 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체에 구리(Cu)를 도핑하여 n형 열전재료를 제조하는 방법을 제공하는 것을 목적으로 한다.In addition, the present invention provides a method of manufacturing an n-type thermoelectric material by doping copper (Cu) into a solid solution of bismuth telluride-based (Bi 2 Te 3 -based) and bismuth selenide-based (Bi 2 Se 3- based). The purpose.
본 발명의 다른 목적 및 이점은 하기의 발명의 상세한 설명, 청구범위 및 도면에 의해 더욱 명확하게 된다.Other objects and advantages of the present invention will become more apparent from the following detailed description, claims, and drawings.
상기한 기술적 과제를 해결하기 위하여, 본 발명에서는 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체를 제조하고 구리(Cu)를 도핑하여 제조된 n형 열전재료를 제공한다.In order to solve the above technical problem, in the present invention, n bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3 based) solid solutions were prepared and doped with copper (Cu). Provides type thermoelectric materials.
또한, 본 발명에서는 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체에 구리(Cu)를 도핑함으로써 열전효율이 향상된 n형 열전재료의 제조방법을 제공한다.In addition, the present invention provides a method for manufacturing an n-type thermoelectric material with improved thermoelectric efficiency by doping copper (Cu) into a solid solution of bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3- based). to provide.
본 발명은, 원자의 치환에 의한 포논 산란 증가로 열전도도를 감소시키기 위해 Bi2Te3-Bi2Se3 고용체(Bi2Te3-ySey)를 형성하고, 도펀트를 첨가하여 전기적 특성을 향상시키는 방법으로 구성될 수 있다. The present invention forms a Bi 2 Te 3 -Bi 2 Se 3 solid solution (Bi 2 Te 3-y Se y ) to reduce thermal conductivity by increasing phonon scattering due to substitution of atoms, and adds a dopant to improve electrical properties. It can be configured in a way to improve it.
본 발명에서는, 밀폐용해법으로 n형 Bi2Te3-ySey 고용체 분말을 합성하고, 구리(Cu)를 첨가하여 열간 압축성형으로 소결하여 n형 열전재료를 제조할 수 있다.In the present invention, an n-type thermoelectric material can be manufactured by synthesizing n-type Bi 2 Te 3-y Se y solid solution powder by a closed dissolution method, adding copper (Cu) and sintering by hot compression molding.
본 발명에서, 성능지수를 향상시키기 위해서는 높은 출력인자와 낮은 열전도도가 요구된다. Bi2Te3계에 Bi2Se3계를 첨가하면 Se원자는 Te원자와 치환되면서 전 조성 범위에서 고용체를 형성하므로 결정격자의 주기성은 유지되지만, 합금화에 따른 격자의 변형으로 인한 단파장의 포논 산란으로 격자 열전도도를 감소시킬 수 있다.In the present invention, a high output factor and low thermal conductivity are required to improve the performance index. When Bi 2 Se 3 is added to the Bi 2 Te 3 system, Se atoms are replaced with Te atoms to form a solid solution in the entire composition range, so the periodicity of the crystal lattice is maintained, but short-wavelength phonon scattering occurs due to lattice deformation due to alloying. This can reduce the lattice thermal conductivity.
또한 도핑에 의한 성분원소의 치환은 전자구조와 전기적 특성에 영향을 미칠 뿐만 아니라 이온화된 불순물에 의한 격자산란으로 열전도도에도 영향을 미칠 수 있다. 격자산란 인자에는 점결함 산란, 결정립 산란, 포논-포논 산란, 전자-포논 산란 등이 있으며, 도핑에 의해 발생한 전자와 포논과의 산란으로 격자 열전도도가 감소할 수 있다. 따라서 도핑을 통해 운반자 농도의 최적화에 의한 출력인자의 향상과 함께 격자 열전도도의 감소도 기대할 수 있다.In addition, substitution of constituent elements by doping not only affects the electronic structure and electrical properties, but can also affect thermal conductivity due to lattice scattering by ionized impurities. Lattice scattering factors include point defect scattering, grain scattering, phonon-phonon scattering, and electron-phonon scattering, and the lattice thermal conductivity may be reduced due to scattering of electrons and phonons generated by doping. Therefore, a decrease in lattice thermal conductivity can be expected along with an improvement in output factor through optimization of carrier concentration through doping.
본 발명은 기존과 차별화된 열전재료에 관한 것으로서, 비스무스 텔루라이드계(Bi2Te3계) 및 비스무스 셀렌나이드계(Bi2Se3계)의 고용체에 구리(Cu)를 도핑하여 n형 열전재료를 제조함으로써, 제벡계수와 전기전도도의 증가로 인한 출력인자(Power factor, PF)의 향상과 열전도도의 감소로 인해 열전소재의 무차원 열전 성능지수(dimensionless figure of merit, ZT)값은 상승하는 효과를 나타낼 수 있다.The present invention relates to a thermoelectric material that is differentiated from the existing one, and is an n-type thermoelectric material by doping copper (Cu) into a solid solution of bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3- based). By manufacturing, the power factor (PF) is improved due to the increase in Seebeck coefficient and electrical conductivity, and the dimensionless thermoelectric figure of merit (ZT) value of the thermoelectric material increases due to the decrease in thermal conductivity. It can show an effect.
도 1은 본 발명에 따른 실험예의 X선 회절(X-ray diffraction)패턴 분석 결과를 나타내는 것이다.
도 2는 본 발명에 따른 실험예의 운반자 농도(Carrier concestration, n) 및 이동도(Mobility, μ) 값의 변화를 분석한 결과를 나타내는 것이다.
도 3은 본 발명에 따른 실험예의 전기전도도(Electrical conductivity, σ) 값의 변화를 분석한 결과를 나타내는 것이다.
도 4는 본 발명에 따른 실험예의 제벡계수(Seebeck coefficient, α)값의 변화를 분석한 결과를 나타내는 것이다.
도 5는 본 발명에 따른 실험예의 출력인자(Power factor, PF)값의 변화를 분석한 결과를 나타내는 것이다.
도 6a는 본 발명에 따른 실험예의 열전도도(Thermal conductivity, κ) 값의 변화를 분석한 결과를 나타내는 것이다.
도 6b는 본 발명에 따른 실험예의 전자 열전도도(Electronic thermal conductivity, κE) 값의 변화를 분석한 결과를 나타내는 것이다.
도 6c는 본 발명에 따른 실험예의 격자 열전도도(Lattice thermal conductivity, κL) 값의 변화를 분석한 결과를 나타내는 것이다.
도 7은 본 발명에 따른 실험예의 무차원 열전성능지수(Dimensionless figure of merit, ZT)값의 변화를 분석한 결과를 나타내는 것이다.
도 8은 본 발명의 일실시예에 대한 제조공정을 개략적으로 나타낸 것이다.Figure 1 shows the results of X-ray diffraction pattern analysis of an experimental example according to the present invention.
Figure 2 shows the results of analyzing changes in carrier concentration (n) and mobility (μ) values of experimental examples according to the present invention.
Figure 3 shows the results of analyzing the change in electrical conductivity (σ) value of an experimental example according to the present invention.
Figure 4 shows the results of analyzing the change in Seebeck coefficient (α) value of an experimental example according to the present invention.
Figure 5 shows the results of analyzing the change in power factor (PF) value of an experimental example according to the present invention.
Figure 6a shows the results of analyzing the change in thermal conductivity (κ) value of an experimental example according to the present invention.
Figure 6b shows the results of analyzing the change in electronic thermal conductivity (κ E ) value of an experimental example according to the present invention.
Figure 6c shows the results of analyzing the change in lattice thermal conductivity (κ L ) value of an experimental example according to the present invention.
Figure 7 shows the results of analyzing the change in the dimensionless thermoelectric figure of merit (ZT) value of the experimental example according to the present invention.
Figure 8 schematically shows the manufacturing process for one embodiment of the present invention.
이하, 첨부된 도면을 참조로 본 발명의 바람직한 실시예를 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 요지에 따라 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 있어서 자명할 것이다.Hereinafter, preferred embodiments of the present invention will be described in more detail with reference to the attached drawings. These examples are only for illustrating the present invention in more detail, and it is understood by those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. It will be self-evident.
본 발명의 특징들은 이하의 실시예를 통해서 더욱 명확히 설명될 수 있다.The features of the present invention can be more clearly explained through the following examples.
본 발명에서, Se 원자의 치환에 의한 포논 산란으로 인해 열전도도를 감소시키기 위해 Bi2Te3-Bi2Se3 고용체(Bi2Te3-ySey)를 형성하고, 도펀트를 첨가하여 전기적 특성을 향상시키고자 하였다. 밀폐용해법으로 합성된 n형 Bi2Te3-ySey 고용체 분말을 열간 압축성형으로 소결하였고, Se고용량과 도핑량에 따른 상 변화 및 열전특성에 대하여 조사하였다.In the present invention, a Bi 2 Te 3 -Bi 2 Se 3 solid solution (Bi 2 Te 3-y Se y ) is formed to reduce thermal conductivity due to phonon scattering by substitution of Se atoms, and a dopant is added to improve electrical properties. wanted to improve. The n-type Bi 2 Te 3-y Se y solid solution powder synthesized by the closed dissolution method was sintered by hot compression molding, and the phase change and thermoelectric properties according to the Se content and doping amount were investigated.
본 발명에서, X선 회절 분석(X-ray diffraction:Bruker, D8-Advance)을 통해 고용체의 상 변화를 조사하였다. CuKα (40 ㎸, 30 ㎃)방사선을 이용하였고, 측정조건은 다음과 같다. 회절 각도 2θ=10~90°, 주사간격 0.02°, 주사속도 3°/min, 파장 0.15405 ㎚로 측정하였다.In the present invention, the phase change of the solid solution was investigated through X-ray diffraction analysis (Bruker, D8-Advance). CuKα (40 kV, 30 mA) radiation was used, and the measurement conditions were as follows. It was measured at a diffraction angle of 2θ = 10 to 90°, a scanning interval of 0.02°, a scanning speed of 3°/min, and a wavelength of 0.15405 nm.
소결체는 전기전도도 및 제벡계수를 측정하기 위해 3 mm × 3 mm × 10 mm의 직육면체의 형태로 만들고, 열전도도 및 홀(Hall) 계수의 측정을 위하여 10 mm × 10 mm × 1mm의 직육면체 형태로 만들었다. 상기 전기전도도 및 제벡계수는 323-573 K 온도범위에서 ZEM-3 (Ulvac-Riko)를 이용하여 헬륨(He) 분위기에서 측정하였고, 열전도도는 323-573 K 온도범위에서 TC-9000H (Ulvac-Riko)를 이용하여 측정하였다.The sintered body was made in the form of a 3 mm × 3 mm × 10 mm rectangular parallelepiped to measure electrical conductivity and Seebeck coefficient, and in the form of a 10 mm × 10 mm × 1 mm rectangular parallelepiped to measure thermal conductivity and Hall coefficient. . The electrical conductivity and Seebeck coefficient were measured in a helium (He) atmosphere using ZEM-3 (Ulvac-Riko) in the temperature range of 323-573 K, and the thermal conductivity was measured in a helium (He) atmosphere in the temperature range of 323-573 K using TC-9000H (Ulvac-Riko). It was measured using Riko).
열전소재의 에너지 변환 효율은 열전재료의 고유의 물성인 제벡계수(α), 전기전도도(σ) 및 열전도도(κ)로 좌우되는 성능지수에 의해 평가되며, 성능지수(Z)는 계산식 1과 같이 정의된다.The energy conversion efficiency of thermoelectric materials is evaluated by the performance index that depends on the Seebeck coefficient (α), electrical conductivity (σ), and thermal conductivity (κ), which are the unique physical properties of the thermoelectric material, and the performance index (Z) is calculated by Equation 1 and are defined together.
여기에 절대온도(T)를 곱한 ZT를 무차원 성능지수(dimensionless figureofmerit)라 하고, 서로 다른 사용온도에서 최대의 성능을 나타내는 열전재료들의 특성을 비교·평가하는 주요 지표로서 사용된다.Here, ZT multiplied by the absolute temperature (T) is called the dimensionless figure of merit, and is used as a key indicator to compare and evaluate the characteristics of thermoelectric materials that exhibit maximum performance at different operating temperatures.
무차원 성능지수(ZT)는 열전재료의 성능을 나타내는 척도이며, 측정된 제벡계수, 전기전도도 및 열전도도로부터 계산식 2에 대입하여 계산하였다.The dimensionless performance index (ZT) is a measure of the performance of thermoelectric materials, and was calculated by substituting the measured Seebeck coefficient, electrical conductivity, and thermal conductivity into Equation 2.
전기전도도와 제벡계수는 어느 한쪽의 성능을 증가시키면 다른 한쪽이 감소하는 상반 관계를 나타내어, 상기 계산식 2에 나타낸 바와 같이, 열전재료의 성능지수를 증가시키기 위해서 제벡계수와 전기전도도는 증가시키고 열전도도는 감소시키기 위한 연구가 진행되어 왔다.Electrical conductivity and Seebeck coefficient show a conflicting relationship in which increasing the performance of one reduces the other. As shown in equation 2 above, in order to increase the performance index of the thermoelectric material, the Seebeck coefficient and electrical conductivity are increased and the thermal conductivity is increased. Research has been conducted to reduce .
제벡계수(α)는 시편의 한쪽을 가열하여 시편 양단의 온도차에 의해 발생하는 열기전력을 측정하는 방식인 온도 미분법을 이용하여 측정하였다. 제벡계수의 부호가 (-)일 때 N-type의 반도체 특성을, (+)일때 P-type의 반도체 특성을 나타낸다. The Seebeck coefficient (α) was measured using the temperature differential method, which is a method of heating one side of the specimen and measuring the thermoelectric power generated by the temperature difference between both ends of the specimen. When the sign of the Seebeck coefficient is (-), it indicates N-type semiconductor characteristics, and when it is (+), it indicates P-type semiconductor characteristics.
전기전도도(σ)는 DC 4단자(4-probe)법으로 측정하였다.Electrical conductivity (σ) was measured using the DC 4-probe method.
제벡계수와 전기전도도는 Ulvac-Riko ZEM3 장비를 사용하였고, 시편의 산화 방지 및 온도 안정화를 위해 헬륨 분위기에서 측정하였다. 측정된 제벡계수와 전기전도도로부터 계산식 3을 이용하여 출력인자(PF: Power Factor)를 계산할 수 있다.Seebeck coefficient and electrical conductivity were measured using Ulvac-Riko ZEM3 equipment and in a helium atmosphere to prevent oxidation and stabilize the temperature of the specimen. The power factor (PF) can be calculated using Equation 3 from the measured Seebeck coefficient and electrical conductivity.
열전도도는 열확산도(D), 비열(Cp) 및 밀도(d)로부터 다음 식을 이용하여 얻을 수 있다. 열확산도는 Ulvac-Riko TC-9000H 장비를 사용하여 레이저 플레쉬(laser-flash)방법으로 측정하였다.Thermal conductivity can be obtained from thermal diffusivity (D), specific heat (Cp), and density (d) using the following equation. Thermal diffusivity was measured using a laser-flash method using Ulvac-Riko TC-9000H equipment.
실험예 1Experimental Example 1
본 발명의 일실시예에 대한 조성은 하기 표 1에 나타내었고, X선 회절패턴 분석 결과는 도 1에 나타내었으며, 운반자 농도 및 이동도 값은 도 2, 전기전도도, 제벡계수, 출력인자, 열전도도 값은 도 3 내지 도 6에 나타내었으며, 열전소재의 무차원 열전 성능지수값은 도 7에 정리하여 나타내었다.The composition of one embodiment of the present invention is shown in Table 1 below, the X-ray diffraction pattern analysis results are shown in Figure 1, and the carrier concentration and mobility values are shown in Figure 2, electrical conductivity, Seebeck coefficient, output factor, and thermal conductivity. The degree values are shown in Figures 3 to 6, and the dimensionless thermoelectric performance index values of thermoelectric materials are summarized and shown in Figure 7.
원소 상태의 Bi, Te, Se 및 도펀트 Cu를 각 조성에 맞게 칭량한 후 석영관에 장입하여 진공상태(10-6 Torr)에서 밀봉하였다. 밀봉된 원료를 1073 K에서 10시간 동안 용해한 후 로냉하였다. 상기 얻어진 잉곳(ingot)을 45 ㎛ 이하로 파쇄 후 초경 몰드에 장입하여 693 K에서 200 ㎫의 압력으로 1시간 동안 열간 압축 성형(Hot press)을 통해 소결하였다.Elemental states of Bi, Te, Se, and dopant Cu were weighed according to each composition, then charged into a quartz tube and sealed under vacuum (10 -6 Torr). The sealed raw material was dissolved at 1073 K for 10 hours and then furnace cooled. The obtained ingot was crushed to 45 ㎛ or less, charged into a carbide mold, and sintered through hot pressing at 693 K and a pressure of 200 MPa for 1 hour.
도 1은 본 실험예에 의한 열전재료 소결체의 X선 회절패턴을 나타낸 것이다. 모든 실험예의 열전재료상은 ICDD 표준회절자료(PDF# 98-061-7187)와 일치하였고, 어떠한 이차상도 발견되지 않는 단일상으로 합성되었다.Figure 1 shows the X-ray diffraction pattern of the sintered thermoelectric material according to this experimental example. The thermoelectric material phase of all experimental examples matched the ICDD standard diffraction data (PDF# 98-061-7187) and was synthesized as a single phase in which no secondary phase was found.
도 2는 본 발명의 실험예에 의한 열전재료 소결체의 전하이동 특성을 나타낸 것이다. 홀(Hall)계수는 음의 값으로 나와 주 캐리어가 전자(electron)인 n-type 반도체임을 확인하였다. Bi2Te2.7Se0.3(표 1의 일실시예 ①)의 캐리어농도는 6.07 × 1019 [/cm3]이고, Bi2Te2.4Se0.6(표 1의 일실시예 ③)의캐리어 농도는 5.00 × 1019 [/cm3]로 Se의 고용량이 증가하였을 때 감소하였다. Bi-Te-Se 고용체에 Cu를 도핑하였을 때는 정공농도를 증가시키는 억셉터로 작용을 하여 캐리어농도가 감소하였다.Figure 2 shows the charge transfer characteristics of the sintered thermoelectric material according to an experimental example of the present invention. The Hall coefficient was found to be a negative value, confirming that it was an n-type semiconductor whose main carrier was an electron. The carrier concentration of Bi 2 Te 2.7 Se 0.3 (Example ① in Table 1) is 6.07 × 10 19 [/cm 3 ], and the carrier concentration of Bi 2 Te 2.4 Se 0.6 (Example ③ in Table 1) is 5.00. × 10 19 [/cm 3 ], which decreased when the solid solution amount of Se increased. When Cu was doped into the Bi-Te-Se solid solution, it acted as an acceptor to increase hole concentration and the carrier concentration decreased.
도 3은 본 발명의 실험예에 의한 열전재료 소결체의 전기전도도 변화를 나타낸 것이다. 모든 시편은 온도가 증가할수록 전기전도도가 감소하는 축퇴반도체 특성을 보였다. Bi2Te2.4Se0.6Cu0.01(표 1의 일실시예 ④)의 경우 온도에 따라 감소하다가 200 ℃구간에서 다시 상승하였다. Se의 고용량이 증가함에 따라 전기전도도는 감소하였고, Cu를 도핑함으로써 전기전도도는 증가하였다.Figure 3 shows the change in electrical conductivity of the sintered thermoelectric material according to an experimental example of the present invention. All specimens showed degenerate semiconductor characteristics in which electrical conductivity decreased as temperature increased. In the case of Bi 2 Te 2.4 Se 0.6 Cu 0.01 (Example ④ in Table 1), it decreased with temperature and then increased again in the 200 ℃ range. As the solid dosage of Se increased, the electrical conductivity decreased, and by doping Cu, the electrical conductivity increased.
도 4는 본 발명의 실험예에 의한 열전재료 소결체의 제벡계수 변화를 나타낸 것이다. 모든 시편은 측정온도 범위에서 다수 캐리어가 전자인 n-type 전도성을 의미하는 음의 제벡계수 값을 나타내었다. 각 Bi-Te-Se 고용체에 Se의 고용량이 증가했을 때, Cu를 도핑하였을 때, 캐리어 농도가 감소하여 제벡계수의 절대값이 증가하였다. Bi2Te2.4Se0.6Cu0.01(표 1의 일실시예 ④)의 제벡계수 절대값이 169~188 [μVK-1]로 전 온도 구간에서 다른 시편들 대비 높은 값을 나타내었다.Figure 4 shows the change in Seebeck coefficient of the sintered thermoelectric material according to an experimental example of the present invention. All specimens showed negative Seebeck coefficient values, indicating n-type conductivity in which the majority carrier is electron, in the measurement temperature range. When the amount of Se in each Bi-Te-Se solid solution increased and Cu was doped, the carrier concentration decreased and the absolute value of the Seebeck coefficient increased. The absolute Seebeck coefficient of Bi 2 Te 2.4 Se 0.6 Cu 0.01 (Example ④ in Table 1) was 169 to 188 [μVK -1 ], which was higher than that of other specimens in all temperature ranges.
도 5는 본 발명의 실험예에 의한 열전재료 소결체의 출력인자 값의 변화를 나타낸 것이다. 출력인자는 전기전도도와 제벡계수에 의해 좌우된다. 각 Bi-Te-Se고용체에 Cu를 도핑하였을 때, 전기전도도의 값과 제벡계수의 값이 모두 증가함으로써 파워팩터 값이 증가하였고, 25~150 ℃구간에서는 Bi2Te2.7Se0.3Cu0.01(표 1의 일실시예 ②)시편이 14.7~16.5 [10-4Wm-1K-2]로 다른 시편들보다 높은 값을 가지며, 250~300℃구간 에서는 Bi2Te2.4Se0.6Cu0.01(표 1의 일실시예 ④)시편이 11.2~12.2 [10-4Wm-1K-2]로 보다 우수한 값을 가진다. 200℃구간에서는 앞서 언급한 두 시편의 값이 약 13.3 [10-4Wm-1K-2]로 매우 미미한 차이를 가진다. 출력인자값은 열전모듈에서 출력을 결정하는 중요한 요소로 알려져 있으며, 본 발명을 통해 Cu의 도핑효과로 인한 출력인자 값의 향상을 확인하였다.Figure 5 shows the change in output factor value of the sintered thermoelectric material according to an experimental example of the present invention. The output factor depends on electrical conductivity and Seebeck coefficient. When Cu was doped into each Bi-Te-Se solid solution, both the electrical conductivity value and the Seebeck coefficient increased, thereby increasing the power factor value, and in the range of 25 to 150 ℃, Bi 2 Te 2.7 Se 0.3 Cu 0.01 (Table Example 1 ②) Specimen has a higher value than other specimens at 14.7~16.5 [10 -4 Wm -1 K -2 ], and in the 250~300℃ range, Bi 2 Te 2.4 Se 0.6 Cu 0.01 (Table 1 One example of ④) specimen has a better value of 11.2~12.2 [10 -4 Wm -1 K -2 ]. In the 200℃ section, the values of the two specimens mentioned above have a very slight difference of approximately 13.3 [10 -4 Wm -1 K -2 ]. The output factor value is known to be an important factor in determining the output in a thermoelectric module, and through the present invention, it was confirmed that the output factor value was improved due to the doping effect of Cu.
도 6a 내지 도 6c는 본 발명의 실험예에 의한 열전재료 소결체의 열전도도를 나타낸 것으로, 열전도도(도 6a)는 전자에 의한 열전도도(도 6b)와 격자에 의한 열전도도(도 6c)의 합으로서 나타내며, 전자열전도도는 Wiedemann-Franz식(κE= LσT, L: Lorenz constant)에 의해 계산될 수 있다(이때 L=1.45×10-8V2K-2로 사용). 전자열전도도는 전기전도도와 관련이 있으므로, Se의 고용량이 증가하였을 때 전자열전도도는 감소하였고, 각 Bi-Te-Se 고용체에 Cu가 도핑되었을 때 전자열전도도는 증가하였다. 격자열전도도는 온도가 증가함에 따라 증가하였고 Se의 고용량이 증가하였을 때 감소하였으며, 각 Bi-Te-Se 고용체에 Cu가 도핑되었을 때 감소하였다. 이는 Se의 고용량 조절과 Cu의 도핑으로 인해 Bi2Te2.4Se0.6Cu0.01(표 1의 일실시예 ④)시편이 전 온도구간에서 다른 시편 대비 낮은 격자열전도도값을 가지며 150~200℃ 구간에서 0.62 [Wm-1K-1]를 나타냈다.FIGS. 6A to 6C show the thermal conductivity of the sintered thermoelectric material according to an experimental example of the present invention. The thermal conductivity (FIG. 6A) is the difference between the thermal conductivity by electrons (FIG. 6B) and the thermal conductivity by lattice (FIG. 6C). It is expressed as a sum, and the electronic thermal conductivity can be calculated by the Wiedemann-Franz equation (κ E = LσT, L: Lorenz constant) (in this case, L = 1.45 × 10 -8 V 2 K -2 is used). Since electronic thermal conductivity is related to electrical conductivity, when the solid solution of Se increased, electronic thermal conductivity decreased, and when Cu was doped into each Bi-Te-Se solid solution, electronic thermal conductivity increased. The lattice thermal conductivity increased as the temperature increased, decreased when the solid solution capacity of Se increased, and decreased when Cu was doped into each Bi-Te-Se solid solution. This is due to the high capacity control of Se and doping of Cu, the Bi 2 Te 2.4 Se 0.6 Cu 0.01 (Example ④ in Table 1) specimen has a lower lattice thermal conductivity value than other specimens in all temperature ranges and in the 150~200℃ range. It showed 0.62 [Wm -1 K -1 ].
도 7은 본 발명의 실험예에 의한 열전재료 소결체의 무차원 열전 성능지수 ZT를 나타낸 것이다. ZT값은 높은 출력인자와 낮은 열전도도를 가질 때 좋은 특성을 나타내는데, Se의 고용량 조절과 Cu를 도핑함으로써 출력인자가 크게 향상되었고, 격자열전도도를 낮춤으로써 Bi2Te2.4Se0.6Cu0.01(표 1의 일실시예 ④)시편이 전 온도 구간에서 다른 시편 대비 우수한 특성을 보였으며, 150 ℃ 구간에서 ZTmax= 0.67을 나타내어 Bi2Te2.4Se0.6Cu0.01(표 1의 일실시예 ④)시편이 본 발명의 최적 조성임을 나타낸다.Figure 7 shows the dimensionless thermoelectric performance index ZT of the sintered thermoelectric material according to an experimental example of the present invention. The ZT value shows good characteristics when it has a high output factor and low thermal conductivity. By adjusting the high capacity of Se and doping Cu, the output factor is greatly improved, and by lowering the lattice thermal conductivity, it is Bi 2 Te 2.4 Se 0.6 Cu 0.01 (Table Example ④) of 1 showed excellent characteristics compared to other specimens in all temperature ranges, and showed ZT max = 0.67 in the 150 ℃ range, Bi 2 Te 2.4 Se 0.6 Cu 0.01 (Example ④ in Table 1) This indicates that this is the optimal composition of the present invention.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 통상의 기술자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현 예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아닌 점은 명백하다. 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항과 그의 등가물에 의하여 정의된다고 할 것이다.As the specific parts of the present invention have been described in detail above, it is clear to those skilled in the art that these specific techniques are merely preferred implementation examples and do not limit the scope of the present invention. Terms or words used in this specification and claims should not be construed as limited to their common or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is. Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
Claims (5)
An n-type thermoelectric with improved thermoelectric performance and efficiency, which is manufactured by manufacturing a solid solution of bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3- based) and doping it with copper (Cu). ingredient.
상기 고용체는 Bi2Te3-Bi2Se3 고용체(Bi2Te3-ySey)를 형성하는 것을 특징으로 하는 열전성능 및 효율이 향상된 n형 열전재료.
According to claim 1,
The solid solution is an n-type thermoelectric material with improved thermoelectric performance and efficiency, characterized in that it forms a Bi 2 Te 3 -Bi 2 Se 3 solid solution (Bi 2 Te 3-y Se y ).
상기 고용체 형성 후 구리(Cu)를 도핑하여 Bi2Te2.4Se0.6Cu0.01로 제조되는 것을 특징으로 하는 열전성능 및 효율이 향상된 n형 열전재료.
According to claim 1,
An n-type thermoelectric material with improved thermoelectric performance and efficiency, characterized in that it is manufactured by doping copper (Cu) after forming the solid solution to Bi 2 Te 2.4 Se 0.6 Cu 0.01 .
상기 고용체에 구리(Cu)를 첨가하여 도핑하는 단계를 포함하는 것을 특징으로 하는 열전성능 및 효율이 향상된 n형 열전재료의 제조방법.
Solid solution synthesis step of bismuth telluride-based (Bi 2 Te 3- based) and bismuth selenide-based (Bi 2 Se 3 based); and
A method of manufacturing an n-type thermoelectric material with improved thermoelectric performance and efficiency, comprising the step of doping the solid solution by adding copper (Cu).
상기 고용체 합성단계에서 밀폐용해법으로 Bi2Te3-ySey 고용체를 합성하는 것을 특징으로 하는 열전성능 및 효율이 향상된 n형 열전재료의 제조방법.
According to claim 4,
A method for manufacturing an n-type thermoelectric material with improved thermoelectric performance and efficiency, characterized in that Bi 2 Te 3-y Se y solid solution is synthesized by a closed dissolution method in the solid solution synthesis step.
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