WO1999054941A1 - Procede de fabrication de corps fritte pour element de conversion thermoelectrique, corps fritte pour element de conversion thermoelectrique et element de conversion thermoelectrique utilisant ce corps fritte - Google Patents

Procede de fabrication de corps fritte pour element de conversion thermoelectrique, corps fritte pour element de conversion thermoelectrique et element de conversion thermoelectrique utilisant ce corps fritte Download PDF

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Publication number
WO1999054941A1
WO1999054941A1 PCT/JP1999/002162 JP9902162W WO9954941A1 WO 1999054941 A1 WO1999054941 A1 WO 1999054941A1 JP 9902162 W JP9902162 W JP 9902162W WO 9954941 A1 WO9954941 A1 WO 9954941A1
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WO
WIPO (PCT)
Prior art keywords
thermoelectric conversion
sintered body
conversion element
powder
powder containing
Prior art date
Application number
PCT/JP1999/002162
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English (en)
Japanese (ja)
Inventor
Kazunori Nakano
Hirofumi Tashiro
Mari Yonetsu
Original Assignee
Toyo Kohan Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Kohan Co., Ltd. filed Critical Toyo Kohan Co., Ltd.
Priority to AU35354/99A priority Critical patent/AU3535499A/en
Publication of WO1999054941A1 publication Critical patent/WO1999054941A1/fr

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur

Definitions

  • thermoelectric conversion element Description Method for producing sintered body for thermoelectric conversion element, sintered body for thermoelectric conversion element, and thermoelectric conversion element using the same
  • the present invention relates to a method for producing a sintered body used for a thermoelectric conversion element, a sintered body for a thermoelectric conversion element produced using the production method, and a thermoelectric conversion element using the sintered body.
  • Thermoelectric conversion elements have a function of converting heat to electricity (Seebeck effect) and a function of converting electricity to heat (Peltier effect), and are expected to be applied to energy conversion technology.
  • Peltier effect it is expected to be used as a module for temperature regulators of optical devices that support optoelectronics.
  • Modules for the temperature controller include a Bi-Te-Sb thermoelectric conversion element (hereinafter referred to as P-type thermoelectric conversion element) and a Bi-Te-Se thermoelectric conversion element (hereinafter n-type thermoelectric conversion element).
  • thermoelectric conversion element As a method of manufacturing the p-type thermoelectric conversion element or the n-type thermoelectric conversion element, a method of dissolving a raw material powder and growing a single-crystal ingot into a rod shape using a unidirectional solidification method (Japanese Patent Laid-Open No. And a method of sintering an alloy powder obtained by pulverizing a polycrystalline ingot obtained by melting a raw material powder into a bulk using a hot pressing method ( Japanese Patent Application Laid-Open No. 1-106748) was used to obtain the obtained ingots and balls.
  • a method has been performed in which an element is obtained by cutting a sintered compact into a desired shape.
  • thermoelectric conversion elements with excellent characteristics can be obtained, they are easily damaged due to processing due to extremely low mechanical strength, and the production yield is poor.
  • the obtained thermoelectric conversion elements often lack dimensional accuracy.
  • a thermoelectric conversion element having a slightly larger mechanical strength than that obtained by the melting method can be obtained, but when a polycrystalline ingot is pulverized, Since the powder surface is oxidized and impurities are mixed, it is difficult to obtain a thermoelectric conversion element having excellent characteristics.
  • thermoelectric conversion element having excellent thermoelectric properties can be obtained, sintering requires a long time and productivity is poor. Since the crystal grains of the sintered body are coarsened, the mechanical strength of the obtained sintered body is small, and it is difficult to process the sintered body into a desired shape, and the processing yield is poor.
  • the present invention provides a method for producing a sintered body for a thermoelectric conversion element, which can provide a thermoelectric conversion element having excellent productivity, high mechanical strength, and excellent thermoelectric conversion characteristics, and a thermoelectric element produced using the production method. It is an object to provide a sintered body for a conversion element and a thermoelectric conversion element using the sintered body.
  • Fig. 1 is a schematic diagram showing a cooling module and a method for evaluating the cooling characteristics of the cooling module.
  • Fig. 2 is a graph showing the cooling characteristics of the cooling module. Disclosure of the invention
  • the method for producing a sintered body for a thermoelectric conversion element according to claim 1 of the present invention comprises the steps of: converting a powder containing at least ⁇ ti, a powder containing at least Te, and a powder containing at least Sb into an organic solvent. Is used as a dispersion medium and filled in a pot while being shielded from the atmosphere And wet-pulverized and mixed, dried in an inert gas atmosphere, then pre-heated in a vacuum at 100 to 25 using a hot press method, and then sintered at 420 to 500 in an inert gas atmosphere.
  • thermoelectric conversion element used for a Te-Sb-based thermoelectric conversion element
  • the powder containing at least Bi is a single element B ⁇ powder
  • the powder containing at least ⁇ Te is a single element Te.
  • the powder is characterized in that the powder containing at least Sb is a single element Sb powder.
  • the method for producing a sintered body for a thermoelectric conversion element according to claim 3 includes a step of mixing a powder containing at least Bi, a powder containing at least Te, and a powder containing at least Se with an organic solvent. Filling the pot as a dispersing medium and shutting it off from the atmosphere
  • the sintered body for a thermoelectric conversion element of the present invention is used for a BiTeSb-based thermoelectric conversion element (in a sintered body made of an intermetallic compound having a composition of BiJe Sl Te-X, the value of X is 0.15 to 0.25, and a sintered body composed of an intermetallic compound having a composition of (Bi 2 Te 3 ) x (Bi 2 Se 3 ) i used for a Bi-Te-Se type thermoelectric conversion element Wherein the value of X is from 0 to 0.1, and the crystal grain of the sintered body used for the Bi-Te-Sb-based thermoelectric conversion element is from 1.0 to 15 m.
  • the sintered body used for the i-TeSe-based thermoelectric conversion element has a crystal grain size of 0.1 to 10 / zm. Further, the sintered body used for the Bi-TeSb-based thermoelectric conversion element has an oxygen content of 0.25 to: L. The oxygen content of the sintered body used in the above is 0.1 to 0.6%. ⁇ Further, it is characterized that the compressive strength of these sintered bodies is 10 kgf / mm 2 or more.
  • thermoelectric conversion element of the present invention is characterized by using the sintered body for a thermoelectric conversion element according to any of the above.
  • thermoelectric material Z The figure of merit Z indicating the performance of the thermoelectric material is represented by the following equation.
  • ⁇ is the Seebeck coefficient (the thermoelectromotive force when a temperature difference of 1 occurs at both ends of the element)
  • ⁇ is the specific resistance
  • ⁇ is the thermal conductivity.
  • thermoelectric material composed of fine crystal grains
  • the appropriate raw material powder was used, and the raw material powder was mixed at a compounding ratio to obtain an alloy composition capable of obtaining suitable thermoelectric conversion characteristics. After crushing and mixing the raw material powder in the appropriate protective atmosphere for the appropriate time, and then sintering in the appropriate atmosphere for the appropriate time, it is made up of finely oxidized fine crystal grains, It has been found that a sintered body for a thermoelectric conversion element having high mechanical strength and excellent thermoelectric conversion characteristics can be obtained.
  • thermoelectric conversion element p-type thermoelectric conversion element
  • a raw material powder an alloy powder containing at least one of Bi, Te, and Sb, for example, an ingot of an alloy obtained by melting Bi, Te, and Sb is obtained by grinding. Alloy powder, etc., which may be used, but single element Bi powder, Te powder, and Sb powder may be used. These raw material powders preferably have a particle size of 200 / xm or less.
  • the raw material powder weighed as described above is pulverized and mixed.
  • the pulverization and mixing may be either dry or wet, but it is necessary to pulverize and mix the raw material powder during pulverization and mixing so as not to be excessively oxidized.
  • After charging the specified amount of raw material powder close the pot with a lid and seal the raw material powder and organic solvent. Even when the lid is fastened to the pot, the pot is sealed so that the air does not remain at the upper end of the pot.
  • the organic solvent alcohols such as ethanol and ethanol and various solvents can be used. However, it is preferable to use acetate because of consideration for the working environment and a high evaporation rate.
  • the raw material powder sealed in the pot together with the organic solvent as described above is pulverized and mixed using a means such as a ball mill for simultaneously mixing and pulverizing.
  • a means such as a ball mill for simultaneously mixing and pulverizing.
  • a planetary ball mill is used.
  • the grinding and mixing time depends on the rotation speed of the pot, but is preferably 1 to 12 hours.
  • the raw material powder is pulverized and mixed into fine powder having an average particle size of 0.05 to 2.5 zm, and the powder surface is appropriately oxidized.
  • Unit as raw material powder When elementary Bi powder, Te powder, and Sb powder are used, mechanical pulverization progresses due to the pulverization and mixing, and the ultrafine alloy of the mechanical alloy is solid-phase sintered in a later sintering process. By sintering, a structure composed of fine crystal grains is obtained.
  • the finely mixed powder which has been pulverized and mixed as described above and appropriately oxidized, is heated and dried while flowing nitrogen in a closed vessel in order to prevent further oxidation.
  • the fine mixed powder dried as described above was filled into a force-bonding die having a predetermined size, and sintered using a hot press.
  • the sintering is performed by preheating in a vacuum at 100 to 25 O: and then sintering at a temperature of 420 to 500 in an inert gas atmosphere for 15 minutes to 2 hours. This preheating in a vacuum allows the powder to be
  • the oxygen adsorbed on the powder is removed, and a sintered body having a predetermined amount of oxygen is obtained. If the preheating temperature is less than 100, the adsorbed oxygen is not sufficiently removed, and a sintered body having a preferable figure of merit Z cannot be obtained. On the other hand, preheating at a temperature exceeding 250 is not preferable because the diffusion of metal proceeds before applying pressure and the crystal grains become coarse. A preheating time of about 5 to 60 minutes is sufficient. After preheating, switch the atmosphere to an inert gas atmosphere such as argon to prevent the powder from evaporating / $ ⁇ , and heat to the sintering soaking temperature.
  • an inert gas atmosphere such as argon
  • Pressing by a hot press is performed with a pressing force of 100 kg Zcm 2 to 1 ton / cm 2 after the sintering temperature is reached.
  • the pressure is less than 100 kg / cm 2
  • the density of the sintered body is insufficiently improved, and a sintered body having a sufficient mechanical strength cannot be obtained.
  • it creates a pressure above 1 ton Z cm 2
  • thermoelectric conversion element p-type thermoelectric conversion element
  • An alloy powder containing at least one of Bi, Te, and Se as a raw material powder for example, an alloy obtained by pulverizing an ingot of an alloy obtained by melting Bi, Te, and Se Powders and the like can be used, but single element Bi powder, Te powder and Se powder may be used.
  • These raw material powders preferably have a particle size of 200 m or less.
  • These raw material powders [0] are stoichiometrically weighed so that the value of X becomes 0 to 0.1 in an intermetallic compound having a composition of (Bi 2 Te 3 ) Mi (Bi 2 Se).
  • the n-type thermoelectric conversion element is more susceptible to the carrier concentration than the p-type thermoelectric conversion element, and increasing the carrier concentration to lower the specific resistance p is advantageous for improving the figure of merit Z. Therefore, as a dopant for increasing the carrier concentration, SbI3 may be added at the time of pulverizing and mixing an alloy powder containing at least one of the above-mentioned Bi, Te, and Se. Sb l 3 is the sum amount Interview of the alloy powder. It is preferable to add more than 0% by weight to 0.2% by weight. When S bl 3 is added in excess of 0.2% by weight, the specific resistance p decreases, but the Seebeck coefficient decreases and the thermal conductivity ⁇ increases, resulting in a decrease in the figure of merit Z.
  • the raw material powder of the sintered body for an n-type thermoelectric conversion element weighed as described above is pulverized and mixed in the same manner as in the case of the raw material powder for a p-type thermoelectric conversion 5 "conversion element, and is finely divided and appropriately oxidized. Let it.
  • the mixed and ground fine powder was sintered in the same manner as in the sintering of the sintered body for the p-type thermoelectric conversion element except that the heating temperature (sintering soaking temperature) was 420 to 520.
  • the heating temperature sintering soaking temperature
  • the lower and upper limits of the sintering temperature are defined by the upper and lower limits of the sintering temperature of the sintered body for P-type thermoelectric conversion elements.
  • the sintered body for a p-type thermoelectric conversion element manufactured as described above has the above-mentioned reason (for an intermetallic compound having a composition of BhTe Sl
  • the sintered body for an n-type thermoelectric conversion element manufactured as described above also has a composition of (Bi 2 Te 3 ) w (Bi 2 Se 3 ) i for the above-described reason.
  • the sintered body for a p-type thermoelectric conversion element and the sintered body for an n-type thermoelectric conversion element manufactured as described above are 1.0 to 15 m, n
  • the sintered body for a thermoelectric conversion element preferably has a crystal grain size of 0.1 to 10 m.
  • the oxygen content of the sintered body for the p-type thermoelectric conversion element is preferably 0.25 to 1.0%, and the oxygen content of the sintered body for the n-type thermoelectric conversion element is 0.1 to 0.6%. %.
  • these sintered bodies have a compressive strength of 1 O kg f Zmm 2 .
  • a sintered body for a p-type thermoelectric conversion element one having a crystal grain size of 1.0 m or more provides a good figure of merit Z
  • a sintered body for an n-type thermoelectric conversion element A good performance index Z can be obtained with a crystal grain size of
  • the oxygen content of the sintered body is less than 0.25% or more than 1.0%, a good figure of merit Z cannot be obtained, and n
  • the oxygen content of the sintered body is less than 0.1%. If it is less than 0.6%, it is not preferable because a good figure of merit Z cannot be obtained.
  • the compressive strength of the sintered body is less than 10 kgf / mm 2 , the strength at the time of working is poor, and the sintered body is easily damaged, which is not preferable.
  • the upper limit of the compressive strength is not particularly limited, it is extremely difficult to obtain a sintered body having a compressive strength exceeding 30 kgf / mm 2 .
  • This raw material powder is placed in an alumina pot and filled with acetone up to the upper edge.
  • the organic solvent was poured as gently as possible so that the raw material powder did not overflow with the organic solvent, and then the lid was closed so that the air did not remain at the upper end of the pot, and the raw material powder and the organic solvent were sealed.
  • the pot in which the raw material powder and the organic solvent were sealed in this way was placed on a planetary ball mill, and rotated at a rotation speed of 250 rpm for the time shown in Table 1, and the raw material powder was mixed and ground.
  • the powder slurry after the mixing and pulverization was taken out of the pot, and heated to 60 to 90 in a closed vessel while flowing nitrogen to dry.
  • the dried fine mixed powder was filled in a force-bonding die and sintered using a hot press.
  • the sintering was pre-heated in a vacuum under the conditions shown in Table 1, and then soaked in an argon atmosphere under the conditions shown in Table 1 for sintering.
  • the rate of temperature rise up to the preheating temperature and the soaking temperature was set to 10 minutes.
  • Pressing by hot pressing was performed under the pressing conditions shown in Table 1 after the sintering temperature was reached. After elapse of the soaking time shown in Table 1, the furnace was cooled. Thus, a sintered body for a p-type thermoelectric conversion element was obtained.
  • thermoelectric conversion element For making sintered body for thermoelectric conversion element
  • the sintered body for the p-type thermoelectric conversion element shown in Sample No. 3 in Table 3 and the sintered body for the n-type thermoelectric conversion element shown in Sample No. 5 Cut out an element of 2 mm x 2 mm and 2.5 mm in height, connect one end of both elements with a Cu plate as shown in Fig. 1, and attach a Cu plate as a terminal to each other. A cooling module was used. Then, the temperature drop generated when a DC current was applied between the cooling modules in a vacuum was measured, and the cooling characteristics were evaluated.
  • thermoelectric conversion element of the present invention exhibits superior cooling characteristics as compared with commercially available thermoelectric conversion elements.
  • the method for producing a sintered body for a thermoelectric conversion element comprises the steps of: using an appropriate raw material powder; mixing the raw material powder in a compounding ratio such that an alloy composition having suitable thermoelectric conversion characteristics is obtained; This is a production method in which the raw material powder is ground and mixed for an appropriate time, and then sintered in an appropriate atmosphere for an appropriate time.
  • thermoelectric conversion element produced from the sintered body for a thermoelectric conversion element of the present invention has excellent thermoelectric conversion characteristics.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)

Abstract

Cette invention se rapporte à un procédé de fabrication d'un corps fritté pour élément de conversion thermoélectrique, en vue de produire un élément de conversion thermoélectrique présentant une excellente productivité, une résistance mécanique élevée et d'excellentes caractéristiques de conversion thermoélectrique; à un corps fritté pour élément de conversion thermoélectrique produit par ce procédé; ainsi qu'à un élément de conversion thermoélectrique utilisant ce corps fritté. Ce procédé consiste à mélanger et à broyer une poudre contenant Bi, Te et Sb et une poudre contenant Bi, Te et Se dans un milieu dont l'oxydation est régulée, à sécher ce produit mélangé et broyé et à fritter le produit ainsi séché dans un milieu inactif, afin d'obtenir un corps fritté pour élément de conversion thermoélectrique constitué de grains de cristaux fins avec des surfaces oxydées à un niveau approprié.
PCT/JP1999/002162 1998-04-23 1999-04-23 Procede de fabrication de corps fritte pour element de conversion thermoelectrique, corps fritte pour element de conversion thermoelectrique et element de conversion thermoelectrique utilisant ce corps fritte WO1999054941A1 (fr)

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Application Number Priority Date Filing Date Title
AU35354/99A AU3535499A (en) 1998-04-23 1999-04-23 Method of manufacturing sintered body for thermoelectric conversion element, sintered body for thermoelectric conversion element and thermoelectric conversion element using it

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Application Number Priority Date Filing Date Title
JP10/128107 1998-04-23
JP12810798 1998-04-23

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WO1999054941A1 true WO1999054941A1 (fr) 1999-10-28

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6958443B2 (en) * 2003-05-19 2005-10-25 Applied Digital Solutions Low power thermoelectric generator
EP1928035A1 (fr) * 2005-09-22 2008-06-04 Ube Industries, Ltd. Materiau de conversion thermoelectrique et son procede de production
US7629531B2 (en) 2003-05-19 2009-12-08 Digital Angel Corporation Low power thermoelectric generator
US7834263B2 (en) 2003-12-02 2010-11-16 Battelle Memorial Institute Thermoelectric power source utilizing ambient energy harvesting for remote sensing and transmitting
US8455751B2 (en) 2003-12-02 2013-06-04 Battelle Memorial Institute Thermoelectric devices and applications for the same
KR101292591B1 (ko) 2012-04-16 2013-08-12 한국과학기술원 비스무스―텔루륨계 페이스트 합성법과 페이스트를 이용한 열전물질의 형성 방법
JP2014007376A (ja) * 2012-05-30 2014-01-16 Denso Corp 熱電変換装置
US9281461B2 (en) 2003-12-02 2016-03-08 Battelle Memorial Institute Thermoelectric devices and applications for the same
JP2016152388A (ja) * 2015-02-19 2016-08-22 トヨタ自動車株式会社 熱電材料の製造方法
JP2017085179A (ja) * 2012-05-30 2017-05-18 株式会社デンソー 熱電変換装置の製造方法、熱電変換装置
CN108644264A (zh) * 2018-08-07 2018-10-12 中国重汽集团济南动力有限公司 一种气压盘式制动器的手动调整装置
CN112531097A (zh) * 2020-11-13 2021-03-19 深圳热电新能源科技有限公司 n型碲化铋基热电材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06216415A (ja) * 1993-01-21 1994-08-05 Idemitsu Petrochem Co Ltd 熱電変換材料の製造方法
JPH09121063A (ja) * 1996-10-28 1997-05-06 Komatsu Ltd 熱電半導体材料の製造方法
JPH09275228A (ja) * 1996-04-01 1997-10-21 Kubota Corp Ｓｂ含有熱電材料成形体及びその製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06216415A (ja) * 1993-01-21 1994-08-05 Idemitsu Petrochem Co Ltd 熱電変換材料の製造方法
JPH09275228A (ja) * 1996-04-01 1997-10-21 Kubota Corp Ｓｂ含有熱電材料成形体及びその製造方法
JPH09121063A (ja) * 1996-10-28 1997-05-06 Komatsu Ltd 熱電半導体材料の製造方法

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7629531B2 (en) 2003-05-19 2009-12-08 Digital Angel Corporation Low power thermoelectric generator
US6958443B2 (en) * 2003-05-19 2005-10-25 Applied Digital Solutions Low power thermoelectric generator
US8455751B2 (en) 2003-12-02 2013-06-04 Battelle Memorial Institute Thermoelectric devices and applications for the same
US9281461B2 (en) 2003-12-02 2016-03-08 Battelle Memorial Institute Thermoelectric devices and applications for the same
US7834263B2 (en) 2003-12-02 2010-11-16 Battelle Memorial Institute Thermoelectric power source utilizing ambient energy harvesting for remote sensing and transmitting
EP1928035A4 (fr) * 2005-09-22 2012-03-07 Ube Industries Materiau de conversion thermoelectrique et son procede de production
EP1928035A1 (fr) * 2005-09-22 2008-06-04 Ube Industries, Ltd. Materiau de conversion thermoelectrique et son procede de production
KR101292591B1 (ko) 2012-04-16 2013-08-12 한국과학기술원 비스무스―텔루륨계 페이스트 합성법과 페이스트를 이용한 열전물질의 형성 방법
JP2014007376A (ja) * 2012-05-30 2014-01-16 Denso Corp 熱電変換装置
JP2017085179A (ja) * 2012-05-30 2017-05-18 株式会社デンソー 熱電変換装置の製造方法、熱電変換装置
US9680079B2 (en) 2012-05-30 2017-06-13 Denso Corporation Production method of thermoelectric converter, production method of electronic device equipped with thermoelectric converter, and thermoelectric converter
US9871181B2 (en) 2012-05-30 2018-01-16 Denso Corporation Production method of thermoelectric converter, production method of electronic device equipped with thermoelectric converter, and thermoelectric converter
JP2016152388A (ja) * 2015-02-19 2016-08-22 トヨタ自動車株式会社 熱電材料の製造方法
CN108644264A (zh) * 2018-08-07 2018-10-12 中国重汽集团济南动力有限公司 一种气压盘式制动器的手动调整装置
CN108644264B (zh) * 2018-08-07 2023-07-25 中国重汽集团济南动力有限公司 一种气压盘式制动器的手动调整装置
CN112531097A (zh) * 2020-11-13 2021-03-19 深圳热电新能源科技有限公司 n型碲化铋基热电材料及其制备方法
CN112531097B (zh) * 2020-11-13 2023-10-10 深圳热电新能源科技有限公司 n型碲化铋基热电材料及其制备方法

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AU3535499A (en) 1999-11-08

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