WO2013009430A1 - Matières thermoélectriques de skutterudite du type à compensation de trous, et procédé de fabrication de celles-ci - Google Patents

Matières thermoélectriques de skutterudite du type à compensation de trous, et procédé de fabrication de celles-ci Download PDF

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WO2013009430A1
WO2013009430A1 PCT/US2012/042345 US2012042345W WO2013009430A1 WO 2013009430 A1 WO2013009430 A1 WO 2013009430A1 US 2012042345 W US2012042345 W US 2012042345W WO 2013009430 A1 WO2013009430 A1 WO 2013009430A1
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thermoelectric material
type
phase
group
material according
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PCT/US2012/042345
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English (en)
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Lidong Chen
Lin He
Xiangyang Huang
Ruiheng Liu
Pengfei Qiu
Xun SHI
Jiong Yang
Wenqing Zhang
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Corning Incorporated
Shanghai Institute Of Ceramics, Chinese Academy Of Sciences
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Publication of WO2013009430A1 publication Critical patent/WO2013009430A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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 disclosure belongs to the field of thermoelectric materials, providing a skutterudite thermoelectric material of hole-compensated type with excellent thermoelectric performance and a method of making the same.
  • Thermoelectric (TE) technology can realize the conversion between thermal energy and electric energy by using Seebeck effect and Peltier effect of
  • p-type and n-type TE materials can be assembled to form ⁇ -type pair of thermoelectric device.
  • Filled-skutterudite compounds are one of the best TE materials that can be used in the medium temperature range (500 - 850K). Atoms with small radii can be filled in the Sb-icosahedral cage of the skutterudite formed by phosphorus family atoms to create a rattling effect due to forming weak bond with peripheral atoms, so as to effectively scatter low frequency thermal transport phonons, thereby suppressing the lattice thermal conductivity (3 ⁇ 4) drastically. Generally, electrical transport properties would be also influenced with changing filling fraction (the lattice thermal conductivity of skutterudite will decrease).
  • TE materials with high ZT values can be obtained by optimizing electrical and thermal transport properties simultaneously via enhancing filling fraction.
  • R e. g. Ba, Eu, Na, K, Yb, etc.
  • y 0.15-0.65
  • just altering the filling fraction can tune the thermoelectric performance and result in materials with high ZT values (> 1.2).
  • most of the fillers can be only filled in the Sb-icosahedral cages with the filling fraction less than 0.15 (e. g. Ce and Nd).
  • the low filling fraction would create less rattling effect to scatter the thermal transport phonons and result in high lattice thermal conductivity and low thermal conductivity.
  • electrical conductivity of these materials is low because a low filling fraction results in fewer electrons introduced by the foreign atoms.
  • the high thermal conductivity and low electrical conductivity contribute low ZT values ( ⁇ 1.2) for these elements filled skutterudites as compared with those skutterudites with high filling fraction.
  • the filling fraction of these compounds is smaller than that of the RyFe 4 Sbi2 compounds since n-type (Co, Ni)-doping introduces additional electron compensation. Therefore, it is meaningful to enhance the filling fraction in both n- and p-type skutterudite compounds for further thermoelectric performance optimization.
  • the filling fraction can be enhanced by the following three methods:
  • the disclosure provides a novel skutterudite thermoelectric material of hole- compensated type and a method of making the same, which has overcome the shortcomings of conventional methods.
  • the electrical conductivity and power factor for the novel n-type materials increases due to the increment of filling fraction; and the maximum ZT value of these materials is increased more than 20%.
  • both carrier concentration and band structure of the novel p-type materials is optimized due to the increment of filling fraction; the enhanced filling fraction results in the increment of Seebeck coefficient and suppression of thermal conductivity; and the maximum ZT value of these materials is enhanced more than 13%.
  • the present disclosure provides a skutterudite thermoelectric material of hole-compensated type having a composition represented by the following formula R y A4- x B x Sbi 2 / z NC, where 0.01 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 1, 0% ⁇ z ⁇ 10%;
  • R is at least one element selected from the group consisting of Ca, Ba, La, Ce, Pr, Nd and Yb;
  • A is at least one element selected from the group consisting of Fe, Co and Ni;
  • B is at least one transition metal element selected from the group consisting of Ti, V, Cr, Mn, Fe Nb, Mo, Tc and Ru such that element(s) B have fewer electrons than element(s) A;
  • NC is a second phase where z is a mole percentage of the second phase in the thermoelectric
  • z 0 and the composition is represented by the following formula Ce 0 . 2 Co3.95Mno.o5Sbi2.
  • 0.1 ⁇ x ⁇ 0.5, 0.5 ⁇ y ⁇ 1 and z 0.
  • z 0 and the composition is represented by the following formula Ceo.95Fe3.8Mno. 2 Sbi2.
  • 0.1 ⁇ x ⁇ 0.5, 0.5 ⁇ y ⁇ 1 and z 0.
  • A is a combination of Fe and Co.
  • x is about 0.15
  • y is about 0.95
  • z 0
  • the composition is represented by the following formula
  • transition metal element(s) B are homogeneously dispersed on element A lattice sites throughout the thermoelectric material.
  • the second phase comprises an insulating material.
  • the second phase comprises a semiconducting material.
  • a particle size of the second phase is in a range of 2 to 500 nm.
  • the second phase is homogeneously dispersed throughout the thermoelectric material.
  • the second phase has a melting point greater than 400°C.
  • the thermoelectric material can be p-type or n- type.
  • thermoelectric material can be polycrystalline.
  • a method of making a skutterudite thermoelectric material of hole-compensated type comprising combining raw materials in a vessel under inert atmosphere; forming a melt of the raw materials within the vessel by heating the raw materials to a temperature of from 800 to 1200°C; quenching the melt to form a solid ingot; and annealing the solid ingot at a temperature of from 400 to 900°C to form an annealed ingot, wherein the raw materials have a composition represented by the following formula R y A4_ x B x Sb 12 / z NC, where 0.01 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 1 , 0% ⁇ z ⁇ 10%; R is at least one element selected from the group consisting of Ca, Ba, La, Ce, Pr, Nd and Yb; A is at least one element selected from the group consisting of Fe, Co and Ni; B is at least one
  • the raw materials can comprise elements and/or compounds.
  • an interior surface of the vessel comprises a carbon coating.
  • the vessel comprises a graphite crucible or a tantalum crucible.
  • a pressure within the vessel during the melting is in a range of 0.1 to 40000 Pa.
  • the method further comprises grinding the annealed ingot into a powder and consolidating the powder.
  • the consolidating comprises spark plasma sintering or hot press sintering at a temperature in a range of 400 to 800°C and a pressure in a range of 10 to 100 MPa.
  • thermoelectric conversion device comprising at least one n-type element including an n-type thermoelectric material, and at least one p-type element including a p-type thermoelectric material, wherein at least one of the n-type thermoelectric material and the p-type thermoelectric material has a composition represented by the following formula R y A4_ x B x Sbi2 / z NC, where 0.01 ⁇ x ⁇ 0.5, 0.01 ⁇ y ⁇ 1 , 0% ⁇ z ⁇ 10%; R is at least one element selected from the group consisting of Ca, Ba, La, Ce, Pr, Nd and Yb; A is at least one element selected from the group consisting of Fe, Co and Ni; B is at least one transition metal element selected from the group consisting of Ti, V, Cr, Mn, Fe Nb, Mo, Tc and Ru such that element(s) B have fewer electrons than element(s) A; and NC is a second phase where z is a mo
  • the increment of Ce-filling fraction is responsible for the enhanced carrier concentration and electrical conductivity;
  • power factor is enhanced in the entire temperature range investigated here due to the increase of electrical conductivity;
  • Seebeck coefficient of Mn- doped sample shows larger Seebeck coefficient than that of the matrix in the entire temperature measured here;
  • Mn-doped sample shows low thermal conductivity as compared with the matrix;
  • the maximum ZT value is increased about 13% due to Mn-doping, and ZT value is notably increased in the whole temperature range;
  • Seebeck coefficient of Mn-doped sample shows larger Seebeck coefficient than that of the matrix in the entire temperature measured here;
  • Mn- doped sample shows low thermal conductivity as compared with the matrix;
  • the increment of filling fraction is responsible for the enhanced carrier concentration and electrical conductivity;
  • power factor (S 2 (j) is enhanced in the entire temperature range investigated here due to the increase of electrical conductivity;
  • power factor is enhanced in the entire temperature range investigated here due to the increase of electrical conductivity;
  • Fig. 17 illustrates processing flow chart of preparing R y A 4-3 ⁇ 4 B J( ;Sb 12 /z NC samples which are hole-compensated by doping according to one embodiment.
  • thermoelectric material Disclosed is a hole-compensation type skutterudite thermoelectric material, wherein in the filled skutterudite matrix, transition metal element B with fewer electrons is used to replace element A, and additional holes can be introduced to enhance the filling fraction and optimize the band structure due to the hole compensation.
  • This kind of TE materials has the general formula as: lz NC, where R represents filler atom (at least one or more of Ce, Nd, Pr, La, Ca, Ba and Yb); y is the filling fraction (0.01 ⁇ y ⁇ 1); A represents at least one or more of Fe, Co or Ni; B represents the transition metals with fewer electron than A, such as, at least one or more of Ti, V, Cr, Mn, Nb, Mo, Tc, Ru or Fe; x is the doping fraction (0.01 ⁇ x ⁇ 0.5); NC is nano-composite second phase, z is mole percentage of NC (0 ⁇ z ⁇ 10).
  • the TE material can be n-type or p-type material.
  • the transition metal element B is homogeneously distributed in NC matrix.
  • the nano-composite second phase NC can be carbides, oxides, GaSb or InSb (insulator or semiconductor), the addition of which will not obviously affect the carrier concentration of matrix.
  • a method for preparing the above TE material including: obtaining melt-blend of R, A, B and Sb, wherein R is at least one or more element selected from the group consisting of Ca, Ba, La, Ce, Pr, Nd and Yb; A is at least one or more element selected from the group consisting of Fe, Co and Ni; and B is at least one or more transition metal element selected from the group consisting of Ti, V, Cr, Mn, Fe Nb, Mo, Tc and Ru such that element(s) B have fewer electrons than element(s) A; during melting, adding nano-composite second phase NC to form melt- blend of R, A, B, Sb and NC, or after annealing the melt-blend of R, A, B and Sb but before sintering the powder, adding nano-composite second phase NC to form melt- blend of R, A, B, Sb and NC; quenching the melt to form a solid ingot; annealing the solid ingot to form
  • the melt-blend can be melt-blended at a melting temperature of 800-1200°C.
  • the quenching medium can be selected from the group consisting of air, water, salted water, oil, or liquid nitrogen.
  • a rotating-throwing method can be used, wherein the cooling rate is between 50 and 10 6o C/sec.
  • an annealing temperature of 400-900°C can be used.
  • the annealed ingot can be grounded into fine powders, so as to make powder.
  • the obtained powder can be consolidated via a pressure sintering technique, so as to form TE material.
  • the obtained powder can be consolidated via spark plasma sintering, or hot- pressed sintering, so as to form a TE material.
  • Tthe sintering temperature can range from 400-800°C; the sintering time can be 2-600 mins with a pressure of 10-100 MPa.
  • Fig. 17 illustrates a processing flow chart for preparing R ASb ⁇ /z NC samples which are hole-compensated by doping according to one embodiment.
  • a process uses one or two transition metals with fewer electrons as doping elements.
  • skutterudites with high filling fraction can be obtained using high temperature melting and consolidating process.
  • the process includes the following steps: raw materials with high purity in the form of element or compound are weighted in an atomic ratio in the glove box under inert gas Ar atmosphere; then the raw materials are sealed into a quartz tube by Ar plasma.
  • the wall of quartz tube can be deposited by a thin carbon film, alternatively, a graphite crucible or tantalum crucible can be inserted to load raw materials; and, the quartz tube is vacuumed during sealing, and the vacuum degree is 0.1-40000 Pa.
  • the quartz tube loaded with raw materials is melted at the temperature range of 800-1200°C, and the holding time is 1-48 h, wherein the heating rate is 0.5-10°C/min.
  • the quench methods can be the following two methods: using quenching mediums or using melt spinning, wherein the quenching medium can be air, water, salted water, oil, or liquid nitrogen, and when using melt spinning, the quenching rate is controlled at 50-10 6o C/sec; the quenched quartz tube is annealed at 400-900°C for 5-300 hrs; and the annealed ingot is grounded into fine powders, then the obtained powder is consolidated via a pressure sintering technique, i.e.
  • spark plasma sintering or hot-pressed sintering, wherein the sintering temperature is 400-800°C; the sintering time is 2-600 min with the pressure at 10-100 MPa, so as to obtain R y A4_ x B A: Sbi2 lz NC skutterudite thermoelectric material.
  • Advantages associated with the disclosed approach include: the maximum ZT value of n-type skutterudites provided is increased more than 20%. The maximum ZT value of p-type skutterudites is increased more than 13%. The maximal theoretical converting efficiency of the TE device built up by such n-type skutterudites is enhanced more than 1 1%.
  • the maximal theoretical converting efficiency of the thermoelectric device built up by such p-type skutterudites is enhanced more than 9%.
  • the novel n- and p-type materials disclosed herein are easy to prepare; the controllable processes are promising for mass production and practical application.
  • the TE materials have attributes that include a high Seebeck coefficient, high power factor and low total thermal conductivity, wherein via introducing hole compensation, some trivalent rare earth metal elements can also have high filling fraction in skutterudites, thus resulting in many new skutterudites with high TE performance. Via introducing hole compensation, the filling fraction is increased, leading to more scattering to thermal transport phonons and thus low thermal conductivity.
  • the transition metal doping can optimize the band structure near the Fermi level, which will increase the Seebeck coefficient and maintain high power factor in p-type skutterudites.
  • Example 1 n-type material
  • the quartz tube containing raw materials mixture were vacuumed and sealed by Ar plasma, whose inner wall was coated with thin carbon film. Then, the mixed raw material was heated to 1100°C at a rate of 3°C/min and melt for 12 hrs. Subsequently, the quartz tube was quenched in salt water at a quenching rate of 300°C/sec, and then the ingot (still in quartz tubes under vacuum) were annealed at 800 °C for 120 hrs. The obtained fine powders of
  • Ceo.2Co3.95Mno.o5Sbi2 grounded from the ingot were consolidated by spark plasma sintering (SPS) at 600 C for 5 min under a pressure of 50 MPa.
  • SPS spark plasma sintering
  • TE properties measurements suggested that Ceo.2Co 3 . 9 5Mno.o5Sbi2 has higher electrical conductivity (Figure 1) and power factor (Figure 2) than those of Ceo.i iCo4Sbi2.
  • Enhanced ⁇ value was obtained for this hole compensated samples.
  • the maximum ZT value is 1.17 at 850 K for Ceo.2Co3.95Mno.o5Sbi2 ( Figure 3), higher than that of Ceo.nCo 4 Sbi 2 .
  • Example 2 p-type material
  • Example 3 p-type material
  • Example 4 n-type material
  • Example 5 n-type material
  • the quartz tube containing raw materials mixture were vacuumed and sealed by Ar plasma, whose inner wall was coated with thin carbon film. Then, the mixed raw material was heated to 1100°C at a rate of 3°C/min and melt for 12 hrs. Subsequently, the quartz tube was quenched in salt water at a quenching rate of about 300°C/sec, and then the ingot (still in quartz tubes under vacuum) were annealed at 800°C for 120 hrs. The obtained fine powders grounded from the ingot were consolidated by spark plasma sintering (SPS) at 600 C for 5 min under a pressure of 50 MPa. TE properties measurements suggested that
  • Ceo.2Co3.95Cro.o5Sbi2/0 at.% NC has higher electrical conductivity (Figure 14) and power factor (Figure 15) than those of Ceo.2Co4Sbi2.
  • Enhanced ZT value was obtained for this hole compensated samples.
  • the maximum ZT value is 1.20 at 850 K ( Figure 16), higher than that of the undoped matrix.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne des matières thermoélectriques de skutterudite du type à compensation de trous, et un procédé de fabrication de celles-ci, qui permet de former une matière thermoélectrique de skutterudite du type à compensation de trous, dont la composition est représentée par la formule suivante: RyA-xBxSb / z NC, dans laquelle 0,01 ≤ x ≤0,5, 0,01 ≤ y ≤1, 0% ≤ z ≤ 10%; R représente au moins un élément sélectionné dans le groupe constitué par Ca, Ba, La, Ce, Pr, Nd et Yb; A représente au moins un élément sélectionné dans le groupe constitué par Fe, Co et Ni; B représente au moins un élément métallique de transition sélectionné dans le groupe constitué par Ti, V, Cr, Mn, Fe Nb, Mo, Tc et Ru, de sorte que le(s) élément(s) B comporte(nt) moins d'électrons que le(s) élément(s) A; et NC représente une deuxième phase, z représentant le pourcentage molaire de la deuxième phase dans la matière thermoélectrique. L'invention concerne aussi des procédés de fabrication d'une matière thermoélectrique de skutterudite du type à compensation de trous.
PCT/US2012/042345 2011-07-12 2012-06-14 Matières thermoélectriques de skutterudite du type à compensation de trous, et procédé de fabrication de celles-ci WO2013009430A1 (fr)

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CN115188877A (zh) * 2022-07-27 2022-10-14 武汉理工大学 一种制备强织构和高热电性能柔性热电薄膜的方法

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JPWO2020067111A1 (ja) * 2018-09-26 2021-03-25 日立金属株式会社 熱電変換材料、およびそれを用いた熱電変換モジュール、並びに熱電変換材料の製造方法
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