Patent Application
20220059746
The present disclosure relates to a thermoelectric conversion material and a thermoelectric conversion device. The present disclosure also relates to a method for obtaining electrical power by using the thermoelectric conversion material and to a method for transporting heat by using the thermoelectric conversion material.
When a temperature difference occurs between opposite ends of a thermoelectric conversion material, an electromotive force is generated in proportion to the temperature difference that has occurred. This phenomenon, in which thermal energy is converted into electrical energy, is known as the Seebeck effect. The thermoelectric generation technology is a technology for converting thermal energy directly into electrical energy by utilizing the Seebeck effect.
As is well known in the technical field of thermoelectric conversion materials, the performance of a thermoelectric conversion material that is used in a thermoelectric conversion device is evaluated by a figure of merit ZT, which is a figure of merit rendered dimensionless by multiplying a figure of merit Z by an absolute temperature T. ZT is represented by ZT=S2σT/κ, which uses a Seebeck coefficient S, an electrical conductivity σ, and a thermal conductivity κ of a material. The higher the ZT value, the higher the thermoelectric conversion efficiency.
Japanese Patent No. 6127281 discloses an n-type thermoelectric conversion material primarily formed of Mg3(Sb, Bi)2. Non-Patent Literature 1 (A. F. May, M. A. McGuire, D. J. Singh, R. Custelcean and G. E. Jellison, Jr., Inorganic Chemistry, 50, 2011, pp. 11127-11133) and Non-Patent Literature 2 (W. Peng and A. Zevalkink, Materials, 12, 2018, p. 586) disclose that a multinary compound of (Ba, Sr, Ca)Mg2Bi2 can be stably synthesized.
One non-limiting and exemplary embodiment provides a novel thermoelectric conversion material.
In one general aspect, the techniques disclosed here feature a thermoelectric conversion material having a composition represented by a chemical formula of Ba1-a-b-cSrbCacKaMg2Bi2-dSbd. In the chemical formula, the following relationships are satisfied: 0.002≤a≤0.1, 0≤b, 0≤c, a+b+c≤1, and 0≤d≤2. In addition, the thermoelectric conversion material has a La2O3-type crystal structure.
The present disclosure provides a novel thermoelectric conversion material.
It should be noted that general or specific embodiments may be implemented as a system, a method, an integrated circuit, a computer program, a storage medium, or any selective combination thereof.
Additional benefits and advantages of the disclosed embodiments will become apparent from the specification and drawings. The benefits and/or advantages may be individually obtained by the various embodiments and features of the specification and drawings, which need not all be provided in order to obtain one or more of such benefits and/or advantages.
Embodiments of the present disclosure will now be described with reference to the drawings.
A thermoelectric conversion material of the present disclosure has a composition represented by the following chemical formula (I).
Ba1-a-b-cSrbCacKaMg2Bi2-dSbd(I)
In the chemical formula, the following relationships are satisfied:
0.002≤a≤0.1,
0≤b,
0≤c,
a+b+c≤1, and
0≤d≤2
The compound represented by formula (1) has a crystal structure called a La2O3 type or a CaAl2Si2 type, as illustrated in
Non-Patent Literature 1 and Non-Patent Literature 2 disclose that a multinary compound of (Ba, Sr, Ca)Mg2Bi2 can be stably synthesized. However, neither Non-Patent Literature 1 nor Non-Patent Literature 2 suggests a dopant that can adjust the concentration of the carrier necessary for improving the figure of merit ZT. The present inventors performed studies to find an optimal dopant and discovered that K (potassium) is an effective dopant for extracting high p-type performance from a material primarily formed of (Ba, Sr, Ca)Mg2Bi2.
The thermoelectric conversion material of the present disclosure has a La2O3-type crystal structure. Typically, the thermoelectric conversion material of the present disclosure has a p-type polarity.
A bulk body of (Ba, Sr, Ca, K)Mg2(Bi, Sb)2 can be manufactured, for example, by a method in which a heating step for forming an alloy, which is a precursor, is combined with mechanical alloying process or a spark plasma sintering process. Another possible method for the manufacturing is a metal flux method as disclosed in Non-Patent Literature 1. Note that these manufacturing methods are non-limiting examples.
The degree to which at least one site selected from the Ba site, the Sr site, and the Ca site is substituted with K can be controlled by varying an amount of K to be included in the starting materials, with respect to an amount of at least one selected from Ba, Sr, and Ca in the starting materials. The degree to which the Bi site is substituted with Sb can be controlled by varying an amount of Sb to be included in the starting materials, with respect to an amount of Bi in the starting materials.
An example of the manufacturing method is described below. Materials including respective necessary elements selected from Ba, Ca, Sr, K, Mg, Bi, and Sb are weighed in a stoichiometric ratio. The weighed materials except the material including Bi are introduced into a crucible. The materials may each be a single element material. The crucible is, for example, a crucible made from boron nitride (BN). Subsequently, the materials in the crucible are melted in an inert gas atmosphere to be alloyed. For the melting, a resistance heating furnace may be used, for example. Examples of the inert gas include argon. A temperature for the melting is greater than or equal to 700° C., for example. Subsequently, the resulting precursor alloy and the material including Bi are subjected to a grinding and mixing process. For the process, a planetary ball mill process may be employed, for example. A typical example of the process is as follows. The precursor alloy and the material including Bi are placed in a stainless steel vessel with stainless steel balls, and after the vessel is sealed in an argon atmosphere, the process using a planetary ball mill process is carried out. Subsequently, the alloy powder produced by the process is sintered by using a spark plasma sintering process, and, accordingly, a bulk sintered body of (Ba, Sr, Ca, K)Mg2(Bi, Sb)2 is obtained. For the spark plasma sintering process, a die made from graphite may be used. Typically, in the spark plasma process, the powder placed in the die is heated by a pulsed current under pressure. For example, the heating temperature is greater than or equal to 700° C. and less than or equal to 800° C. For example, the heating time is greater than or equal to 20 minutes. Using this method, manufacturing of a dense sintered body having, for example, a relative mass density of greater than 95% can be achieved.
The thermoelectric conversion material of the present disclosure enables a realization of a thermoelectric conversion device. As illustrated in
In the above-described thermoelectric conversion device, electrical power can be obtained when a temperature difference is formed such that, for example, the first end of the p-type thermoelectric converter 2 and the first end of the n-type thermoelectric converter 3 have a high temperature, whereas the second end of the p-type thermoelectric converter 2 and the second end of the n-type thermoelectric converter 3 have a low temperature.
Furthermore, in the thermoelectric conversion device described above, when a current is applied, heat is transported from the first end of the p-type thermoelectric converter 2 and the first end of the n-type thermoelectric converter 3 to the second end of the p-type thermoelectric converter 2 and the second end of the n-type thermoelectric converter 3. When the polarity of the current is reversed, the direction in which heat is transported is also reversed, that is, heat is transported from the second end of the p-type thermoelectric converter 2 and the second end of the n-type thermoelectric converter 3 to the first end of the p-type thermoelectric converter 2 and the first end of the n-type thermoelectric converter 3.
With the thermoelectric conversion device described above, a thermoelectric conversion module can be constructed, for example. As illustrated in
In the present embodiment, for example, an electrode may be provided at a first end of the thermoelectric conversion material of present disclosure, another electrode may be provided at a second end thereof, and a temperature difference may be formed such that the first end has a high temperature, and the second end has a low temperature; in this case, the p-type carriers migrate from the first end to the second end, and, accordingly, electrical power can be obtained.
Furthermore, in the present embodiment, a current may be applied to the thermoelectric conversion material of present disclosure; in this case, the Peltier effect is produced, and, accordingly, heat is transported from a first end of the thermoelectric conversion material to a second end thereof. Using this method, cooling and heat regulation that use a thermoelectric conversion material can be achieved.
The thermoelectric conversion material of the present disclosure will now be described in more detail with reference to examples. Note that the thermoelectric conversion material of the present disclosure is not limited to the specific embodiments described below.
Preparation of (Ba, Sr, Ca, K)Mg2(Bi, Sb)2
Bulk sintered bodies of (Ba, Sr, Ca, K)Mg2(Bi, Sb)2 were prepared by the above-described method in which a heating step for forming an alloy, which is a precursor, was combined with a spark plasma sintering process. The crucible used was a crucible made from BN. The melting was carried out in an argon atmosphere. For the melting, a resistance heating furnace set to 700° C. was used. The grinding and mixing process was carried out according to the typical example described above. For the spark plasma sintering process, a die made from graphite was used. The heating temperature and the heating time were set to be 700° C. and 30 minutes, respectively.
Non-Patent Literature 2 discloses that regarding (Ba, Sr, Ca)Mg2Bi2 crystal materials, a solid solution phase can be formed among BaMg2Bi2, SrMg2Bi2, and CaMg2Bi2, and that the crystal structure of such a material belongs to the space group P3-m1. The crystal structure of each of the prepared sintered bodies was determined on the basis of an X-ray crystal diffraction method. For the X-ray crystal diffraction method, a RINT-TTR, manufactured by Rigaku Corporation, was used.
The chemical composition of each of the prepared sintered bodies was analyzed by using energy dispersive X-ray spectroscopy. For the analysis, an XFlash 6|10, manufactured by Bruker Corporation, was used.
Each of the prepared sintered bodies was cut into a strip shape and a pellet shape to form specimens. The Seebeck coefficient S and the electrical conductivity σ within a temperature range of 330 to 570K were evaluated by using the strip-shaped specimen. The thermal conductivity κ within the temperature range of 330 to 570K was evaluated by using the pellet-shaped specimen. For the evaluation of the Seebeck coefficient and the electrical conductivity, a ZEM-3, manufactured by Advance Riko, Inc., was used. For the evaluation of the thermal conductivity, an LFA 457, manufactured by Netzsch, was used. The temperatures set for evaluating the properties were 330K, 370K, 430K, 470K, 530K, and 570K.
For details of a method for evaluating the Seebeck coefficient, see U.S. patent application Ser. No. 14/847,321 (International Application No. PCT/JP2014/001882), U.S. patent application Ser. No. 14/847,362 (International Application No. PCT/JP2014/001883), and U.S. patent application Ser. No. 14/718,491 (International Application No. PCT/JP2014/001885).
The following tables 1 to 3 show the composition of the prepared sintered bodies and the results of evaluation of the thermoelectric conversion properties at a temperature of 330K of the sintered bodies. Tables 1 to 3 also show a figure of merit ZTmax, which is a figure of merit at 470K or 570K, at which the highest figure of merit ZT was achieved. The compositions of the sintered bodies were controlled by selection of the elements to be included in the materials and the weighing ratio between the materials.
Table 1 shows properties of a thermoelectric conversion material having a composition of Ba1-aKaMg2Bi2, in which the Ba site was substituted with K. In the thermoelectric conversion material, a p-type property, in which S is a positive value, was achieved; in addition, the electrical conductivity 330K was higher by an order of magnitude than that of Comparative Example 1, and ZT was improved over a wide temperature range of 330 to 570K.
Table 2 shows properties of a thermoelectric conversion material having a composition of Ca1-aKaMg2Bi2, in which the Ca site was substituted with K. In the thermoelectric conversion material, a p-type property, in which S is a positive value, was achieved; in addition, the electrical conductivity σ330K was higher by an order of magnitude than that of Comparative Example 2, and ZT was improved over a wide temperature range of 330 to 570K.
Table 3 shows properties of a thermoelectric conversion material having a composition of SrbCacKaMg2Bi2, a thermoelectric conversion material having a composition of Ba1-a-cCacKaMg2Bi2, and a thermoelectric conversion material having a composition of Ba1-a-cCacKaMg2Bi2-dSbd. In these thermoelectric conversion materials, a p-type property, in which S is a positive value, was achieved, and in addition, ZT was further improved as a result of employing a quinary or higher composition.
As shown in Tables 1 to 3, p-type high thermoelectric conversion properties were achieved by substituting the (Ba, Sr, Ca)Mg2(Bi, Sb)2 solid solution system with K.
In addition, the thermoelectric conversion properties in the composition represented by the chemical formula of Ba1-a-b-cSrbCacKaMg2Bi2-dSbd were predicted by using a computational science technique. The technique for the prediction is described below.
The BaMg2Bi2 crystal materials disclosed in Non-Patent Literature 1 and 2 do not include intentionally introduced defects. Accordingly, in these materials, an insufficient number of carriers are present, and, therefore, a high figure of merit ZT cannot be expected. One conceivable way to achieve a high figure of merit ZT is to, for example, substitute the crystal structure of BaMg2Bi2 with a different element. Regarding defects for generating a p-type carrier, the present inventors performed studies on defects formed by replacing each of the element Ba, the element Mg, and the element Bi with a different element. The studies were based on the premise that the La2O3-type structure, which is the crystal structure of BaMg2Bi2, would be maintained even after a defect was introduced. In other words, an assumption was made that all of the materials described below, which were the subjects of the computation, had a La2O3-type structure.
A defect formation energy Eform was calculated for the instances in which the Ba site, the Mg site, or the Bi site was substituted with a different element in the crystal structure of BaMg2Bi2. The calculation revealed that in an instance where the Ba site is substituted with K, the p-type carrier concentration increases, whereas in an instance where the Bi site is substituted with Ge, Sn, or Pb, the p-type carrier concentration remains low. The defect formation energy Eform was evaluated based on the following relational equation (1).
E
form(μi,q,EF)=Edefect−Epure−Σniμi+q(EVBM+EF) (1)
In the equation, Edefect is the total energy for the instance in which a defect is present, Epure is the total energy of a perfect crystal, that is, the total energy for the instance in which no defects are present, ni is an amount of increase or decrease in an ith constituent element resulting from a defect, P is the chemical potential of the ith element, q is an amount of electrical charge possessed by a defect, EVBM is the electron volt of the valence band upper edge of BaMg2Bi2, which is a semiconductor, and EF is the Fermi energy of the electrons. When particular defect species having a q of less than 0 have an Eform that is lower than an Eform of other defect species and the absolute value of which is also low, it can be understood that using such a particular defect species contributes to a stable hole-doped state and facilitates achievement of a high p-type carrier concentration.
Regarding the defect to be formed by substituting the Ba site with a different element, studies were conducted on Ge, Sn, and Pb for the possibility of using any of these elements as the different element. These elements were also candidates for the element to be used to substitute the Bi site. Ge, Sn, and Pb were selected as the candidates because these elements have a lower valence than Bi and have an ionic radius substantially equal to that of Bi. The defect formation energy Eform for the instance in which a defect was present was calculated. The calculation revealed that in the instance where the Ba site is substituted with Ge, Sn, or Pb, the p-type carrier concentration remains low. Based on the studies, the present inventors arrived at the concept of forming a defect by substitution with K to enable the generation of p-type carriers in a BaMg2Bi2 crystal material.
The thermoelectric conversion efficiency is determined by the figure of merit ZT of a material. ZT is defined by the following relational equation (2).
ZT=S
2
σT/(κe+κlat) (2)
In the equation, S is the Seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature in the evaluation environment, κe is the thermal conductivity of the electrons, and κlat is a lattice thermal conductivity. For S, σ, and κe, the prediction was performed by using a combination of a density functional theory (DFT) computation technique, which utilizes the VASP code, and a parabolic band model (see Non-Patent Literature 3 (H. J. Goldsmid, “Introduction to Thermoelectricity”, Chapter 3, 2010)). The following equations (3) to (6) are computation equations for determining the physical quantities according to the parabolic band model.
S(η)=kB/e×[2F1(η)/F0(η)−η] (3)
σ(η)=e(2kBT)3/2/3π2(h/2π)3×md3/2μ×F0(η) (4)
κe=(2kB)3/2T1/2/3eπ2(h/2π)3×md3/2μ×[F2(η)−F12(η)/F0(η)] (5)
F
i(η)=∫∞0xidx/(exp[x−η]+1) (6)
These physical quantities are determined when a density of state effective mass md, a mobility μ, and reducing Fermi energy η(=−EF/kBT) are given. The reducing Fermi energy was calculated from a defect concentration, as will be described below. The density of state effective mass md was determined by fitting the density of states obtained from the VASP code to the following relational equation (7).
D
VB(E−EF)=4η(2md)3/2/h3×(EF−E)1/2 (7)
The mobility p, which is a parameter for determining a, was calculated according to the following theoretical equation (8) (see Non-Patent Literature 5 (H. Wang et al., in Thermoelectric Nanomaterials, ed. K. Koumoto and T. Mori, Springer, Berlin Heidelberg, vol. 182, ch. 1, 2013, pp. 3-32)).
μ=Σi(8π)1/2(h/2π)4eB/3mimd3/2(kBT)3/2g2 (8)
In the equation, e is the elementary charge, mi is the carrier effective mass of the band that appears in the valence band upper edge, B is an elastic constant, and g is deformation potential. mi, B, and g were computed by using a DFT technique that uses the VASP code. Furthermore, g was computed according to a relational equation of g=−Δε/(Δl/l), which is disclosed in Non-Patent Literature 4 (J. Chen et al., “First-Principles Predictions of Thermoelectric Figure of Merit for Organic Materials: Deformation Potential Approximation”, Journal of Chemical Theory and Computation, 8, 2012, pp. 3338-3347). Δε is the rate of change in the band edge energy level in an instance in which a lattice constant l is changed by Δl.
The lattice thermal conductivity κlat was computed according to the following equations (9) to (11), based on the Callaway theory, which is disclosed in Non-Patent Literature 6 (J. Yang, G. P. Meisner and L. Chen, Applied Physics Letters, 85, 2004, pp. 1140-1142).
κlat=κlat,pure×tan−1(u)/u (9)
u
2=π2θdV/hv2×κlat,pure×Γ (10)
Γ=ΓM+ΓS (11)
In the equations, θd is the Debye temperature, ΓM is a parameter representing a fluctuation in the atomic mass, and ΓS is a parameter representing a fluctuation in strain. Each of the parameters was calculated from a composition of the thermoelectric conversion material in accordance with a method disclosed in Non-Patent Literature 6.
A lattice thermal conductivity κlat, pure, which is a lattice thermal conductivity in an instance in which there is no lattice disorder, was computed by using the following empirical equation (12), which is based on the Debye-Callaway model, which is disclosed in Non-Patent Literature 7 (J. Yang et al., “Material descriptors for predicting thermoelectric performance”, Energy & Environmental Science, 8, 2015, pp. 983-994).
κlat,pure=A1Mv3/V2/3n1/3+A2v/V2/3(1−1/n2/3) (12)
In the equation, M is an average atomic mass, v is a longitudinal acoustic wave velocity, V is a volume per atom, and n is the number of atoms present in the unit cell. A1 and A2 were determined such that experimental values of the lattice thermal conductivity of a (Ba, Sr, Ca)Mg2(Bi, Sb)2 system could be reproduced. The use of the experimental values enables an accurate determination of A1 and A2, compared to instances in which the technique disclosed in Non-Patent Literature 7 is used.
Computational prediction of the figure of merit ZT involves two steps: a step of calculating the Fermi energy from the composition, or, more specifically, from the defect concentration; and a step of calculating each of the physical quantities in accordance with the calculated Fermi energy.
The reducing fermi energy and the defect concentration are associated with each other by the following relational equations (13) and (14).
p(EF)=C×NK (13)
p(EF)=1−∫DVB(E)[1−f(E;EF)]dE (14)
In the equations, p is the carrier concentration in the valence band, C is a carrier activation ratio, and NK is the concentration of K atoms, which are the dopant. The carrier activation ratio C was estimated to be 0.2 based on the relationship between the concentration of the introduced K and the measured value of the carrier concentration.
The relational equations (13) and (14) were solved in combination, and, accordingly, the Fermi energy, which was a parameter necessary for predicting the thermoelectric conversion properties, was estimated.
The thermoelectric conversion properties were evaluated by using the above-described computation techniques. Table 4, Table 5, Table 6, Table 7, and Table 8 show the results of evaluation of the thermoelectric conversion properties of materials at temperatures of 330K and 470K or 570K. Table 4 relates to materials having a composition represented by the formula of Ba1-aKaMg2Bi2; Table 5 relates to materials having a composition represented by the formula of Sr1-aKaMg2Bi2 (a+b+c=1 and c=0, that is, b=1−a); Table 6 relates to materials having a composition represented by the formula of Ca1-aKaMg2Bi2 (a+b+c=1 and b=0, that is, c=1−a); Table 7 relates to materials having a composition represented by the formula of Ba0.98-b-cSrbCacK0.02Mg2Bi2; and Table 8 relates to materials having a composition represented by the formula of Ba0.49Ca0.49K0.02Mg2Bi2-dSbd.
Table 4 shows that in each of the Examples, 0.002≤a≤0.1 was satisfied, and thermoelectric conversion properties comparable to those of Example 1, in which a thermoelectric conversion material was actually synthesized and evaluated, were achieved. Furthermore, a ZT330K value greater than those of Comparative Examples 1, 2, and 3 was achieved.
Table 5 shows that in each of the Examples, 0.002≤a≤0.1 was satisfied, and a ZT330K value greater than those of Comparative Examples 1, 2, and 4 was achieved.
Table 6 shows that in each of the Examples, 0.002≤a≤0.1 was satisfied, and thermoelectric conversion properties comparable to those of Example 2, in which a thermoelectric conversion material was actually synthesized and evaluated, were achieved. Furthermore, a ZT330K value greater than those of Comparative Examples 1, 2, and 5 was achieved.
Table 7 shows that in each of the Examples, 0≤b+c≤1−a was satisfied, and thermoelectric conversion properties comparable to those of Example 3 or 4, in which a thermoelectric conversion material was actually synthesized and evaluated, were achieved. Furthermore, a ZT value greater than those of Comparative Examples 1 and 2 was achieved.
Table 8 shows that in each of the Examples, 0≤d≤2 was satisfied, and thermoelectric conversion properties comparable to those of Example 5, in which a thermoelectric conversion material was actually synthesized and evaluated, were achieved. Furthermore, a ZT value greater than those of Comparative Examples 1 and 2 was achieved.
Thermoelectric conversion materials of the present disclosure can be used in thermoelectric conversion devices and thermoelectric conversion modules for converting thermal energy into electrical energy.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2019-163902 | Sep 2019 | JP | national |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2020/027534 | Jul 2020 | US |
| Child | 17517043 | US |
