Thermoelectric conversion module
10454012 ยท 2019-10-22
Assignee
Inventors
- Akinori NISHIDE (Tokyo, JP)
- Yosuke KUROSAKI (Tokyo, JP)
- Jun HAYAKAWA (Tokyo, JP)
- Shin YABUUCHI (Tokyo, JP)
- Hiroyuki Yamamoto (Tokyo, JP)
Cpc classification
H10N10/17
ELECTRICITY
International classification
Abstract
The present invention aims at providing a thermoelectric conversion module with low toxicity, which exhibits conversion efficiency equivalent to that of BiTe. The thermoelectric conversion module of the present invention employs a full Heusler alloy as the material for forming the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit. The material for forming the N-type thermoelectric conversion unit contains at least any one of Fe, Ti, and Si and Sn.
Claims
1. A thermoelectric conversion module comprising: a P-type thermoelectric conversion unit and an N-type thermoelectric conversion unit; and a substrate on which the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit are mounted, wherein a full Heusler alloy is used as a material for forming the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit, wherein the full Heusler alloy forming the N-type thermoelectric conversion unit consists of Fe, Ti, at least one of Si or Sn, and an additive material of at least one of Nb, V, Mo, W, or Zr, wherein an amount of the additive material is smaller than an amount of Ti in the full Heusler alloy forming the n-type thermoelectric conversion unit, wherein the full Heusler alloy forming the P-type thermoelectric conversion unit is different from the full Heusler alloy forming the N-type thermoelectric conversion unit, wherein a ratio of a cross-section area of the P-type thermoelectric conversion unit on a plane orthogonal to a normal direction of the substrate to a sum total of the cross-section area of the P-type thermoelectric conversion unit on the plane and a cross-section area of the N-type thermoelectric conversion unit on the plane is in a range from 0.42 to less than 0.5, wherein the cross-section area of the N-type thermoelectric conversion unit is larger than the cross-section area of the P-type thermoelectric conversion unit, and wherein a length of the P-type thermoelectric conversion unit in the normal direction of the substrate and a length of the N-type thermoelectric conversion unit in the normal direction are in a range from 6 mm to 14.5 mm.
2. The thermoelectric conversion module according to claim 1, wherein a ratio of the length of the P-type thermoelectric conversion unit in the normal direction of the substrate to a square root of the cross-section area of the N-type thermoelectric conversion unit on the plane or a ratio of the length of the N-type thermoelectric conversion unit in the normal direction to the square root of the cross-section area of the N-type thermoelectric conversion unit on the plane is in a range from 0.6 to 1.8.
3. The thermoelectric conversion module according to claim 1, wherein the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit are electrically connected in series via an electrode.
4. The thermoelectric conversion module according to claim 3, wherein Cu, Au or Ta is used as a material for forming the electrode.
5. The thermoelectric conversion module according to claim 3, wherein the full Heusler alloy forming the P-type thermoelectric conversion unit contains Fe, V, and Al.
6. A thermoelectric conversion module comprising: a P-type thermoelectric conversion unit and an N-type thermoelectric conversion unit; and a substrate on which the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit are mounted, wherein a full Heusler alloy is used as a material for forming the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit, wherein the full Heusler alloy forming the P-type thermoelectric conversion unit contains Fe, V, and Al, wherein the full Heusler alloy forming the N-type thermoelectric conversion unit consists of Fe, Ti, at least one of Si or Sn, and an additive material of at least one of Nb, V, Mo, W, or Zr, wherein an amount of the additive material is smaller than an amount of Ti in the full Heusler alloy forming the n-type thermoelectric conversion unit, wherein the full Heusler alloy forming the P-type thermoelectric conversion unit is different from the full Heusler alloy forming the N-type thermoelectric conversion unit, wherein a ratio of a cross-section area of the P-type thermoelectric conversion unit on a plane orthogonal to a normal direction of the substrate to a sum total of the cross-section area of the P-type thermoelectric conversion unit on the plane and a cross-section area of the N-type thermoelectric conversion unit on the plane is in a range from 0.42 to less than 0.5, wherein the cross-section area of the N-type thermoelectric conversion unit is larger than the cross-section area of the P-type thermoelectric conversion unit, and wherein a length of the P-type thermoelectric conversion unit in the normal direction of the substrate and a length of the N-type thermoelectric conversion unit in the normal direction are in a range from 0.5 mm to 14.5 mm.
7. The thermoelectric conversion module according to claim 6, wherein a ratio of the length of the P-type thermoelectric conversion unit in the normal direction of the substrate to a square root of the cross-section area of the N-type thermoelectric conversion unit on the plane or a ratio of the length of the N-type thermoelectric conversion unit in the normal direction to the square root of the cross-section area of the N-type thermoelectric conversion unit on the plane is in a range from 0.6 to 1.8.
8. A thermoelectric conversion module comprising: a P-type thermoelectric conversion unit and an N-type thermoelectric conversion unit; and a substrate on which the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit are mounted, wherein a full Heusler alloy is used as a material for forming the P-type thermoelectric conversion unit and the N-type thermoelectric conversion unit, wherein the full Heusler alloy forming the N-type thermoelectric conversion unit consists of Fe, Ti, at least one of Si or Sn, and an additive material of at least one of Nb, V, Mo, W, or Zr, wherein an amount of the additive material is smaller than an amount of Ti in the full Heusler alloy forming the n-type thermoelectric conversion unit, wherein a ratio of a length of the P-type thermoelectric conversion unit in a normal direction of the substrate to a square root of a cross-section area of the N-type thermoelectric conversion unit on a plane orthogonal to the normal direction or a ratio of a length of the N-type thermoelectric conversion unit in the normal direction to the square root of the cross-section area of the N-type thermoelectric conversion unit on the plane is in a range from 0.6 to 1.8, wherein a cross-section area of the N-type thermoelectric conversion unit on the plane orthogonal to the normal direction is larger than the cross-section area of the P-type thermoelectric conversion unit, and wherein the length of the P-type thermoelectric conversion unit in the normal direction of the substrate or the length of the N-type thermoelectric conversion unit in the normal direction is in a range from 0.5 mm to 14.5 mm.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
DESCRIPTION OF EMBODIMENTS
First Embodiment
Module Structure
(8)
(9) The P-type thermoelectric conversion unit 11 and the N-type thermoelectric conversion unit 12 are bonded and arranged so as to be alternately and electrically connected in series through the electrode 13. A group formed by connecting the P-type thermoelectric conversion units 11 and the N-type thermoelectric conversion units 12 in series will be called a PN element. The PN element is vertically interposed between the substrates 14 and 15 so that the PN element is mounted on the substrate. The structure is configured to transfer heat to the respective thermoelectric conversion units via the substrate 14 and 15. Each of the thermoelectric conversion units is electrically arranged in series, and thermally in parallel.
First Embodiment
Principle for Improvement of Conversion Performance
(10) The principle for improving the conversion performance of the thermoelectric conversion material will be described. Various types of candidates for the material that replaces the BiTe alloy have been studied. A certain type of full Heusler alloy is one of the candidate materials for the low temperature region. The full Heusler alloy which exhibits the thermoelectric conversion performance represented by Fe.sub.2VAl has an electronic state so called pseudo gap. General relationship between the thermoelectric conversion performance and the electronic state will be described in order to clarify the correlation of the pseudo gap with the thermoelectric conversion performance.
(11) The performance index of the thermoelectric conversion material is derived from the following Formula 1, taking the dimensionless number referred to as ZT as the index.
(12)
S: Seebeck coefficient, : thermal conductivity, : resistivity, T=room temperature (300 K).
(13) The larger the Seebeck coefficient S becomes, and the lower the resistivity and thermal conductivity become, the larger the performance index becomes. The Seebeck coefficient S and the resistivity are physical quantity determined by the electronic state of the substance. The Seebeck coefficient S has a relationship as expressed by the following Formula 2.
(14)
E: binding energy, N: state density.
(15) According to the Formula 2, the Seebeck coefficient S is inversely proportional to the absolute value of the density of states (DS) N at Fermi level, and proportional to the energy gradient. This clearly shows that the substance with low density of states at the Fermi level, which sharply changes rise-up of the density of states, is allowed to have high Seebeck coefficient S.
(16) Meanwhile, the resistivity has the correlation as expressed by the following Formula 3.
(17)
.sub.F: mean free path of electron at Fermi level, .sub.F: electron velocity at Fermi level
(18) According to the Formula 3, the resistivity is inversely proportional to the density of states N. Therefore, the resistivity becomes small when the Fermi level is at the energy position with large absolute value of the density of states N.
(19) Resuming the explanation of the electronic state of the pseudo gap, the band structure of the pseudo gap is in the electronic state where the density of states around the Fermi level is markedly dropped. Typically, when the composition ratio of the compound is changed, the band structure of Fe.sub.2VAl based alloy takes a behavior like rigid band model to change only the energy position at the Fermi level without significantly changing the band structure. The Fe.sub.2VAl based alloy has electrons doped or hole-doped by changing the composition ratio or composition of the compound so that the Fermi level is controlled to the energy position at which the density of states sharply changes, and the absolute value of the density of states is optimized. This is thought to optimize the relationship between the Seebeck coefficient and the resistivity. Furthermore, the Fe.sub.2VAl based alloy is the matter system which can be realized into both p-type and n-type. Positive usage of the energy level that causes sharp change in the density of states by the Fe.sub.2VAl for realizing the thermoelectric conversion performance is expected to further improve the performance.
(20) The thermal conductivity may be regarded as the sum of the lattice thermal conductivity p for heat transfer through lattice vibration and the electron heat conductivity e for heat transfer through the electron serving as a medium. It is said that the electron heat conductivity e becomes high as the resistivity becomes lower in accordance with Wiedemann-Franz law, and depends on the pseudo gap electronic state. Meanwhile, the following Formula 4 clearly shows that the lattice thermal conductivity p depends on the lattice size. To summarize, the thermal conductivity may be expressed as follows.
[Formula 4]
=k.sub.fC.sub.pFormula 4
(21)
material density, d: particle size, C.sub.p: sample's specific heat at constant pressure, .sub.f: time taken for heat transfer from the back surface to the upper surface of the particle.
(22) Formulae 4 and 5 clearly show that the thermal conductivity becomes small as the particle size of the sample is reduced. In this way, the full Heusler alloy remarkably improves the thermoelectric conversion performance by controlling the electronic state of the alloy to reduce the particle size of the sample.
(23) As described above, in the present invention, the full Heusler alloy is employed as the thermoelectric conversion material. The Fe.sub.2Val based alloy which exhibits the P-type characteristic is used as the material for forming the P-type thermoelectric conversion unit 11, and Fe.sub.2TiSiSn based alloy which exhibits the N-type characteristic is used as the material for forming the N-type thermoelectric conversion unit 12.
(24) The pseudo gap structure that determines the thermoelectric conversion characteristic of the full Heusler alloy has a distinctive band structure called flat band. It is suggested that the flat band mainly determines the thermoelectric conversion material. It is thought that the thermoelectric conversion characteristic is improved by controlling the flat band into appropriate states.
(25)
(26) As
(27) In the case where at least any one of Nb, V, Mo, W and Zr is added as the additive material for adjusting the total amount of electrons, the characteristic similar to the one as shown in
(28) According to the present invention, the alloy composition which can be practically formed and exhibit high performance thermoelectric conversion characteristic is selected from those suggested as a result of the first-principle calculation. Especially the Fe.sub.2TiSiSn based alloy has the flat band around the Fermi level as indicated by the view of the band shown in
First Embodiment
Structure Example of Thermoelectric Conversion Module 10
(29) An example of the structure of the thermoelectric conversion module 10 produced in accordance with the aforementioned principle will be described. This example uses Fe.sub.2VAl alloy as the material for forming the P-type thermoelectric conversion unit 11, and Fe.sub.2TiSiSn based alloy as the material for forming the N-type thermoelectric conversion unit 12. It is configured to use Ta as the material for forming the electrode 13, and AlN for forming the substrates 14 and 15. The material with high heat conductivity and high strength may be used for forming the framework. The steel is used in this example.
(30)
(31) The respective thermoelectric conversion units may be produced through the sintering method with a hot press. The powder element as the material is filled in the carbon die for sintering while adjusting the weight so that the alloy element composition ratio becomes as designed.
(32) The Fe.sub.2TiVSi based alloy is produced by weighing the powder of the elements including Fe, Ti, V and Si to be filled in the carbon die so that the element composition ratio corresponds to the compositional formula as described above, for example, Fe:Ti:V:Si=2.1:0.8:0.2:1.2 (=0.1, x=0.8, y=0.2, z=1.2, q=0). It is subjected to reaction sintering at the temperature of 800 C. for 5000 seconds, for example. In order to improve the degree of order of the crystal structure of the sintered body resulting from the reaction sintering, the heating process may be applied, for example, at 600 C. for two days. The additive material V is mixed with the composition in order to improve the performance of the thermoelectric conversion material and to stabilize the crystal structure. The thus produced pellet is processed to have the aforementioned dimensions so as to be mounted on the thermoelectric conversion module 10.
(33) In the structure example, Fe.sub.2VAl is used as the material for forming the P-type thermoelectric conversion unit 11, which is not limited thereto. For example, it is possible to use Fe.sub.2NbAl, FeS.sub.2 and the like. It is possible to use GaN as the material for forming the substrates 14 and 15, and use Cu or Au as the material for forming the electrode 13.
(34) In the structure example, the material composition of the N-type thermoelectric conversion unit is set to Fe.sub.2.1Ti.sub.0.8V.sub.0.2Si.sub.1.2, which is not limited thereto. It is possible to use the alloy composition with characteristic as the full Heusler alloy that exhibits the N-type characteristic as shown in
(35) In the case where at least any one of Nb, V, Mo, W and Z is added as the additive material, it is considered necessary to make the total of the composition ratios of those additive materials smaller than the composition ratio of Ti. If the total composition ratio of the additive materials becomes larger, it will deviate from the range of the Fe.sub.2TiSiSn based alloy as described in
First Embodiment
Summary
(36) The thermoelectric conversion module 10 according to the first embodiment uses the full Heusler alloy as the material for forming both the P-type thermoelectric conversion unit 11 and the N-type thermoelectric conversion unit 12. The material for forming the N-type thermoelectric conversion unit 12 is the Fe.sub.2TiSiSn based full Heusler alloy which contains at least any one of Fe, Ti, and Si and Sn. This makes it possible to provide the thermoelectric conversion module with high thermoelectric conversion efficiency and low toxicity.
Second Embodiment
(37) The thermoelectric conversion performance of the thermoelectric conversion module is likely to be influenced by the heat flow Q into the module in addition to the conversion efficiency of the thermoelectric conversion material. The heat flow Q is a variable influenced by the structure (especially each size of the components) of the thermoelectric conversion module. It is therefore important to design the module structure suitable for the characteristic of the selected thermoelectric conversion material. In the second embodiment of the present invention, optimization of each size of the respective components of the thermoelectric conversion module 10 will be examined on the assumption that the thermoelectric conversion material as described in the first embodiment is employed. The other structure of the thermoelectric module 10 is similar to the one as described in the first embodiment.
(38)
(39) The x-axis of
(40) As
(41)
(42) As
(43)
(44) The x-axis of
(45)
(46)
(47) The (pattern a) may be read that the maximum output is obtained in accordance with the value L. This clarifies that substantially the same results as those shown in
(48) The (pattern b) may be read that, assuming that the L takes the same value, the output of the PN element is increased to reach the maximum value as the value of L/An.sup.1/2 changes from small side to large side, that is, the Ap and An change from large side to small side, and thereafter, the output of the PN element decreases as the value of L/An.sup.1/2 becomes large, that is, the Ap and An become integrally small.
(49)
(50)
(51) The aforementioned tendency is not changed irrespective of the value L. However, the optimum values of L/An.sup.1/2 vary in accordance with the value L. The value L/An.sup.1/2 that provides the output approximate to the maximum value cannot be found from the L that takes any value.
(52) Results shown in
(53) Referring to
Second Embodiment
Summary
(54) On the assumption that the thermoelectric conversion material described in the first embodiment is employed, the optimum dimension of the thermoelectric conversion module 10 is examined based on various calculation results in the second embodiment. This makes it possible to find the optimum values for sizes of the respective components. Employment of the thermoelectric conversion material described in the first embodiment and the module structure described in the second embodiment ensures to optimize efficiency of the thermoelectric conversion module 10.
LIST OF REFERENCE SIGNS
(55) 10: thermoelectric conversion module, 11: P-type thermoelectric conversion unit, 12: N-type thermoelectric conversion unit, 13: electrode, 14 and 15: substrate