THERMOELECTRIC CONVERSION ELEMENT AND THERMOELECTRIC CONVERSION DEVICE
20200212282 ยท 2020-07-02
Inventors
Cpc classification
H10N10/17
ELECTRICITY
International classification
Abstract
A thermoelectric conversion element is made of a material with a band structure having Weyl points in the vicinity of Fermi energy. The thermoelectric conversion element has a thermoelectric mechanism for generating electromotive force by the anomalous Nernst effect. A thermoelectric conversion device includes a substrate; and a power generator provided on the substrate and including a plurality of thermoelectric conversion elements. Each of the plurality of thermoelectric conversion elements has a shape extending in one direction, and is made of a material identical to that of the above-mentioned thermoelectric conversion element. The plurality of thermoelectric conversion elements is arranged in parallel to one another in a direction perpendicular to the one direction and electrically connected in series to one another in a serpentine shape.
Claims
1. A thermoelectric conversion element made of a material with a band structure having Weyl points in a vicinity of Fermi energy, wherein the thermoelectric conversion element has a thermoelectric mechanism for generating electromotive force by anomalous Nernst effect.
2. The thermoelectric conversion element according to claim 1, wherein a density of states of the material has energy dependence having an extreme value in the vicinity of the Fermi energy.
3. The thermoelectric conversion element according to claim 1, wherein a thermoelectric coefficient that defines the electromotive force has temperature dependence proportional to TlogT, where T is a temperature.
4. The thermoelectric conversion element according to claim 1, wherein the material shows ferromagnetism.
5. The thermoelectric conversion element according to claim 1, wherein the material has a cubic crystal structure.
6. The thermoelectric conversion element according to claim 1, wherein the material has a full Heusler crystal structure.
7. The thermoelectric conversion element according to claim 1 herein the Weyl points of the material exist within a range of 0.1 eV from the Fermi energy.
8. The thermoelectric conversion element according to claim 1, wherein the band structure of the material is obtained from first-principles calculations.
9. The thermoelectric conversion element according to claim 1, wherein the thermoelectric conversion element has a thickness greater than or equal to 0.1 m.
10. A thermoelectric conversion device comprising: a substrate; and a power generator provided on the substrate and including a plurality of thermoelectric conversion elements, wherein each of the plurality of thermoelectric conversion elements has a shape extending in one direction, and is made of a material identical to that of the thermoelectric conversion element according claim 1, and in the power generator, the plurality of thermoelectric conversion elements is arranged in parallel to one another in a direction perpendicular to the one direction and electrically connected in series to one another in a serpentine shape.
11. A thermoelectric conversion device comprising: the thermoelectric conversion element according to claim 1; and a hollow member, wherein the thermoelectric conversion element is a sheet-shaped element covering an outer surface of the hollow member.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENT
[0031] Exemplary embodiments of the present invention will be described below with reference to the accompanying drawings.
[0032] In recent years, it is theoretically known that topological electronic structures relate to a thermoelectric mechanism based on the anomalous Nernst effect. In particular, recent studies have indicated that the Berry curvature of Weyl points residing in the vicinity of Fermi energy E.sub.F can potentially enhance the anomalous Nernst effect, and it is therefore expected that search for materials containing the Weyl fermions and new material synthesis are effective in development of a thermoelectric conversion device using the anomalous Nernst effect.
[0033] The Weyl fermions are massless fermions defined by the Dirac equation. As shown in
[0034] Recent first-principles calculations have shown that metals with composition Co.sub.2TX are potential Weyl metals in which Weyl points exist in the momentum space near the Fermi energy E.sub.F. Here, T is a transition metal, and X is one of Si, Ge, Sn, Al, and Ga. As an example of such metals, the following embodiments are directed to Co.sub.2MnGa, which is a full Heusler ferromagnet.
[0035]
[0036] Next, a thermoelectric conversion element according to the embodiments of the present invention and a thermoelectric mechanism thereof will be described with reference to
[0037] Reference will now be made to a verification experiment of the anomalous Nernst effect of the thermoelectric conversion element 1.
[0038] Single crystals of Co.sub.2MnGa were prepared by the Czochralski method after making polycrystalline samples by arc-melting Co, Mn, and Ga with an appropriate ratio. X-ray diffraction showed that the produced Co.sub.2MnGa had a lattice constant a=5.77(3) angstroms. In the experiment, three box-shaped samples with a size of 7.52.01.3 mm.sup.3 were produced as the thermoelectric conversion element 1. The three samples are distinguished according to crystal orientations parallel to directions of magnetic fields B, and a B||[100] sample, a B||[110] sample, and a B||[111] sample are denoted by #100, #110, and #111, respectively. In the embodiments, transport phenomena (the Nernst effect, the Seebeck effect, and the Hall effect) were measured for each sample by using a known method.
[0039]
[0040] A graph a in
[0041] A ratio of the observed value S.sub.yx to the Seebeck coefficient S.sub.xx indicated by a graph b in
[0042] As shown in graphs c and d of
[0043] Graphs e and f in
[0044] The observed Hall resistivity |.sub.yx15 cm is one of the largest known for the anomalous Hall effect. Similarly, the Hall conductivity is also exceptionally large. A graph a in
[0045] The Nernst coefficient S.sub.yx can be defined by the Peltier coefficient .sub.yx. In general, electric current is generated by both electric field and temperature gradient T and expressed by J=.Math..Math.T. Here, J, and are an electric current density tensor, an electric conductivity tensor, and a thermoelectric conductivity tensor, respectively. Assuming that the direction of the magnetic field B is parallel to the direction z and the temperature gradient T is parallel to the direction x, and setting J=0, the following is obtained: J.sub.y=.sub.yxS.sub.xx+.sub.xxS.sub.yx.sub.yx=0. Here, a cubic symmetry provides .sub.xx=.sub.yy. That is, the Peltier coefficient, which is a transverse thermoelectric coefficient, is given by the following Expression (1):
Peltier coefficient .sub.yx=Hall conductivity .sub.yxSeebeck coefficient S.sub.xx+longitudinal conductivity .sub.xxNernst coefficient S.sub.yx (1).
[0046] According to Expression (1), the Peltier coefficient determines the magnitude of the Nernst coefficient, and it is effective to evaluate the Peltier coefficient for determination of the anomalous Nernst effect.
[0047] A graph b in
[0048] .sub.yxT behavior at low temperatures is consistent with the Mott formula, which defines the relation between .sub.yx at low temperatures (k.sub.BT<<E.sub.F) and the energy derivative of the Hall conductivity .sub.yx at T=0 (.sub.yx(.sup.2k.sub.B.sup.2T/3e) (.sub.yx/E.sub.F)). Here, k.sub.B is the Boltzmann constant. On the other hand, .sub.yxTlogT behavior at high temperatures (between T30 K and T400 K) indicates violation of the Mott formula. The TlogT behavior of the thermoelectric coefficient can be understood in terms of Weyl fermions, as will be described below.
[0049] To provide evidence for the existence of Weyl points, the focus is first put on a Fermi surface closest to the Fermi energy E.sub.F of Co.sub.2MnGa.
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[0052] The right handed (+) and left handed () Weyl fermions are described by low-energy Hamiltonians, as given by Expression (2).
Here, v.sub.1, v.sub.2, and v.sub. are three independent velocity parameters, and h is the Planck constant. According to the first-principles calculations of Co.sub.2MnGa described above, the Weyl fermions are located at k.sub.0(2/a)0.15 in the vicinity of E.sub.020 meV, and a tilt parameter v.sub.2/v.sub.1=0.99 and v.sub.110.sup.5 m/s are obtained. The tilt parameter v.sub.2/v.sub.1=1 corresponds to a quantum critical point, v.sub.2/v.sub.1<1 corresponds to type-I Weyl fermions, and v.sub.2/v.sub.1>1 corresponds to type-II Weyl fermions. In the type-I Weyl fermions (v.sub.2/v.sub.1<1), the density of states at the Weyl points is zero, whereas in the type-II Weyl fermions (v.sub.2/v.sub.1>1), the density of states at the Weyl points is finite so that electron and hole pockets touch.
[0053] At the quantum critical point (v.sub.2/v.sub.1=1), the energy derivative of the Hall conductivity .sub.yx/E displays log divergent behavior at low energy. The low energy theory suggests that .sub.yx(T, ) indicating temperature and chemical potential dependence of the Peltier coefficient in the vicinity of the quantum critical point can be expressed in terms of a dimensionless scaling function G over a wide range of temperatures (see
[0054] That is, based on the scaling function of the low energy theory, the logarithmic divergence of .sub.yx/E at the quantum critical point can lead to .sub.yxTlog(|E.sub.F-E.sub.0|/(hv.sub.1k.sub.0/2)) behavior at low temperatures. On the other hand, this logarithmic divergence can lead to .sub.yxTlog(k.sub.BT/(hv.sub.1k.sub.0/2)) behavior at high temperatures k.sub.BT>|E.sub.F-E.sub.0|, which does not follow the Mott formula (.sub.yxT) . Thus, the temperature dependence of .sub.yx can be understood in terms of a scaling function of the low energy theory in the vicinity of the quantum critical point between the type I and the type II over a decade of temperatures.
[0055] When the chemical potential is tuned to the Weyl points (=E.sub.0), the scaling function does not follow the Mott formula even at any low temperature (broken line in
[0056] A graph a in
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[0058] As described above, the first-principles calculations of Co.sub.2MnGa show the existence of the type-I Weyl fermions, which are located at k.sub.0(2/a)0.15 in the vicinity of E.sub.020 meV and have the tilt parameter of v.sub.2/v.sub.1=0.99, thereby obtaining the Nernst coefficient in the vicinity of the quantum critical point.
[0059] To provide further evidence for the existence of Weyl fermions in Co.sub.2MnGa, measurements of magnetic field dependence of the longitudinal conductivity .sub.xx with different electric current directions and measurements of angle dependence of magneto-conductivity .sub.xx(B)-.sub.xx(0) with different electric current directions were performed on the thermoelectric conversion element 1.
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[0062] Next, reference will be made to a thermoelectric conversion device including the thermoelectric conversion element according to the embodiments in the form of modules.
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[0064] The substrate 22 has a first surface 22a on which the power generator 23 is placed, and a second surface 22b opposite to the first surface 22a. Heat from a heat source (not shown) is applied onto the second surface 22b.
[0065] The power generator 23 includes a plurality of thermoelectric conversion elements 24 and a plurality of thermoelectric conversion elements 25, each having a three-dimensional L shape and being made of a material identical to that of the thermoelectric conversion element 1 shown in
[0066] The plurality of thermoelectric conversion elements 24 and the plurality of thermoelectric conversion elements 25 are arranged such that magnetization M1 of the thermoelectric conversion elements 24 is oriented opposite to a direction of magnetization M2 of the thermoelectric conversion elements 25. Further, the plurality of thermoelectric conversion elements 24 has the Nernst coefficient with the same sign as that of the Nernst coefficient of the plurality of thermoelectric conversion elements 25.
[0067] Each of the thermoelectric conversion elements 24 has a first end face 24a and a second end face 24b, both of which are parallel to the longitudinal direction (direction x) of each of the thermoelectric conversion elements 24. Each of the thermoelectric conversion elements 25 has a first end face 25a and a second end face 25b, both of which are parallel to the longitudinal direction (direction x) of each of the thermoelectric conversion elements 25. The first end face 25a of the thermoelectric conversion element 25 is connected to the second end face 24b of one thermoelectric conversion element 24 adjacent thereto on one side thereof, and the second end face 25b of the thermoelectric conversion element 25 is connected to the first end face 24a of another thermoelectric conversion element 24 adjacent thereto on the opposite side thereof. With this structure, the plurality of thermoelectric conversion elements 24 and the plurality of thermoelectric conversion elements 25 are electrically connected in series to one another. That is, the power generator 23 is provided on the first surface 22a of the substrate 22 in a serpentine shape.
[0068] When heat is applied from the heat source onto the second surface 22b of the substrate 22, the heat current Q flows in the direction +z toward the power generator 23. When the heat current Q creates a temperature difference, the anomalous Nernst effect causes each of the thermoelectric conversion elements 24 to generate electromotive force E1 in the direction (direction x) perpendicular to both the direction of the magnetization M1 (direction y) and the direction of the heat current Q (direction +z). The anomalous Nernst effect causes each of the thermoelectric conversion elements 25 to generate electromotive force E2 in the direction (direction +x) perpendicular to both the direction of the magnetization M2 (direction +y) and the direction of the heat current Q (direction +z).
[0069] Since the thermoelectric conversion elements 24 and the thermoelectric conversion elements 25, which are arranged in parallel to one another, are electrically connected in series to one another as described above, the electromotive force E1 generated in one thermoelectric conversion element 24 can be applied to the adjacent thermoelectric conversion element 25. Since the direction of the electromotive force E1 generated in the one thermoelectric conversion element 24 is opposite to the direction of the electromotive force E2 generated in the adjacent thermoelectric conversion element 25, the electromotive force in the thermoelectric conversion element 24 and the electromotive force in the adjacent thermoelectric conversion element 25 are added up, thereby increasing an output voltage V.
[0070] As a modification of the thermoelectric conversion device 20 in
[0071] Aspects of the thermoelectric conversion device according to the embodiments should not be limited to the above-described embodiment shown in
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[0073] In
[0074] The thermoelectric conversion device 20 and the thermoelectric conversion device 30 can be used for a variety of apparatuses. For example, a heat flux sensor provided with the thermoelectric conversion device enables evaluation of heat insulation performance of buildings. Further, an exhaust system of a motorcycle or other vehicles provided with the thermoelectric conversion device allows utilization of heat of exhaust gas (waste heat) for power generation. It is therefore possible to make effective use of the thermoelectric conversion device as an auxiliary power supply.
[0075] The embodiments have focused on the electric voltage generated by the anomalous Nernst effect. Instead, the output voltage can be increased by virtue of synergy among the electric voltage generated by the Seebeck effect resulting from a temperature difference, the Hall effect that occurs based on the electric voltage generated by the Seebeck effect, and the electric voltage generated by the anomalous Nernst effect.
[0076] The embodiments have been described in which Co.sub.2MnGa is a material that enhances the anomalous Nernst effect based on the existence of Weyl fermions. In addition to Co.sub.2MnGa, examples of potential materials that are likely to enhance the anomalous Nernst effect based on the existence of Weyl fermions may include Co.sub.2MnAl, Co.sub.2MnIn, Mn.sub.3Ga, Mn.sub.3Ge, Fe.sub.2NiGa, CoTiSb, CoVSb, CoCrSb, CoMnSb, and TiGa.sub.2Mn.
REFERENCE SIGNS LIST
[0077] 1, 24, 25, 32 Thermoelectric conversion element [0078] 20, 30 Thermoelectric conversion device [0079] 22 Substrate [0080] 23 Power generator [0081] 31 Hollow member