Half-Heusler Compounds for Use in Thermoelectric Generators
20170141282 ยท 2017-05-18
Inventors
Cpc classification
F01N5/025
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
C22C27/02
CHEMISTRY; METALLURGY
H10N10/8556
ELECTRICITY
H10N19/101
ELECTRICITY
Y02T10/12
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
A thermoelectric generator includes a hot side heat exchanger, a cold side heat exchanger, a plurality of n-type semiconductor legs arranged between the hot side heat exchanger and the cold side heat exchanger, and a plurality of p-type semiconductor legs arranged between the hot side heat exchanger and the cold side heat exchanger and alternating electrically in series with the plurality of n-type semiconductor legs. At least one of the plurality of n-type semiconductor legs and the plurality of p-type semiconductor legs is formed of an alloy having a half-Heusler structure and comprising Si and Sn with molar fractions of x Sn and 1-x Si, and x is less than 1.
Claims
1. A thermoelectric generator comprising: a hot side heat exchanger; a cold side heat exchanger; a plurality of n-type semiconductor legs arranged between the hot side heat exchanger and the cold side heat exchanger; and a plurality of p-type semiconductor legs arranged between the hot side heat exchanger and the cold side heat exchanger and alternating electrically in series with the plurality of n-type semiconductor legs, wherein at least one of the plurality of n-type semiconductor legs and the plurality of p-type semiconductor legs is formed of an alloy having a half-Heusler structure and comprising Si and Sb with molar fractions of x Sb and 1-x Si, and x is less than 1.
2. The thermoelectric generator of claim 1, wherein the alloy comprises NbCoSi.sub.1-xSn.sub.x and x is greater than 0.27.
3. The thermoelectric generator of claim 1, wherein the alloy comprises TaCoSi.sub.1-xSn.sub.x and x is greater than 0.21.
4. The thermoelectric generator of claim 1, wherein the alloy comprises TiNiSi.sub.1-xSn.sub.x and x is greater than 0.36.
5. The thermoelectric generator of claim 1, wherein the alloy comprises VCoSi.sub.1-xSn.sub.x and x is greater than 0.27.
6. A vehicle comprising: an engine; an exhaust system operably connected to the engine so as to receive exhaust from the engine and discharge the exhaust to an outlet, the exhaust system including a thermoelectric generator comprising: a hot side heat exchanger; a cold side heat exchanger; a plurality of n-type semiconductor legs arranged between the hot side heat exchanger and the cold side heat exchanger; and a plurality of p-type semiconductor legs arranged between the hot side heat exchanger and the cold side heat exchanger and connected alternating electrically in series with the plurality of n-type semiconductor legs, wherein at least one of the plurality of n-type semiconductor legs and the plurality of p-type semiconductor legs is formed of an alloy having a half-Heusler structure and comprising Si and Sb with molar fractions of x Sb and 1-x Si, and x is less than 1.
7. The vehicle of claim 6, wherein the alloy comprises NbCoSi.sub.1-xSn.sub.x and x is greater than 0.27.
8. The vehicle of claim 6, wherein the alloy comprises TaCoSi.sub.1-xSn.sub.x and x is greater than 0.21.
9. A semiconductor alloy comprising: a first element selected from one of group IV-B and group V-B; a second element selected from group VIII; Sn with a molar fraction of x; Si with a molar fraction of 1-x; and a doping agent, wherein the semiconductor alloy has a half-Heusler structure and x is less than 1.
10. The semiconductor alloy of claim 9, wherein the first element includes one element selected from the group consisting of Nb, Ta, Ti, and V.
11. The semiconductor alloy of claim 10, wherein the second element includes one element selected from the group consisting of Co and Ni.
12. The semiconductor alloy of claim 11, wherein the first element is Nb, the second element is Co, and x is greater than 0.27.
13. The semiconductor alloy of claim 12, wherein x is between 0.27 and 0.50.
14. The semiconductor alloy of claim 11, wherein the first element is Ta, the second element is Co, and x is greater than 0.21.
15. The semiconductor alloy of claim 14, wherein x is between 0.21 and 0.50.
16. The semiconductor alloy of claim 11, wherein the first element is Ti, the second element is Ni, and x is greater than 0.36.
17. The semiconductor alloy of claim 16, wherein x is between 0.36 and 0.50.
18. The semiconductor alloy of claim 11, wherein the first element is V, the second element is Co, and x is greater than 0.27.
19. The semiconductor alloy of claim 11, wherein the semiconductor alloy is an n-type semiconductor element formulated as ABSi.sub.[(1-x)(1-y)]Sn.sub.[x(1-y)]D.sub.y, wherein A is the first element, B is the second element, and D is the doping agent.
20. The semiconductor alloy of claim 11, wherein the semiconductor alloy is a p-type semiconductor element formulated as A.sub.1-yBSi.sub.(1-x)Sn.sub.xD.sub.y, wherein A is the first element, B is the second element, and D is the doping agent.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0026]
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[0028]
[0029]
[0030]
[0031]
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[0033]
[0034]
DETAILED DESCRIPTION
[0035] For the purposes of promoting an understanding of the principles of the embodiments described herein, reference is now made to the drawings and descriptions in the following written specification. No limitation to the scope of the subject matter is intended by the references. This disclosure also includes any alterations and modifications to the illustrated embodiments and includes further applications of the principles of the described embodiments as would normally occur to one skilled in the art to which this document pertains.
[0036]
[0037] A thermoelectric generator 120 is incorporated into the exhaust system and in particular integrated into the exhaust pipe 104 to transform heat generated by exhaust gases into electrical energy/power. The thermoelectric generator 120 is operably connected to an energy storage device 124 and is configured to store the generated electrical energy in the storage device 124, which, in some embodiments, includes a rechargeable battery configured to provide the electrical energy to various vehicle systems VS.sub.1, VS.sub.2 . . . VS.sub.n as desired. In various embodiments, the vehicle systems VS.sub.1, VS.sub.2 . . . VS.sub.n include engine controls, exhaust system controls, a door lock system, window lifting mechanism, interior lighting, interior electronics, the vehicle drivetrain, etc.
[0038] In some embodiments, a controller 128 is operably connected to the storage device 124 and/or the thermoelectric generator 120 to control the storage and usage of the electrical energy generated by the thermoelectric generator 120.
[0039] In some embodiments, a temperature control device 132 is operably connected to the exhaust pipe 104, such as in the exhaust pipe 104 upstream of the thermoelectric generator 120. The temperature control device 132 is a cooling device 136 that cools heated exhaust gases to temperatures within a specified temperature range that is between the upper and lower temperature limits of materials used to construct the thermoelectric generator 120. These cooled exhaust gases are then communicated to an inlet 140 to the thermoelectric generator 120.
[0040] In various embodiments, the cooling device 136 includes different types of cooling components. For example, in one embodiment, the cooling device 136 includes a fluid cooled heat exchanger, while in another embodiment, the cooling device 136 includes air or water injection for cooling. In another embodiment, the cooling device 136 has an air gap pipe combined with air injection or forced air cooling, which provides both cooling and a potential reduction in thermal inertia to avoid faster heat up. In further embodiments, the cooling device 136 is configured to incorporate the function of a compression assembly, discussed below, in particular by directing coolant or cooling effects to the cold-side heat exchanger of the thermoelectric generator 120.
[0041] In some embodiments, no cooling device is positioned between the thermoelectric generator 120 and the engine 108, for example in embodiments in which the materials of the thermoelectric generator 120 are configured to receive exhaust at high temperatures.
[0042] As the exhaust gases pass through the thermoelectric generator 120, waste heat from the exhaust gases is transformed into electrical energy. The exhaust gas then exits the thermoelectric generator 120 via an outlet 144. The illustrated configuration is a non-bypass arrangement, in which all of the exhaust gases flow through the thermoelectric generator 120. In other embodiments, only a portion of the exhaust gases flow through the thermoelectric generator 120, while the remainder of the exhaust gases bypass the thermoelectric generator 120. In a further embodiment, the exhaust system includes multiple thermoelectric generators 120 arranged in parallel in the exhaust pipe 104, and the exhaust pipe 104 is branched so as to split the exhaust gases between the thermoelectric generators 120.
[0043] The key components of the thermoelectric generator 120 are the thermoelectric modules which convert the heat flux into electric power. The configuration and operation of the thermoelectric module 200 is depicted in
[0044] The legs 204 and 208 and conductor elements 212 are sandwiched between a cold side substrate 216 and a hot side substrate 220. The temperature gradient between the cold side substrate 216 and the hot side substrate 220 drives the electric current 224 in each leg according to the Seebeck effect, E.sub.emf=sT, where S is the Seebeck coefficient which is a property of the local material, and V T is the temperature gradient across the semiconductor legs.
[0045] The materials used for the n-type and p-type semiconductor legs 204 and 208, respectively, have a significant impact on the efficiency of the power generation by the thermoelectric generator. In particular, as discussed above, the thermal conductivity, electrical conductivity, and Seebeck coefficient of a material impact the figure of merit (ZT). As is discussed in more detail below, one or both of the n-type and p-type semiconductor legs 204 and 208, respectively, are formed of a half-Heusler phase alloy containing Silicon (Si) and Tin (Sn) in a molar fraction Si.sub.1-xSn.sub.x.
[0046] In various embodiments, the n-type and/or p-type semiconductor legs 204, 208 are formed of materials having the chemical formula XYZD, where X is typically a transition metal in the IV-B or V-B group, for example Titanium (Ti), Zirconium (Zr), Hafnium (Hf), Vanadium (V), Niobium (Nb), or Tantalum (Ta). Y is typically selected from group VIII of the transition metals, for example Cobalt (Co), Rhodium (Rh), Iridium (Ir), Nickel (Ni), Palladium (Pa), or Platinum (Pt). The Z represents the Si.sub.1-xSn.sub.x portion of the alloy discussed above.
[0047] D represents a doping agent, or charge carrier, which is added in small amounts to the alloy in place of one of the above elements so that the semiconductor has extra electrons (in n-type semiconductors) or holes, which are open spaces for electrons (in p-type semiconductors). In n-type semiconductors, the doping agent is generally an element having one more valence electron than the Z element, and replaces a small portion of the Z element. For example, in some embodiments, Antimony (Sb), which is in group V-A, replaces a small portion of the Si.sub.1-xSn.sub.x portion of the alloy. In p-type semiconductors, the doping agent is typically a transition element having one less valence electron than the X element (i.e. is one group to the left of the X element in the Periodic Table). For example, in some embodiments, Ti (group IV-B) is the doping agent in an alloy in which the X element is Ta (group V-B), such that Ti replaces a small portion of the Ta to produce holes in the semiconductor.
[0048] The crystalline structure of the alloy compound also affects the figure of merit of the alloy. Depending on the elements used in an alloy, an alloy may be stable in an orthorhombic structure or a half-Heusler structure. As an example,
[0049] The half-Heusler structure of
[0050] As discussed above, the figure of merit (ZT) is directly proportional to the electrical conductivity () of the material used in the thermoelectric generator. Thus, it is advantageous to use semiconductors having a greater electrical conductivity, and thus a narrower band gap. Consequently, materials in the half-Heusler phase typically have a greater figure of merit compared to materials in the orthorhombic phase, and it is therefore desirable to use alloys that are stable in the half-Heusler phase as the semiconductors in the thermoelectric generators.
[0051] Certain materials having Si as the Z element have been calculated to have promising thermoelectric properties when in the half-Heusler phase. In particular, NbCoSi and TaCoSi are projected to have promising thermoelectric properties. The compositions of these materials are similar to the Sn-based alloys, NbCoSn and TaCoSn, which are disclosed in Publication No. WO 2015/130364, the contents of which are hereby incorporated by reference in their entirety.
[0052]
TABLE-US-00001 TABLE 1 p-type n-type (molar fraction of (molar fraction of Ti doped in place Sb doped in place of Nb or Ta) of Si or Sn) NbCoSi 0.02 0.002 TaCoSi 0.05 0.02 NbCoSn 0.06 0.03 TaCoSn 0.06 0.02
[0053] According to the Landolt-Bornstein database, however, the half-Heusler phase of NbCoSi is not stable. In other words, the half-Heusler phase has a greater thermodynamic energy compared to the orthorhombic phase. Since compounds naturally react toward lower thermodynamic energy states, the half-Heusler phase of NbCoSi naturally reacts to become the orthorhombic phase. As such, NbCoSi cannot be used as a semiconductor element in a thermodynamic generator.
[0054] Even though the pure Si phases are not stable, however, it has been discovered that enhanced thermoelectric performance is obtained by alloying the Si phases of certain materials with the stable Sn-based half-Heusler phases of the compounds. Such alloys have the formula X.sub.1Y.sub.1Si.sub.1-xSn.sub.x. For the sake of simplicity, the doping agent D is omitted in the following discussion with the understanding that the preferred quantity of doping agent is calculated and added to replace the X compound (for p-type semiconductors) or the Si.sub.1-xSn.sub.x (for n-type semiconductors), as is generally described in WO ______ [PCT/US2014/068588].
[0055] According to the Landolt-Bornstein database, NbCoSi exists in the orthorhombic phase, while NbCoSn exists in the half-Heusler phase; TaCoSi exists in the orthorhombic phase, while TaCoSn exists in the half-Heusler phase; TiNiSi exists in the orthorhombic phase, while TiNiSn exists in the half-Heusler phase; and VCoSi exists in the orthorhombic phase, while VCoSn exists in the half-Heusler phase. In various embodiments, however, the half-Heusler phase of NbCoSi.sub.1-xSn.sub.x, TaCoSi.sub.1-xSn.sub.x, TiNiSi.sub.1-xSn.sub.x, and VCoSi.sub.1-xSn.sub.x alloys are stable at particular values of x. While the above alloys are described herein in detail, the reader should appreciate that in some embodiments, other X and Y compounds, such as those discussed above, are mixed with the Si and Sn to form semiconductor elements having the desired thermoelectric properties.
[0056]
[0057] As can be seen from
[0058] In some embodiments of the thermoelectric module 200 in which the n-type semiconductor legs 204 are formed of the NbCoSi.sub.1-xSn.sub.x alloy (also referred to as the NbCo alloy), the alloy is doped with a fraction y of Sb replacing the Sn and Si in amounts proportional to x. In such embodiments, the chemical formula for the n-type semiconductor legs 204 is:
NbCoSi.sub.[(1-x)(1-y)]Sn.sub.[x(1-y)]Sb.sub.y.
In embodiments of the n-type semiconductor legs 204 formed from the NbCo alloy, the doping amount y is between 0.002 and 0.03.
[0059] In embodiments of the thermoelectric module in which the p-type semiconductor legs 208 are formed of the NbCo alloy, the alloy is doped with a fraction of Ti replacing a portion of the Nb. The chemical formula for the p-type semiconductor legs 208 is
Nb.sub.1-yCoSi.sub.1-xSn.sub.xTi.sub.y.
In some embodiments of the p-type semiconductor legs 208 formed from the NbCo alloy, the doping amount is between 0.02 and 0.06.
[0060] In one particular embodiment, the molar fraction x in the NbCoSi.sub.1-xSn.sub.x alloy is between 0.27 and 0.75, while in another particular embodiment x is between 0.27 and 0.5, and in another embodiment x is between 0.27 and 0.35. In one particular embodiment of the NbCoSi.sub.1-xSn.sub.x alloy, x is between 0.27 and 0.28.
[0061] As seen in
[0062] In other embodiments, one or both of the n-type and p-type semiconductor legs 204 and 208, respectively, are formed of TaCoSi.sub.1-xSn.sub.x, TiNiSi.sub.1-xSn.sub.x, or VCoSi.sub.1-xSn.sub.x alloys.
[0063] It can be seen from
TABLE-US-00002 TABLE 2 Half-Heusler, Orthorombic, Pnma F-43m (216) (62) NbCoSi.sub.1xSn.sub.x Stable at x >0.27 Stable at x <0.27 TaCoSi.sub.1xSn.sub.x Stable at x >0.21 Stable at x <0.21 TiNiSi.sub.1xSn.sub.x Stable at x >0.36 Stable at x <0.36 VCoSi.sub.1xSn.sub.x Stable at x >0.27 Stable at x <0.27
[0064] In some embodiments the n-type semiconductor legs 204 are formed of TaCoSi.sub.1-xSn.sub.x doped with a fraction of Sb y, which replaces a Sn and Si in amounts proportional to x. In such embodiments, the chemical formula for the n-type semiconductor legs 204 is:
TaCoSi.sub.[(1-x)(1-y)]Sn.sub.[x(1-y)]Sb.sub.y
In one embodiment, the fraction y of Sb doped in the n-type semiconductor legs 204 is 0.02.
[0065] In other embodiments, the p-type doped semiconductor legs 208 are formed of TaCoSi.sub.1-xSn.sub.x doped with a fraction of Ti, which replaces a portion of the Ta. The chemical formula for the p-type semiconductor legs 208 is:
Ta.sub.1-yCoSi.sub.1-xSn.sub.xTi.sub.y
In one embodiment, fraction y of Ti doped in the p-type semiconductor legs 208 is between 0.05 and 0.06.
[0066] In one embodiment in which the n-type and/or the p-type semiconductor legs 204 and 208, respectively, are formed of TaCoSi.sub.1-xSn.sub.x, the molar fraction x of Sn to Si in TaCoSi.sub.1-xSn.sub.x is between 0.21 and 0.75. In another particular embodiment, x is between 0.21 and 0.5, and in another embodiment x is between 0.21 and 0.35. In one particular embodiment of TaCoSi.sub.1-xSn.sub.x, the molar fraction x is between 0.21 and 0.22.
[0067] In another embodiment, the n-type semiconductor legs and/or the p-type semiconductor legs 204 and 208, respectively, are formed of TiNiSi.sub.1-xSn.sub.x. In one embodiment, the molar fraction x in TiNiSi.sub.1-xSn.sub.x is between 0.36 and 0.75, while in another particular embodiment x is between 0.36 and 0.5, and in another embodiment x is between 0.36 and 0.40. In one specific embodiment of TiNiSi.sub.1-xSn.sub.x, the molar fraction x is between 0.36 and 0.37.
[0068] In a further embodiment, the n-type semiconductor legs and/or the p-type semiconductor legs 204 and 208, respectively, are formed of VCoSi.sub.1-xSn.sub.x. In one embodiment, the molar fraction x in VCoSi.sub.1-xSn.sub.x is between 0.27 and 0.75, while in another particular embodiment x is between 0.27 and 0.5, and in another embodiment x is between 0.27 and 0.35. In one embodiment of VCoSi.sub.1-xSn.sub.x, x is between 0.27 and 0.28.
[0069] Alloying the Si and Sn in the above compounds also results in increased mass order scattering in the alloys. Mass order scattering is a result of the disorder due to the random distribution of the Si and Sn atoms through the alloy. Increased mass disorder scattering reduces the lattice part of the thermal conductivity (.sub.lat), which results in increased ZT.
[0070] The alloys for the semiconductor legs 204, 208 of the thermoelectric elements 200 are formed using known powder metallurgy processes. In one particular embodiment, nanopowders are mixed in the molar proportions required to produce the desired alloy and subsequently pressed using a hot-press method so as to produce the semiconductor elements. The production of the semiconductor elements is described in further detail in Joshi, Giri et al. Enhancement in Thermoelectric Figure-Of-Merit of an N-Type Half-Heusler Compound by the Nanocomposite Approach. Advanced Energy Materials, vol. 1, no. 4, p. 643, 2011, the contents of which are hereby incorporated by reference in their entirety.
[0071] It will be appreciated that variants of the above-described and other features and functions, or alternatives thereof, may be desirably combined into many other different systems, applications or methods. Various presently unforeseen or unanticipated alternatives, modifications, variations or improvements may be subsequently made by those skilled in the art that are also intended to be encompassed by the foregoing disclosure.