Source: https://patents.justia.com/patent/10658560
Timestamp: 2020-07-03 11:10:26
Document Index: 365086475

Matched Legal Cases: ['Application No. 61', 'Application No. 2015', 'Application No. 13740424', 'Application No. 2015', 'Application No. 14820390', 'Application No. 2013800360335', 'Application No. 2013800360335', 'Application No. 2013286602', 'Application No. 14820390', 'Application No. 2016', 'Application No. 13740424', 'Application No. 14820390', 'Application No. 2016', 'Application No. 14820390', 'Application No. 13740424', 'Application No. 2']

US Patent for Thermoelectric materials based on tetrahedrite structure for thermoelectric devices Patent (Patent # 10,658,560 issued May 19, 2020) - Justia Patents Search
Justia Patents US Patent for Thermoelectric materials based on tetrahedrite structure for thermoelectric devices Patent (Patent # 10,658,560)
May 24, 2017 - Board of Trustees of Michigan State University
This application is a continuation of U.S. patent application Ser. No. 14/413,196, filed Jan. 6, 2015 (now U.S. Pat. No. 9,673,369); which is a National Stage Entry of PCT/US2013/049350, filed Jul. 3, 2013; which claims the benefit of U.S. Provisional Application No. 61/668,766, filed Jul. 6, 2012. The entire disclosures of each of the above applications are incorporated herein by reference.
This invention was made with government support under DE-SC0001054 awarded by the U.S. Department of Energy. The government has certain rights in the invention.
According to another teaching, a thermoelectric device is provided having a pair of conductors and a layer of tetrahedrite disposed between the pair of conductors. The tetrahedrite comprises Cu12-xMxSb4-yAsyS13 where M is selected from the group consisting of Ag, Zn, Fe, Mn, Hg and combinations thereof; 0<x<2; and 0≤y<4.
According to another teaching a thermoelectric material is presented formed of sintered tetrahedrite having Cu12-xMxSb4-yAsyS13. M is selected from the group of Zn at a concentration 0<x<2.0, Fe at a concentration 0<x<1.5, and combinations thereof, and 0≤y<4.
FIG. 3a total lattice thermal conductivities of Cu12-xZnxSb4S13, where circles represent x=0, squares represent x=0.5, triangles represent x=1, and diamonds represent x=1.5;
FIG. 3b represents lattice thermal conductivities of Cu12-xZnxSb4S13, where circles represent x=0, squares represent x=0.5, triangles represent x=1, and diamonds represent x=1.5;
FIG. 4a represents the dimensionless thermoelectric figure of merit ZT as a function of temperature for tetrahedrite Cu12-xZnxSb4S13, where circles represent x=0, squares represent x=0.5, triangles represent x=1, and diamonds represent x=1.5;
FIGS. 12-13 represent various material properties for Cu12-xZnxSb4S13 where x is 0, 0.5, 1, and 1.5;
FIGS. 14-15 represent various material properties for Cu12-xFexSb4S13, where x is 0, 0.2, 0.5, and 0.7; and
FIG. 16 shows a Brillouin zone model for tetrahedrite Cu12-xMxSb4.09S13, Cu12-xMxSb4S13, where M is Fe or Zn and x is 2, or Cu12-xMxSb4S13, where M is Fe or Zn and has a Brillouin zone occupation fraction of 0-1.
Example embodiments will now be described more fully with reference to the accompanying drawings. Thermoelectric materials can convert waste heat into electricity, potentially improving the efficiency of energy usage in both industry and everyday life. Unfortunately, known good thermoelectric materials often are comprised of elements that are in low abundance and/or toxic, and frequently require careful doping and complex synthesis procedures. Here, high thermoelectric figure of merit in compounds of the form Cu12-xTMxSb4S13, where TM is a transition metal, such as Zn or Fe, and 0<x<2. In these compounds the dimensionless figure of merit reaches 0.9 around 673K, comparable to that of other state of art p-type thermoelectric materials in the same temperature range. Importantly, the figure of merit remains high for a wide range of values of x. The subject compositions are among those that form the class of natural minerals known as tetrahedrites. Thermoelectrics comprised of earth-abundant elements will pave the way to many new, low cost thermoelectric energy generation opportunities.
Described below in detail is the synthesis and measurement of the thermoelectric properties of tetrahedrite-based compounds. Generally, pure Cu12Sb4S13 exhibits a ZT value of 0.56 at 673K (400° C.). This pure 12-4-13 composition does not occur in natural minerals. Rather, natural tetrahedrite is of typical composition Cu12-x MxSb4S13 and is a very commonly occurring sulfosalt, found quite typically with M=Zn and Fe. The most common substitution elements are Zn and Fe on Cu sites, up to 15% in the natural mineral ZT values of up to 0.91 near 673 K in Cu12-x (Zn,Fe)xSb4S13 with x=0-1.5 and x=0-0.7 for Zn and Fe, respectively have been measure. This result highlights the potential of directly using natural tetrahedrite minerals as source thermoelectric materials, without the need for time and energy consuming synthetic procedures or precise doping.
Pure Cu12Sb4S13 and compounds with substitution of Fe and Zn on the Cu site were synthesized using a vacuum, annealing, and hot-pressing procedure. The samples are single phase and at a density of ≥95%, and preferably ≥98% theoretical density. FIG. 2a shows the electrical resistivity of Cu12-xZnxSb4S13 in the temperature range 373 K 673 K with x ranging from 0 to 1.5, with circles representing x=0; squares representing x=0.5, triangles representing x=1, and diamonds representing x=1.5. FIGS. 2a-4b share these indicators. The low temperature resistivity shows semiconductor-like characteristics but it cannot be fit with a simple activated behavior; rather, the conductivity behavior is more consistent with a hopping-type mechanism. Attempts to measure hole concentration using the Hall effect proved unsuccessful; even in large field a Hall coefficient RH close to zero is measured. In terms of the crystal-chemical argument given above, this would imply that at least some of the nominally divalent Cu ions are in a monovalent or mixed valent state, giving rise to a partially filled Brillouin zone and metallic behavior.
In order to understand the relationship between filling of the Brillouin-zone and the resulting ZT values, the notion of the occupation fraction of the Brillouin-zone: occupation fraction=number of substituting atoms*contributed electrons/2. For example, for x=0.5 Fe substitution, the fraction is 0.5 while for x=0.5 Zn substitution, the fraction is 0.25. FIG. 4b displays the relationship between occupation fraction and the measured ZT values. For both substitutions, the maximum ZT values are reached at 0.5 and ZT begins to diminish for higher occupation fraction. From this plot, ZT values above 0.6 can be attained over a surprisingly large range of Brillouin zone occupation; high ZT is extremely robust against impurity substitution on the copper site in Cu12Sb4S13, with high values maintained up to occupation fraction of 0.8, even if the substitution is a mixture comprising Fe and Zn.
As shown in FIG. 9, Cu12Sb4S13 samples can be synthesized by direct solid state reaction of the starting elements—Cu (99.99%, Alfa-Aesar), Sb (99.9999%, Alfa-Aesar), and S, Zn, Fe (99.999%, Alfa-Aesar). These raw materials were loaded in stoichiometric ratios into quartz ampoules that were evacuated to <10−5 Torr. The loaded ampoules were then placed into a vertical furnace and heated at 0.3° C. min−1 to 650° C. and held at that temperature for 12 hours. Subsequently, they were slowly cooled to room temperature at the rate of 0.4° C. min−1. The resulting reacted material was placed into a stainless vial and ball milled for five minutes in a SPEX sample preparation machine. These ball-milled powders were then cold pressed into a pellet and re-ampouled under vacuum for annealing for two weeks at 450° C. The final product after annealing was ball milled for 30 minutes into fine powders, hot-pressed under argon atmosphere at 80 MPa pressure and 430° C. for 30 minutes, and sliced. All the hot pressed samples used in this study were greater than 98% theoretical density, as measured using the Archimedes method.
The reacted material was placed into a stainless vial and ball milled for five minutes in a SPEX sample preparation machine. These ball-milled powders were then cold pressed into a pellet and re-ampouled under vacuum for annealing for two weeks at 450° C. It is envisioned the material can be annealed for less time or at a different temperature. The final product after annealing was ball milled for 30 minutes into fine powders and hot-pressed under argon atmosphere at 80 MPa pressure and 430° C. for 30 minutes. All the hot pressed samples used in this study were greater than 98% theoretical density, as measured using the Archimedes method. It is envisioned hot pressed samples can have a theoretical density of ≥95%. Synthesized two batches each of Cu12-xZn2-xSb4S13 and Cu12-xFe2-xSb4S13 samples. The high temperature thermoelectric property results presented herein were all gathered from the same pellet for each of the compositions. For some of the low temperature data, different pellets of the same nominal composition were used.
FIG. 7 shows a plot of conductivity versus T−1, as one might expect for carrier activation, for the Zn-containing samples. The results do not fill well to this model. Rather the data are better-described by a hopping type model. The Fe-containing samples can be described similarly. Low temperature Seebeck coefficients were measured on a series of Zn-containing samples in a flow cryostat using a steady state method. One end of a prism-shaped sample was attached to the cold head of the cryostat, while a small metal film heater/resistor embedded in copper was affixed to the other end. Two copper—constantan thermocouples were attached along the length of the sample to detect the temperature difference dT. The copper legs of the thermocouples were used to measure the Seebeck voltage. Both the high and low temperature Seebeck measurements by also measuring a bismuth telluride Seebeck standard sample (NIST SRM-xxxx), and found differences between measurements and the calibration values of no more than 5% over the range 80-573 K. Low temperature Seebeck measurements for the Zn-containing samples are shown in FIG. 6c. Values near room temperature differ slightly from those shown in FIG. 2c, because the samples measured at low temperature were from a different batch of the same nominal composition. Slight differences in absolute value from sample to sample are expected, because the properties depend on the actual content of Zn.
Compounds of base composition Cu12-xMxSb4S13 with x=Fe, Zn, or Mn and 0<x<2 are synthesized as described below. Briefly, stoichiometric ratios of the desired elements are melted together in a quartz ampoule under vacuum. The resulting ingot is ground into a powder, pressed into a pellet, and annealed. The pellet can be re-ground into a powder and hot pressed into a pellet of density >98%. Compositions with x=0 have low resistivity (10−3 ohm cm at 300 K), modest Seebeck coefficient (75 dV/K at 300 K) and moderately low thermal conductivity (1 W/m/K). Doping with Fe, Zn, or Mn increases both the resistivity and Seebeck coefficient, and substantially lowers the thermal conductivity. Over a wide range of Zn concentration (0<x<2.0 and preferably 0.5<x<1.5) or a wide range of Fe concentration (between 0<x<1.5 and preferably 0.2<x<1.0) the thermoelectric figure of merit remains in the range of 0.6-0.9 at 673 K, similar to or even exceeding that of the best state of the art thermoelectric materials in this temperature range. Importantly, the compositions which exhibit good thermoelectric properties span the range of the widespread natural mineral tetrahedrite compounds Cu12-xMx(Sb,As)4S13 with M=Ag, Zn, Fe, Mn, or Hg. Optionally, tellium can be substituted as a percentage of the S, or Cd can be substituted for Cu at certain fractions. This means that these natural minerals may be used directly or with small compositional modification as source materials for thermoelectric devices once processed into a pelletized or film structure.
FIGS. 12-15 represent material properties for various materials according to the present teachings with 0<x<1.5 (FIGS. 12 and 13) and x=0, 0.2, 0.5, and 0.7 (FIGS. 14 and 15), and FIG. 16 shows Brillouin zone models for tetrahedrite. The potential uses of this teaching are widespread. Thermoelectric devices using this material can be used for converting heat to electricity or electricity to cause a heat gradient. As such, they may be used, for example, to convert waste heat from an automobile engine or other vehicle to useful electrical power. Other potential industry targets include waste heat conversion in power generation (coal- and natural gas-burning power plants), steel production, and in residential/commercial boilers and water heaters. Further, thermoelectric materials are being developed for direct conversion of solar thermal energy to electricity, thereby acting to complement traditional solar cell technology. As shown in FIG. 8, thermoelectric device 98 can have a pair of conductors 100 and a layer of tetrahedrite 102 disposed between the pair of conductors. The layer of tetrahedrite has Cu12-xMxSb4S13, M is selected from the group of Zn, Fe, and combinations thereof. Alternatively with M being selected from the group consisting of Zn at a concentration 0<x<2.0 (FIGS. 12 and 13) or Fe at a concentration between 0<x<1.5 (FIGS. 14 and 15), or combinations thereof.
1. A thermoelectric composition comprising Cu12-xMxSb4-yAsyS13, where M is Zn and 0<x<2, Fe and 0<x<1.5, or a combination thereof, and 0≤y<4.
2. The thermoelectric composition according to claim 1, wherein the composition comprises Cu12-xMxSb4S13.
3. The thermoelectric composition according to claim 1, wherein M is Zn and Fe.
4. The thermoelectric composition according to claim 1, wherein M is Zn and 0<x<2.0.
5. The thermoelectric composition according to claim 1, wherein M is Fe and 0<x<1.5.
6. A method of producing a thermoelectric composition comprising Cu12-xMxSb4S13 where M is Zn and 0<x<2, Fe and 0<x<1.5, or a combination thereof, the method comprising:
preparing a stoichiometric mixture of Cu, Sb, S and at least one of Zn and Fe;
heating the mixture to a temperature of 650° C.;
cooling the mixture at a rate of 0.4° C./min;
ball milling the mixture to form a powder; and
hot pressing the powder to form a pellet comprising the thermoelectric composition.
7. The method according to claim 6, wherein the pellet has a density of greater than 95%.
8. A thermoelectric composition comprising Cu12-xMxSb4S13, where M is Zn at a concentration of 0<x<1.5, at a concentration of 0.2<x<1, or a combination thereof.
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Patent Publication Number: 20170331023
Application Number: 15/604,011
International Classification: H01L 35/16 (20060101); C04B 35/626 (20060101); C04B 35/645 (20060101); C04B 35/547 (20060101); H01L 35/18 (20060101);