Thermoelectrically active materials and generators containing them
AssigneeBASF SE
InventorHans-Josef Sterzel
Life of this patent
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Abstract
In a generator comprising a p-doped or n-doped semiconductor material, said semiconductor material is at least one ternary material selecting from one of the following substance classes and formed by combining at least two compounds of the substance class: suicides, borides, germanides, tellurides, sulfides, selenides, antimonides, plumbides and semiconductor oxides.
Claims10
A thermoelectric generator comprising a p-doped or n-doped semiconductor material, wherein said semiconductor material is at least one ternary material selected from one of the following substance classes and formed by combining at least 2 compounds of the substance class:
- (1) Silicides
- U3Si5, BaSi2, CeSi2, GdSi, NdSi2, CoSi, CoSi2, CrSi2, FeSi, FeSi2, MnSi, MoSi2, WSi2, VSi, TiSi2, ZrSi2, VSi2, NbSi2 and TaSi2
- (2) Borides
- UB2, UB4, UB12, CeB6, AlB12, CoB, CrB2, CrB4, FeB, MnB, MnB2, MnB12, MoB, MoB4, SiB4, SiB6, SiB12, TiB2, VB2, YB4, ZrB2, CuB24, NiB12, BaB6, MgB2, MgB4 and MgB12, where the aluminum-containing borides may additionally contain one carbon atom per boron atom,
- (3) Germanides
- U5Ge3, BaGe, GdGe, Dy5Ge3, Fr5Ge3 and Ce3Ge5
- (4) Tellurides, sulfides and selenides
- LaS, NdS, Pr2S3, DyS, USe, BaSe, GdSe, LaSe, Nd3Se4, Nd2Se3, PrSe, FrSe, UTe, GdTe, LaTe, NdTe, PrTe, SmTe, DyTe and ErTe
- (5) Antimonides
- USb, CeSb, GdSb, LaSb, NdSb, PrSb, DySb, AlSb, CeSb, CrSb, FeSb, Mg3Sb2, Ni5Sb2, CeSb3 and NiSb3
- (6) Plumbides
- CePb, Gd5Pb3, La5Pb3 and Dy5Pb4,
- where, in the substance classes (1) to (6), up to 10 atom % of the elements may be replaced by Na, K, Rb, Cs, Zn, Cd, Al, Ga, Zr, Mg, S, Cu, Ag, Au, Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni or mixtures thereof, providing they are not already present in the combinations,
- (7) Semiconductor oxides
- UO2, Bi2O3, CuO, Cu2O, SnO, PbO, ZnO, In2O3, WO3, V2O5, Sb2O3, CoO, NiO, Ce2O4, FeO, Fe2O3, NbO2, CeO2 and BaO,
- where up to 10 mol % of the oxides may be replaced by Na2O, K2O, CdO, SrO, Al2O3, Ga2O3, Cr2O3 or mixtures thereof, and
- wherein ternary suicides formed by combining CrSi2 and FeSi2 are of formula
- CrxFe1−xSi1+x
- wherein x is from 0.01 to 0.99.
A thermoelectric generator comprising a p-doped or n-doped semiconductor material, wherein the semiconductor material is formed by combining and reacting from 30 to 50% by weight of one or more of semiconductor-forming elements selected from the group consisting of B, Si, Ge, Sb, Bi, S, Se and Te with from 50 to 70% by weight of one or more elements selected from the group consisting of Al, Fe, Ni, Co, Zn, Cd, Ti, Zr, Y, Cu, V, Mo, W, Mn, Nb, Ta and U.
A semiconductor material wherein said semiconductor material is at least one ternary material selected from one of the following substance classes and formed by combining at least 2 compounds of the substance class:
- (1) Silicides
- U3Si5, BaSi2, CeSi2, GdSi, NdSi2, CoSi, CoSi2, CrSi2, FeSi, FeSi2, MnSi, MoSi2, WSi2, VSi, TiSi2, ZrSi2, VSi2, NbSi2 and TaSi2
- (2) Borides
- UB2, UB4, UB12, CeB6, AlB12, CoB, CrB2, CrB4, FeB, MnB, MnB2, MnB12, MoB, MoB4, SiB4, SiB6, SiB12, TiB2, VB2, YB4, ZrB2, CuB24, NiB12, BaB6, MgB2, MgB4, and MgB12, wherein the aluminum-containing borides may additionally contain one carbon atom per boron atom,
- (3) Germanides
- UCGe3, BaGe, GdGe, Dy5Ge3, Fr5Ge3 and Ce3Ge5
- (4) Tellurides, sulfides, and selenides
- LaS, NdS, Pr2S3, DyS, USe, BaSe, GdSe, LaSe, Nd3Se4, Nd2Se3, PrSe, FrSe, UTe, GdTe, LaTe, NdTe, PrTe, SmTe, DyTe and ErTe
- (5) Antimonides
- USb, CeSb, GdSb, LaSb, NdSb, PrSb, DySb, AlSb, CeSb, CrSb, FeSb, MN3Sb2, Ni5Sb2, CeSb3 and NiSb3
- (6) Plumbides
- CePb, Gd5Pb3, La5Pb3 and Dy5Pb4
- wherein, in the substance classes (1) to (6), up to 10 atom % of the elements may be replaced by Na, K, Rb, Cs, Zn, Cd, Al, Ga, Zr, Mg, S, Cu, Ag, Au, Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni or mixtures thereof, providing they are not already present in the combination,
- (7) Semiconductor oxides
- UO2, Bi2O3, CuO, Cu2O, SnO, PbO, ZnO, In2O3, WO3, V2O5, Sb2O3, CoO, NiO, Ce2O4, FeO, Fe2O3, NbO2, CeO2 and BaO, where up to 10 mol % of the oxides may be replaced by Na2O, K2O, CdO, SrO, Al2O3, Ga2O3, Cr2O3 or mixtures thereof, and wherein the silicides formed by combining CrSi2 and FeSi2 are of formula
- CrxFe1−xSi1+x
- wherein x is form 0.01 to 0.99.
A process for combinatorial preparation and testing of semiconductor materials for thermoelectric generators, wherein the semiconductor materials are ternary materials selected from one of the following substance classes and formed by combining at least 2 compounds of the substance class:
- (1) Silicides
- U3Si5, BaSi2, CeSi2, GdSi, NdSi2, CoSi, CoSi2, CrSi2, FeSi, FeSi2, MnSi, MoSi2, WSi2, VSi, TiSi2, ZrSi2, VSi2, NbSi2 and TaSi2
- (2) Borides
- UB2, UB4, UB12, CeB6, AlB12, CoB, CrB2, CrB4, FeB, MnB, MnB2, MnB12, MOB, MoB4, SiB4, SiB6, SiB12, TiB2, VB2, YB4, ZrB2, CUB24, NiB12, BaB6, MgB2, MgB4 and MgB12, where the aluminum-containing borides may additionally contain one carbon atom per boron atom,
- (3) Germanides
- U5Ge3, BaGe, GdGe, Dy5Ge3, Fr5Ge3 and Ce3Ges
- (4) Tellurides, sulfides and selenides
- LaS, NdS, Pr2S3, DyS, USe, BaSe, GdSe, LaSe, Nd3Se4, Nd2Se3, PrSe, FrSe, UTe, GdTe, LaTe, NdTe, PrTe, SmTe, DyTe and ErTe
- (5) Antimonides
- USb, CeSb, GdSb, LaSb, NdSb, PrSb, DySb, AlSb, CeSb, CrSb, FeSb, Mg3Sb2, Ni5Sb2, CeSb3 and NiSb3
- (6) Plumbides
- CePb, Gd5Pb3, La5Pb3 and Dy5Pb4,
- where, in the substance classes (1) to (6), up to 10 atom % of the elements may be replaced by Na, K, Rb, Cs, Zn, Cd, Al, Ga, Zr, Mg, S, Cu, Ag, Au, Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni or mixtures thereof, providing they are not already present in the combinations,
- (7) Semiconductor oxides
- UO2, Bi2O3, CuO, Cu2O, SnO, PbO, ZnO, In2O3, WO3, V2O5, Sb2O3, CoO, NiO, Ce2O4, FeO, Fe2O3, NbO2, CeO2 and BaO,
- where up to 10 mol % of the oxides may be replaced by Na2O, K2O, CdO, SrO, A12O3, Ga2O3, Cr2O3 or mixtures thereof, which comprises producing an array of dots of the semiconductor materials of different composition on a conductive sheet substrate, bringing the substrate carrying the array to a desired measuring temperature and contacting each of the dots with a cooled measuring pin, the voltage without load, current and voltage at decreasing load resistance and/or short-circuit current being measured, subsequently stored and analyzed.
A process for combinatorial preparation and testing of semiconductor materials for thermoelectric generators, wherein the semiconductor materials are ternary materials selected from one of the following substance classes and formed by combining at least 2 compounds of the substance class:
- (1) Silicides
- U3Si5, BaSi2, CeSi2, GdSi, NdSi2, CoSi, CoSi2, CrSi2, FeSi, FeSi2, MnSi, MoSi2, WSi2, VSi, TiSi2, ZrSi2, VSi2, NbSi2 and TaSi2
- (2) Borides
- UB2, UB4, UB12, CeB6, AlBl2, CoB, CrB2, CrB4, FeB, MnB, MnB2, MnB12, MOB, MoB4, SiB4, SiB6, SiB12, TiB2, VB2, YB4, ZrB2, CuB24, NiB12, BaB6, MgB2, MgB4 and MgB12, where the aluminum-containing borides may additionally contain one carbon atom per boron atom,
- (3) Germanides
- U5Ge3, BaGe, GdGe, Dy5Ge3, Fr5Ge3 and Ce3Ge5
- (4) Tellurides, sulfides and selenides
- LaS, NdS, Pr2S3, DyS, USe, BaSe, GdSe, LaSe, Nd3Se4, Nd2Se3, PrSe, FrSe, UTe, GdTe, LaTe, NdTe, PrTe, SmTe, DyTe and ErTe
- (5) Antimonides
- USb, CeSb, GdSb, LaSb, NdSb, PrSb, DySb, AlSb, CeSb, CrSb, FeSb, Mg3Sb2, Ni5Sb2, CeSb3 and NiSb3
- (6) Plumbides
- CePb, Gd5Pb3, La5Pb3 and Dy5Pb4,
- where, in the substance classes (1) to (6), up to 10 atom % of the elements may be replaced by Na, K, Rb, Cs, Zn, Cd, Al, Ga, Zr, Mg, S, Cu, Ag, Au, Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni or mixtures thereof, providing they are not already present in the combinations,
- (7) Semiconductor oxides
- UO2, Bi2O3, CuO, Cu2O, SnO, PbO, ZnO, In2O3, WO3, V2O5, Sb2O3, CoO, NiO, Ce2O4, FeO, Fe2O3, NbO2, CeO2 and BaO,
- where up to 10 mol % of the oxides may be replaced by Na2O, K2O, CdO, SrO, A12O3, Ga2O3, Cr2O3 or mixtures thereof, which comprises producing an array of dots of the semiconductor materials of different composition on a conductive sheet substrate, contacting the dots on the side located opposite the substrate with a conductive nonmagnetic plate and maintaining the substrate and the plate at different temperatures and electrically connecting them, the plate being scanned by means of a magnetic field probe and the measuring data being stored and analyzed.
An array consisting of at least 10 different semiconductor materials on a conductive substrate, wherein the semiconductor materials are ternary materials selected from one of the following substance classes and formed by combining at least 2 compounds of the substance class:
- (1) Silicides
- U3Si5, BaSi2, CeSi2, GdSi, NdSi2, CoSi, CoSi2, CrSi2, FeSi, FeSi2, MnSi, MoSi2, WSi2, VSi, TiSi2, ZrSi2, VSi2, NbSi2 and TaSi2
- (2) Borides
- UB2, UB4, UB12, CeB6, AlB12, CoB, CrB2, CrB4, FeB, MnB, MnB2, MnB12, MoB, MoB4, SiB4, SiB6, SiB12, TiB2, VB2, YB4, ZrB2, CuB24, NiB12, BaB6, MgB2, MgB4 and MgB12, where the aluminum-containing borides may additionally contain one carbon atom per boron atom,
- (3) Germanides
- U5Ge3, BaGe, GdGe, Dy5Ge3, Fr5Ge3 and Ce3Ge5
- (4) Tellurides, sulfides and selenides
- LaS, NdS, Pr2S3, DyS, USe, BaSe, GdSe, LaSe, Nd3Se4, Nd2Se3, PrSe, FrSe, UTe, GdTe, LaTe, NdTe, PrTe, SmTe, DyTe and ErTe
- (5) Antimonides
- USb, CeSb, GdSb, LaSb, NdSb, PrSb, DySb, AlSb, CeSb, CrSb, FeSb, Mg3Sb2, Ni5Sb2, CeSb3 and NiSb3
- (6) Plumbides
- CePb, Gd5Pb3, La5Pb3 and Dy5Pb4,
- where, in the substance classes (1) to (6), up to 10 atom % of the elements may be replaced by Na, K, Rb, Cs, Zn, Cd, Al, Ga, Zr, Mg, S, Cu, Ag, Au, Ti, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni or mixtures thereof, providing they are not already present in the combinations,
- (7) Semiconductor oxides
- UO2, Bi2O3, CuO, Cu2O, SnO, PbO, ZnO, In2O3, WO3, V2O5, Sb2o3, CoO, NiO, Ce2O4, FeO, Fe2O3, NbO2, CeO2 and BaO,
- where up to 10 mol % of the oxides may be replaced by Na2O, K2O, CdO, SrO, Al2O3, Ga2O3, Cr2O3 or mixtures thereof.
Dependencies are inferred from the claim text.