THERMOELECTRIC MATERIALS BASED ON TETRAHEDRITE STRUCTURE FOR THERMOELECTRIC DEVICES
Thermoelectric materials based on tetrahedrite structures for thermoelectric devices and methods for producing thermoelectric materials and devices are disclosed.
1 .- 55 . (canceled)
56 . A thermoelectric device comprising:
a pair of conductors; and
a mechanically alloyed tetrahedrite Cu 12-x M x Sb 4-y As y S 13-z Se z disposed between the conductors, wherein M is selected from the group of Zn at a concentration 0<x<2.0, Fe at a concentration 0<x<1.5, and Ni at a concentration 0<x<2.0, where 0≤z<3.0, 0<y<2.0, and combinations thereof.
57 . The thermoelectric device according to claim 56 , comprises
Cu 12-x M x , where M is selected from the group consisting of Ag, Zn, Fe, Mn, Hg, Cd, and combinations thereof.
58 . The thermoelectric device according to claim 56 , comprising a pnictogen.
59 . The thermoelectric device according to claim 58 , wherein the pnictogen comprises Sb, As, and Te.
60 . The thermoelectric device according to claim 56 , comprising a chalcogen.
61 . The thermoelectric device according to claim 56 , wherein the tetrahedrite comprises Cu 12-x M x Sb 4-y As y S 13-z Se z ; with M being selected from the group consisting of Zn at a concentration 0<x<2.0, Fe at a concentration between 0<x<1.5, and combinations thereof.
62 . The thermoelectric device according to claim 56 , wherein the tetrahedrite is a p-type material.
63 . The thermoelectric device according to claim 56 , wherein M is Ni at 0<x<2.0.
64 . The thermoelectric device according to claim 56 , wherein the tetrahedrite comprises Cu 12-x M x Sb 4-y As y S 13-z Se z , where M is selected from the group consisting of Ag, Zn, Fe, Mn, Hg, and combinations thereof.
65 . The thermoelectric device according to claim 61 , comprising tellurium.
66 . The thermoelectric device according to claim 56 , wherein the tetrahedrite is a sintered powder.
67 . The thermoelectric device according to claim 56 , wherein the tetrahedrite is a sintered powder having a density of greater than about 95%.
68 . A thermoelectric material comprising:
sintered tetrahedrite comprising Cu 12-x M x Sb 4-y As y S 13-z Se z , wherein M is selected from the group of Zn at a concentration 0<x<2.0, Fe at a concentration 0<x<1.5, and Ni at a concentration 0<x<2.0, where 0≤z<3.0, 0<y<2.0, and combinations thereof.
69 . The thermoelectric material according to claim 68 , wherein the sintered tetrahedrite further comprises Cu 12-x M x Sb 4-y As y S 13-z Se z , where X is a concentration of 0<x<1.5.
70 . The thermoelectric material according to claim 68 , wherein the sintered tetrahedrite is a sintered powder having a density of greater than about 95% of bulk tetrahedrite.
71 . The thermoelectric material according to claim 68 , wherein M is a combination of Ni and Zn, x is 1.5, y is 0, and z is 0.
72 . The thermoelectric material according to claim 71 , wherein the thermoelectric material is Cu 10.5 Ni 1.3 Zn 0.2 Sb 4 S 13 .
73 . The thermoelectric material according to claim 71 , wherein the thermoelectric material is Cu 10.5 Ni 1.0 Zn 0.5 Sb 4 S 13 .
74 . The thermoelectric material according to claim 71 , wherein the thermoelectric material is Cu 10.5 Ni 0.5 Zn 1.0 Sb 4 S 13 .
75 . A thermoelectric material comprising:
tetrahedrite comprising natural tetrahedrite ore having a first stoichiometric ratio mechanically alloyed with one or more substantially pure powdered elemental materials having a second stoichiometric ratio different from the first stoichiometric ratio to form tetrahedrite powder of Cu 12-x M x Sb 4 S 13-z Se z .
76 . The thermoelectric material according to claim 75 , wherein 0<x<2.0.
77 . The thermoelectric material according to claim 75 , wherein the natural tetrahedrite ore having a first stoichiometric ratio has a weight greater than 50% of a weight of the tetrahedrite powder.
78 . A thermoelectric device comprising:
a pair of conductors;
an n-type material; and
a p-type thermoelectric material disposed between the conductors, the p-type thermoelectric material comprising a solidified tetrahedrite powder of Cu 12-x M x Sb 4-y As y S 13-z Se z disposed between the conductors, the tetrahedrite powder comprising an alloy of a tetrahedrite material and one or more powdered elemental materials, where M includes one or more transition metals.
79 . The thermoelectric device according to claim 78 , wherein M includes one or more elements selected from the group consisting of Ag, Zn, Fe, Hg, Mn, and combinations thereof.
80 . The thermoelectric device according to claim 78 , wherein 0<x<2.0.
81 . A method of producing a thermoelectric device comprising:
mechanically alloying a mixture comprising natural tetrahedrite ore and one or more substantially pure elemental materials to form a tetrahedrite powder of Cu 12-x M x Sb 4-y As y S 13-z Se z , wherein 0<x<2.0, and wherein the tetrahedrite powder includes more than 50% by weight natural tetrahedrite ore and the materials;
solidifying the tetrahedrite powder under heat, pressure, or a combination of heat and pressure to form solidified tetrahedrite; and
disposing the solidified tetrahedrite between a pair of electrical conductors.
82 . The method of producing a thermoelectric device according to claim 81 , wherein the Cu 12-x M x Sb 4-y As y S 13-z Se z has a tetrahedrite crystal structure.
83 . The method of producing a thermoelectric device according to claim 81 , further comprising:
sintering the mixture to form the tetrahedrite powder.
84 . The method of producing a thermoelectric device according to claim 81 , wherein the solidifying comprises hot pressing the tetrahedrite powder to form the solidified tetrahedrite, the solidified tetrahedrite being a pellet having a density greater than 95%.
85 . The method of producing a thermoelectric device according to claim 81 , wherein the solidified tetrahedrite is a p-type material.