Thermoelectric materials based on tetrahedrite structure for thermoelectric devices
View Patent ↗Thermoelectric materials based on tetrahedrite structures for thermoelectric devices and methods for producing thermoelectric materials and devices are disclosed. The thermoelectric device has a pair of conductors and a p-type thermoelectric material disposed between the conductors. The thermoelectric material is at least partially formed of a hot pressed high energy milled tetrahedrite formed of tetrahedrite ore and pure elements to form a tetrahedrite powder of Cu12-xMxSb4S13 disposed between the conductors, where M is at least one of Zn and Fe.
1. A method of forming a thermoelectric device, the method comprising:
high energy milling a natural tetrahedrite ore with a powder selected from the group consisting of elemental Cu, elemental Sb, elemental S, and combinations thereof to form a tetrahedrite composition having a stoichiometric ratio of Cu 12-x M x Sb 4-y As y S 13 , wherein M is a transition metal, 0<x<2.0, and 0=<y=<4.0; and
placing a layer of the tetrahedrite composition between a pair of thermal conductors.
2. The method of forming a thermoelectric device according to claim 1 , wherein the layer of tetrahedrite comprises Cu 12-x M x Sb 4 S 13 ; with M being selected from the group consisting of Zn at a concentration 0<x<2.0 or Fe at a concentration between 0<x<1.5, or combinations thereof.
3. The method of forming a thermoelectric device according to claim 1 , wherein the tetrahedrite comprises Cu 12-x M x Sb 4-y As y S 13 where M is selected from the group consisting of Ag, Zn, Fe, Mn, Hg or combinations thereof.
4. The method of forming a thermoelectric device according to claim 1 , comprising tellurium (Te) as a portion of the S.
5. A method of forming a thermoelectric device, the method comprising:
making a tetrahedrite powder by high energy milling a natural tetrahedrite ore with a powder material selected from the group consisting of pure elemental Cu, pure elemental Sb, pure elemental S, and combinations thereof to form a powdered material having stoichiometric ratio Cu 12-x M x Sb 4-y As y S 13 , wherein M is a transition metal, 0<x<2.0, and 0=<y=<4.0;
solidifying the powdered material to form solidified tetrahedrite; and
placing a layer of the solidified tetrahedrite between a pair of thermal conductors.
6. The method of forming a thermoelectric device according to claim 5 , wherein the layer of solidified tetrahedrite comprises Cu 12-x M x Sb 4 S 13 ; with 0<x<2.
7. The method of forming a thermoelectric device according to claim 5 , wherein M includes a transition metal selected from the group consisting of Ag, Zn, Fe, Mn, Hg and combinations thereof.
8. The method of claim 1 further comprising:
solidifying the tetrahedrite composition under heat, pressure, or a combination of heat and pressure.
9. The method according to claim 8 , wherein M includes one or more transition metals selected from the group consisting of Ag, Zn, Fe, Hg and Mn.