Lithium-ion-conducting materials
View Patent ↗Lithium-ion-conducting ceramic materials are disclosed having characteristics of high lithium-ion conductivity at low temperatures, good current efficiency, and stability in water and corrosive media under static and electrochemical conditions. Some general formulas for the lithium-ion-conducting materials include M I 1+x+z−δ M III x M IVa y M IVb 2−x−y M V z P 3−z O 12 and M I 1+x+4z−δ M III x M IVa y M IVb 2−x−y−z P 3 O 12 , wherein M I comprises Li, Na, or mixtures thereof; 0.05<x<0.5, 0.05<y<2, 0≦z<3, and 0≦δ<0.5; M III comprises Al, Hf, Sc, Y, La, or mixtures thereof; M IVa comprises Zr, Ge, Sn, or mixtures thereof; M IVb comprises Ti; and M V comprises Si, Ge, Sn, or mixtures thereof. In some cases, the lithium-ion conducting materials are formed through a process in which the materials' powdered precursors are milled after being calcined and before being sintered. The milling process may include using milling media of multiple sizes.
1. A lithium ion conducting ceramic material having the general formulation:
M I 1+x+z−δ M III x M IVa y M IVb 2−x−y M V z P 3−z O 12
wherein M I comprises Li, Na, or a mixture thereof;
wherein 0.05<x<0.5, 0.05<y<2, 0≦z<3, 0<δ<0.5;
wherein M III comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein M IVa comprises Zr, Ge, Sn, or mixtures thereof;
wherein M IVb comprises Ti; and
wherein M V comprises Si, Ge, Sn, or mixtures thereof.
2. The lithium ion conducting ceramic material according to claim 1 , wherein 0<z<3.
3. The lithium ion conducting ceramic material according to claim 1 , wherein M I comprises Li.
4. The lithium ion conducting ceramic material of claim 1 , wherein M III comprises Al.
5. The lithium ion conducting ceramic material of claim 1 , wherein M IVa comprises Zr.
6. The lithium ion conducting ceramic material of claim 1 , wherein M V comprises Si.
7. The lithium ion conducting ceramic material of claim 1 , wherein M I comprises Li, wherein M III comprises Al, wherein M IVa comprises Zr, and wherein M V comprises Si.
8. A lithium ion conducting ceramic material having the general formulation:
M I 1+x+4z−δ M III x M IVa y M IVb 2−x−y−z P 3 O 12
wherein M I comprises Li, Na, or mixtures thereof;
wherein 0.05<x<0.5, 0.05<y<2, 0≦z<3, 0<δ<0.5;
wherein M III comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein M IVa comprises Zr, Ge, Sn, or mixtures thereof; and
wherein M IVb comprises Ti.
9. The lithium ion conducting ceramic material according to claim 8 , wherein 0<z<3.
10. The lithium ion conducting ceramic material of claim 8 , wherein 0.05≦x≦0.45.
11. The lithium ion conducting ceramic material of claim 8 , wherein 0.05≦y≦0.4.
12. The lithium ion conducting ceramic material of claim 8 , wherein M I comprises Li.
13. The lithium ion conducting ceramic material of claim 8 , wherein M III comprises Al.
14. The lithium ion conducting ceramic material of claim 8 , wherein the material is substantially devoid of M IVa .
15. A lithium ion conducting ceramic material having the general formulation selected from (i)
M I 1+x+z−δ M III x M IVa y M IVb 2−x−y M V z P 3−z O 12
and (ii)
M I 1+x+4z−δ M III x M IVa y M IVb 2−x−y−z P 3 O 12 ,
wherein M I comprises Li, Na, or mixtures thereof;
wherein 0.05<x<0.5, 0.05<y<2, 0≦z<3, 0<δ<0.5;
wherein M III comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein M IVa comprises Zr, Ge, Sn, or mixtures thereof;
wherein M IVb comprises Ti;
M V comprises Si, Ge, Sn, or mixtures thereof; and
wherein the lithium ion conducting ceramic material is hermetic to helium gas.
16. The lithium ion conducting ceramic material of claim 15 , wherein the ceramic material is produced through a process in which powdered precursors of the material are milled for over 80 hours, after being calcined and before being sintered.
17. The lithium ion conducting ceramic material of claim 16 , wherein the milling process includes using a first size of milling media and a second size of milling media that is large than the first size of milling media.
18. The lithium ion conducting ceramic material of claim 17 , wherein the first size of milling media comprises a diameter between about 3 mm and about 7 mm in diameter.
19. The lithium ion conducting ceramic material of claim 17 , wherein the second size of milling media comprises a diameter between about 8 mm and about 12 mm in diameter.
20. A lithium ion conducting ceramic material having the general formulation:
M I 1+x+4z−δ M III x M IVa y M IVb 2−x−y−z P 3 O 12
wherein M I comprises Li;
wherein 0≦x≦0.5, 0≦y≦2, 0≦z≦3, 0<δ≦1;
wherein M III comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein M IVa comprises Zr, Ge, Sn, or mixtures thereof; and
wherein M IVb comprises Ti.
21. A lithium ion conducting ceramic material having the general formulation:
M I 1+x+4α−β M III x M IVa y M IVb 2−x−y−α M V z P 3−z O 12
wherein M I comprises Li;
wherein 0.05≦x≦0.5, 0.05≦y≦2, 0≦z≦1, 0.05<α≦0.5, 0<β≦1;
wherein M III comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein M IVa comprises Zr, Ge, Sn, or mixtures thereof;
wherein M IVb comprises Ti. and
wherein M V comprises Si, Ge, Sn, or mixtures thereof.