Thin film coatings on mixed metal oxides
View Patent ↗The invention relates to lithiated mixed metal compositions having ultrathin film coatings of varying thicknesses on lithium ion sites and on metal oxide sites, wherein the thickness of the ultrathin film at least partially covering the metal oxide sites is greater than the thickness of the ultrathin film at least partially covering the lithium ion sites. Also disclosed is a method for forming the compositions, comprising selectively coating one area of a multi-component substrate. Materials such as mixed metal oxides, for use in lithium battery electrodes, may be improved by a coating which preferentially deposits onto one or more elements in the mixed material but not another.
1. A substrate comprising:
a lithiated metal oxide cathode material comprising lithiated metal oxide particles having M-oxide sites and lithium ion sites, wherein M is at least one non-lithium metal;
a first ultrathin film comprising a metal fluoride film, the first ultrathin film having a thickness up to 4 nanometers, the first ultrathin film at least partially covering the M-oxide sites and the lithium ion sites; and
a second ultrathin film comprising a non-lithium-containing metal oxide film, the second ultrathin film having a thickness up to 4 nanometers,
wherein the first ultrathin film and the second ultrathin film are semicontinuous,
wherein a thickness of the first ultrathin film at least partially covering the M-oxide sites is greater than a thickness of the first ultrathin film at least partially covering the lithium ion sites, and
wherein the metal fluoride film comprises one or more of MnF 2 and HfF 4 .
2. The substrate of claim 1 , wherein the thickness of the first ultrathin film or the thickness of the second ultrathin film is up to 3 nanometers.
3. The substrate of claim 1 , wherein the substrate comprises Li exposed on a surface of the substrate.
4. The substrate of claim 1 , wherein the metal fluoride film further comprises at least one of CaF 2 and SrF 2 .
5. The substrate of claim 1 , wherein an average diameter of the lithiated metal oxide particles is from 0.05 micrometers to 60 micrometers and wherein the lithiated metal oxide particles comprise lithium nickel cobalt manganese iron oxide.
6. The substrate of claim 1 , wherein the non-lithium-containing metal oxide film comprises at least one of MgO, Al 2 O 3 , SiO 2 , TiO 2 , ZnO, SnO 2 , ZrO 2 , NbO 3 , and B 2 O 3 .
7. The substrate of claim 1 , wherein the lithiated metal oxide is selected from the group consisting of at least one of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt manganese iron oxide, lithium nickel cobalt aluminum oxide, and lithium titanate.
8. The substrate of claim 1 , wherein the lithiated metal oxide is LiNi 0.33 Mn 0.33 CO 0.33 O 2 .
9. The substrate of claim 1 , wherein the first ultrathin film comprises MnF 2 .
10. The substrate of claim 3 , wherein the thickness of the first ultrathin film ranges from zero to about 3 nanometers.
11. The substrate of claim 1 , wherein the first ultrathin film or the second ultrathin film is deposited by atomic layer deposition (ALD) using from 2 ALD cycles to 11 ALD cycles.
12. The substrate of claim 11 , wherein the first ultrathin film or the second ultrathin film is deposited by atomic layer deposition (ALD) using from 3 ALD cycles to 10 ALD cycles.
13. The substrate of claim 12 , wherein the first ultrathin film or the second ultrathin film is deposited by atomic layer deposition (ALD) using from 3 ALD cycles to 6 ALD cycles.
14. An atomic layer deposition process to prepare the lithiated metal oxide particles of claim 4 , wherein the particles are batch-processed in at least one of a fluidized bed, a rotating tube or cylinder, and a rotating blender.
15. An atomic layer deposition process to prepare the lithiated metal oxide particles of claim 4 , wherein the particles are processed semi-batch or semi-continuously using at least one of sequential fluidized beds, rotating cylinders, and fixed mixers in series to move substrate particles through reaction zones.
16. An atomic layer deposition process to prepare the lithiated metal oxide particles of claim 4 , wherein the particles are agitated and processed continuously and spatially, and move through successive zones where reactant gases and substrate particles are flowed continuously.
17. An atomic layer deposition process to prepare the lithiated metal oxide particles of claim 4 , wherein the process is a vibrating bed process incorporating directional vibration, and wherein a gas velocity is below a minimum fluidization velocity of the particles such that the particles are not fluidized.
18. An atomic layer deposition process to prepare the lithiated metal oxide particles of claim 4 , wherein the process is a vibrating bed process operated in a manner such that a gas velocity is sufficient to fluidize the particles.
19. An electrode comprising the substrate according to claim 1 , wherein the first ultrathin film or the second ultrathin film is deposited by atomic layer deposition (ALD) using from 2 ALD cycles to 4 ALD cycles.
20. The substrate of claim 1 , wherein the first ultrathin film comprises HfF 4 .