Fluorinated cation-disordered rocksalt materials and methods of making thereof

1. A method for manufacturing lithium metal oxyfluoride having a general formula Li 1+x (MM′) z O 2-y F y , wherein 0.6≤z≤0.95, wherein 0<y≤0.67, and wherein 0.05≤x≤0.4, the lithium metal oxyfluoride having a cation-disordered rocksalt structure, comprising:

providing at least one lithium-based precursor;

providing at least one redox-active transition metal-based precursor;

providing at least one redox-inactive transition metal-based precursor;

providing at least one fluorine-based precursor comprising a fluoropolymer; and

mixing the at least one lithium-based precursor, the at least one redox-active transition metal-based precursor, the at least redox-inactive transition metal-based precursor, and the at least one fluorine-based precursor comprising a fluoropolymer to form a mixture.

2. The method of claim 1 , wherein the fluoropolymer is selected from a group consisting of polytetrafluoroethylene (PTFE), fluorinated ethylene propylene (FEP), perfluoroalkoxy (PFA), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), perfluoropolyether (PFPE) tetrafluoroethylene propylene (FEPM), ethylene tetrafluoroethylene (ETFE), polychlorotrifluoroethylene (PCTFE), and polyethylenechlorotrifluoroethylene (ECTFE).

3. The method of claim 1 , wherein the fluoropolymer is polytetrafluoroethylene (PTFE).

4. The method of claim 1 , wherein M is selected from a group consisting of Ni, Mn, Fe, Co, V, Cr, W, Mo, and combinations thereof.

5. The method of claim 1 , wherein M′ is selected from a group consisting of Ti, Zr, Nb, Ta, W, Mo, and combinations thereof.

6. The method of claim 1 , wherein the at least one redox-active transition metal-based precursor is selected from a group consisting of NiO, Ni 2 O 3 , MnO, Mn 2 O 3 , FeO, Fe 2 O 3 , Co 2 O 3 , V 2 O 3 , VO 2 , Cr 2 O 3 , Mo 2 O 3 , W 2 O 3 , and combinations thereof, and wherein the at least one redox-inactive transition metal-based precursor is selected from a group consisting of TiO 2 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 , WO 3 , MoO 3 , and combinations thereof.

7. The method of claim 1 , wherein the at least one lithium-based precursor is selected from a group consisting of Li 2 CO 3 , LiOH, Li 2 O, Li 2 SO 4 , LiCl, LiNO 3 , and combinations thereof.

8. The method of claim 1 , wherein stoichiometric amounts of the at least one lithium-based precursor, the at least one redox-active transition metal-based precursor, the at least redox-inactive transition metal-based precursor, and the at least one fluorine-based precursor comprising a fluoropolymer are mixed, and wherein the lithium-based precursor is added in up to 15% excess of a specified lithium composition.

9. The method of claim 1 , wherein the mixing comprises ball milling.

10. The method of claim 1 , further compromising:

after the mixing, annealing the mixture at about 700° C. to 1200° C. for about 5 hours to 18 hours under an inert atmosphere.

11. The method of claim 1 , wherein the lithium metal oxyfluoride includes about 0.1 weight % to 5 weight % carbon.

12. The method of claim 1 , wherein the lithium metal oxyfluoride is Li 1.2 Mn 0.8 Nb x O 2-y F y , wherein 0≤x≤0.1, and wherein 0.2≤y≤0.4, or wherein the lithium metal oxyfluoride is Li 1+x Mn a Ti b O 2-y F y , wherein 0≤x≤0.4, wherein 0.6<a≤0.9, wherein 0<b≤0.20, and wherein 0<y≤0.2.

13. The method of claim 1 , wherein the lithium metal oxyfluoride is selected from a group consisting of Li 1.2 Mn 0.625 Nb 0.175 O 1.95 F 0.05 (F2.5), Li 1.2 Mn 0.65 Nb 0.15 O 1.9 F 0.1 (F5), Li 1.2 Mn 0.675 Nb 0.125 O 1.85 F 0.15 (F7.5), Li 1.2 Mn 0.7 Nb 0.1 O 1.8 F 0.2 (F10), Li 1.2 Mn 0.725 Nb 0.075 O 1.75 F 0.25 (F12.5), Li 1.2 Mn 0.75 Nb 0.05 O 1.7 F 0.3 (F15), Li 1.2 Mn 0.8 O 1.6 F 0.4 (F20), Li 1.3 Mn 0.7 Ti 0.1 O 1.8 F 0.2 , and Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 .