Lithiated transition metal oxides
Process for the fabrication of an electrode structure comprising an electrochemically active material suitable for use in an energy storage device. The method includes electrodepositing the electrochemically active material onto an electrode in electrodeposition bath containing a non-aqueous electrolyte. The electrode structure can be used for various applications such as electrochemical energy storage devices including high power and high-energy lithium-ion batteries.
1. A cathode structure comprising a conformal coating of a lithiated transition metal oxide material formed by co-depositing via electrodeposition from a lithium source and a transition metal source on a substrate immersed in a non-aqueous electrolyte.
2. The cathode structure of claim 1 , wherein the cathode structure comprises a composite structure having anopen pore porous structure.
3. The cathode structure of claim 2 , wherein the composite structure has a void volume fraction (porosity) of at least 95%.
4. The cathode structure of claim 2 , wherein the composite structure is an open cell porous structure comprising unit cells having an average size in a range of 10 nm to 100 μm.
5. A primary or secondary battery comprising the cathode structure according to claim 1 .
6. The primary or secondary battery of claim 5 , wherein the cathode structure comprises the conformal coating of the lithiated transition metal oxide material on a metal current collector.
7. The cathode structure of claim 1 , wherein the substrate is selected from the group consisting of metals, metal alloys, ceramics, conductive oxides, carbon and all allotropes thereof, electrically conductive polymers, and electrically conductive composite materials.
8. The cathode structure of claim 7 , wherein the substrate comprises a metals or metal alloy selected from the group consisting of aluminum, copper, chromium, cobalt, manganese, nickel, silver, gold, tin, platinum, palladium, zinc, tungsten, tantalum, rhodium, molybdenum, titanium, iron, zirconium, vanadium, hafnium, and the alloys thereof.
9. The cathode structure of claim 8 , wherein the substrate is aluminum or alloy thereof.
10. The cathode structure of claim 7 , wherein the substrate comprises a ceramic selected from the group consisting of borides, carbide, and silicides.
11. The cathode structure of claim 10 , wherein the substrate comprises a ceramic selected from the group consisting of titanium boride, hafnium boride, magnesium boride, chromium boride, vanadium boride, aluminum boride, tungsten carbide, titanium carbide, chromium carbide, molybdenum carbide, hafnium carbide, tantalum carbide, vanadium carbide, tungsten silicide, titanium silicide, vanadium silicide, nickel silicide, platinum silicide, chromium silicide, copper silicide, and zirconium silicide.
12. The cathode structure of claim 7 , wherein the substrate comprises a conductive oxide selected from the group consisting of indium tin oxide, fluorinated tin oxide, and combinations thereof.
13. The cathode structure of claim 7 , wherein the substrate comprises any one of carbon and allotropes thereof, selected from the group consisting of conductive carbon particles, carbon nanotubes, carbon fibers, fullerenes, graphene, graphite, glassy carbon, and pyrolitic carbon.
14. The cathode structure of claim 7 , wherein the substrate comprises electrically conductive polymers selected from the group consisting of polyaniline, polyacetylene and polypyrrole.
15. The cathode structure of claim 7 , wherein the substrate comprises electrically conductive composite materials comprising polymeric materials containing a sufficient amount of a conductive filler material in the shape of particles, fibers, or sheets, the conductive filler material comprising any one of the carbon and allotropes thereof.
16. The cathode structure of claim 1 , wherein the conformal coating has a thickness in the range of 1 nm to 50 μm.
17. The cathode structure of claim 1 , wherein the conformal coating has a thickness in the range of 100 nm to 10 μm.
18. The cathode structure of claim 1 , wherein the conformal coating has a thickness in the range of 10 nm to 100 μm.
19. The cathode structure of claim 1 , wherein a thickness of the conformal coating has a variation of less than 20% of an average thickness value.
20. The cathode structure of claim 1 , wherein a thickness of the conformal coating has a variation of less than 10% of an average thickness value.
21. The cathode structure of claim 1 , wherein the cathode structure comprises a composite structure comprising the conformal coating of the lithiated transition metal oxide material electrodeposited on a carbon scaffold.
22. The cathode structure of claim 21 , wherein the carbon scaffold consists of a single layer carbon scaffold.
23. The cathode structure of claim 1 , wherein the cathode structure comprises a monolithic open porous structure.
24. The cathode structure of claim 1 , wherein the cathode structure is formed by electrodepositing the lithiated transition metal oxide material from the non-aqueous electrolyte at a temperature in excess of the melting temperature of the non-aqueous electrolyte.
25. The cathode structure of claim 1 , wherein the cathode structure comprising the conformal coating of the lithiated transition metal oxide material is formed by removing the electrodeposited lithiated transition metal oxide material from the substrate, combining the lithiated transition metal oxide material with a conductive material and binder to form a mixture, and applying the mixture to a current collector.
26. The cathode structure of claim 1 , wherein the lithiated transition metal oxide material has the formula Li x M y O n , where x is greater than 0 and less than 1.2, y is 0.5 to 1, n is 1.5 to 2.5, and the ratio (2n−x)/y ranges from 2.5 to 3.7, and where M comprises one or more metals selected from the group consisting of Ti, V, Cr, Mn, Co, Ni, Mo, W, Zr, Mg, Al, Cu, Fe, and Zn.
27. The cathode structure of claim 26 , wherein M comprises one or more metals selected from the group consisting of Co, Ni, and Mn.
28. The cathode structure of claim 1 , wherein the lithiated transition metal oxide material comprises LiCoO 2 , LiMnO 2 , lithiated nickel oxide, or LiNi a Mn b Co 1-a-b O 2 where a is greater than 0 and less than 1, b is greater than 0 and less than 1, and a+b is greater than 0 and less than 1.
29. The cathode structure of claim 1 , wherein the transition metal source is selected from the group consisting of nitrates, nitrites, sulfates, halides, hydroxides, oxides, alkoxides and acetates of a transition metal.
30. The cathode structure of claim 29 , wherein the transition metal comprises cobalt and the transition metal source comprises CoO, Co 2 O 3 , Co(OH) 2 , Co 3 O 4 , CoCl 2 , CoSO 4 , Co(NO 3 ) 2 , Co(NO 2 ) 2 , Co(C 2 H 3 O 2 ) 2 .
31. The cathode structure of claim 29 , wherein the transition metal comprises manganese and the transition metal source comprises MnCl 2 , MnSO 4 , Mn(CH 3 COO) 2 , Mn(NO 3 ) 2 , or Mn(NO 2 ) 2 .
32. The cathode structure of claim 29 , wherein the transition metal comprises nickel and the transition metal source comprises NiCl 2 , NiSO 4 , Ni(CH 3 COO) 2 , Ni(NO 3 ) 2 , or Ni(NO 2 ) 2 .
33. The cathode structure of claim 1 , wherein the source of lithium comprises a lithium containing molten salt comprising any one or more of LiOH, LiF, LiCl, LiBr, LiI, LiNO 3 , LiNO 2 , and Li 2 SO 4 .
34. The cathode structure of claim 1 , wherein the substrate has a thickness of at least 1 micron.
35. The cathode structure of claim 34 , wherein the substrate has a thickness of at least 10 microns.