Positive electrode active materials with composite coatings for high energy density secondary batteries and corresponding processes

Abstract

A composite coated form of lithium cobalt oxide is described that can achieve improved cycling at higher voltages. Liquid phase and combined liquid and solid phase coating processes are described to effectively form the composite coated powders. The improved cycling positive electrode materials can be effectively combined with either graphitic carbon negative electrode active materials or silicon based high capacity negative electrode active materials. Improved battery designs can achieve very high volumetric energy densities in practical battery formats and with reasonable cycling properties.

What is claimed is: 
     
       1. A particulate material comprising a core of lithium cobalt oxide, a partial coating with domains of a lithium manganese nickel cobalt oxide, and a distinct inert stabilization nanocoating, and having from about 2 weight percent to about 19 weight percent lithium manganese nickel cobalt oxide evaluated according to weight of added metal during coating formation. 
     
     
       2. The particulate material of  claim 1  wherein the material comprises from about 1 weight percent to about 35 weight percent lithium manganese nickel cobalt oxide approximately represented by the formula Li 1+b Ni α Mn β Co γ A δ O 2−z F z , b ranges from −0.15 to about 0.3, α ranges from about 0.1 to about 0.4, β ranges from about 0.2 to about 0.65, γ ranges from about 0 to about 0.46, δ ranges from about 0 to about 0.15, and z ranges from 0 to about 0.2, and where A is Na, K, Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, W, Si, Li or combinations thereof, and from about 0.05 weight percent to about 8 weight percent inert stabilization coating. 
     
     
       3. The particulate material of  claim 2  wherein where α+β+γ+δ˜1−b, α ranges from about 0.1 to about 0.3, β range from about 0.3 to about 0.65, γ ranges from about 0.05 to about 0.4, z=0 and δ=0. 
     
     
       4. The particulate material of  claim 2  wherein b ranges from 0.01 to 0.1. 
     
     
       5. The particulate material of  claim 1  having from about 3 weight percent to about 15 weight percent lithium manganese nickel cobalt oxide. 
     
     
       6. The particulate material of  claim 1  having an average particle size from about 5 microns to about 30 microns. 
     
     
       7. The particulate material of  claim 1  comprising from about 0.05 weight percent to about 8 weight percent inert stabilization coating. 
     
     
       8. The particulate material of  claim 1  comprising from about 0.2 weight percent to about 2 weight percent inert stabilization coating. 
     
     
       9. The particulate material of  claim 1  wherein the inert stabilization coating comprises from 1 to 6 atomic deposited layers. 
     
     
       10. The particulate material of  claim 1  wherein the inert stabilization coating comprises a metal halide. 
     
     
       11. The particulate material of  claim 1  wherein the inert stabilization coating comprises aluminum halide. 
     
     
       12. The particulate material of  claim 1  wherein the inert stabilization coating comprises an inert metal oxide. 
     
     
       13. The particulate material of  claim 1  wherein the inert stabilization coating comprises aluminum zinc oxide. 
     
     
       14. The particulate material of  claim 1  having a specific discharge capacity against lithium of at least about 170 mAh/g discharged from 4.52V to 3V at a rate of C/3. 
     
     
       15. A cell comprising:
 a cathode comprising an active material comprising the particulate material of  claim 1 , wherein the cathode tested against a lithium foil electrode exhibits a discharge specific capacity of at least about 185 mAh/g at a rate of C/3 cycled between 4.52V and 3V; 
 an anode comprising a lithium intercalation/alloying compound; and 
 a nonaqueous electrolyte comprising lithium ion, 
 
       the cell cycling between about 4.47V and 2.5V with a discharge specific capacity at the 100th cycle at a rate of C/3 that is at least about 85% of the 5th cycle discharge capacity. 
     
     
       16. The cell of  claim 15  wherein the anode comprises graphite. 
     
     
       17. The cell of  claim 16  having a discharge specific capacity at the 250th cycle at a rate of C/3 that is at least about 80% of the 5th cycle discharge capacity. 
     
     
       18. The cell of  claim 15  wherein the anode comprises silicon oxide. 
     
     
       19. The cell of  claim 18  having a discharge capacity at the 150th cycle that is at least about 80% of the 5th cycle discharge capacity when cycled from the 5th cycle to the 150th cycle at a discharge rate of C/3 from 4.4V to 2.5. 
     
     
       20. The cell of  claim 18  having a specific energy of at least about 335 Wh/kg and an energy density of at least about 840 Wh/L. 
     
     
       21. The cell of  claim 15  wherein the articulate material has from about 0.05 weight percent to about 8 weight percent inert stabilization coating. 
     
     
       22. The cell of  claim 21  wherein the lithium manganese nickel cobalt oxide is approximately described by the formula Li 1+b Ni α Mn β Co γ A δ O 2−z F z , where b ranges from −0.15 to about 03, α ranges from about 0.1 to about 0.4, β ranges from about 0.2 to about 0.65, γ ranges from about 0 to about 0.46, δ ranges from about 0 to about 0.15, and z ranges from 0 to about 0.2, and where A is Na, K, Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, W, Si, Li or combinations thereof. 
     
     
       23. A cell comprising:
 a cathode comprising an active material comprising the particulate material of  claim 1 ; 
 an anode comprising silicon oxide; and 
 a nonaqueous electrolyte comprising lithium ion, 
 
       the cell having a specific energy of at least about 275 Wh/kg and an energy density of at least about 750 Wh/L wherein the cathode and anode are wound together separated by a separator or the cell comprises a plurality of the cathodes and a plurality of the anodes in an electrode stack. 
     
     
       24. The cell of  claim 23  having a discharge capacity at the 150th cycle that is at least about 80% of the 5th cycle discharge capacity when cycled from the 5th cycle to the 150th cycle at a discharge rate of C/3 from 4.4V to 2.5. 
     
     
       25. A method for forming a particulate composite coated material, the method comprising:
 annealing a combination of a manganese nickel cobalt precursor, a lithium source and lithium cobalt oxide powder to form a lithium manganese nickel cobalt oxide coated lithium cobalt oxide particles wherein the manganese nickel cobalt precursor is a coating on the lithium cobalt oxide formed by co-precipitating the manganese nickel cobalt precursor in a dispersion of lithium cobalt oxide and wherein the annealing is performed with a first heating step to a temperature from about 300° C. to about 700° C. to form a metal oxide composition and a second heating step to a temperature from about 750° C. to about 1200° C.; and 
 coating the lithium manganese nickel cobalt oxide coated lithium cobalt oxide particles with an inert inorganic stabilization nanocoating to form composite coated stabilized lithium cobalt oxide particles, 
 wherein the particulate composite coated material has from about 2 weight percent to about 19 weight percent lithium manganese nickel cobalt oxide. 
 
     
     
       26. The method of  claim 25  wherein the manganese nickel cobalt precursor compound comprises a hydroxide or a carbonate. 
     
     
       27. The method of  claim 25  wherein the manganese nickel cobalt precursor compound comprises a hydroxide or a carbonate, and the annealing is performed in a single heating step from about 700° C. to about 1200° C. for from about 6 hours to about 48 hours. 
     
     
       28. The method of  claim 25  wherein the material comprises from about 1 weight percent to about 35 weight percent lithium manganese nickel cobalt oxide approximately represented by the formula Li 1+b Ni α Mn β Co γ A δ O 2−z F z , where b ranges from −0.15 to about 0.3, α ranges from about 0.1 to about 0.4, β ranges from about 0.2 to about 0.65, γ ranges from about 0 to about 0.46, δ ranges from about 0 to about 0.15, and z ranges from 0 to about 0.2, and where A is Na, K, Mg, Sr, Ba, Cd, Zn, Al G, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, W, Si, Li or combinations thereof, and from about 0.05 weight percent to about 8 weight percent inert stabilization coating. 
     
     
       29. A lithium ion cell comprising:
 an anode comprising a lithium intercalation or allying active composition;   a cathode comprising an active composition comprising a particulate material of lithium cobalt oxide, polymer binder, and an electrically conductive particles, the cathode having a specific capacity cycled against lithium foil electrode of at least 170 mAh/g discharged from 4.52V to 3V at a rate of C/3; and   a non-aqueous electrolyte comprising lithium ions,   where in the lithium ion cell can be cycled for at least 300 cycles between 4.47V and 3V at a discharge rate of C/3 without a drop of more than 20% of the capacity from the 5th cycle capacity.   
     
     
       30. The lithium ion cell of claim 29 wherein the anode comprises a silicon based active material. 
     
     
       31. The lithium ion cell of claim 30 wherein the anode comprises silicon oxide. 
     
     
       32. The lithium ion cell of claim 30 wherein the anode comprises a silicon oxide/silicon/carbon composite. 
     
     
       33. The lithium ion cell of claim 30 wherein the anode comprises from 5 wt % to 55 wt % graphite. 
     
     
       34. The lithium ion cell of claim 29 wherein the anode comprises graphite. 
     
     
       35. The lithium ion cell of claim 29 wherein the positive electrode having a specific capacity cycled against lithium metal of at least 185 mAh/g discharged from 4.52V to 3V at a rate of C/3. 
     
     
       36. The lithium ion cell of claim 29 wherein the lithium cobalt oxide is doped. 
     
     
       37. The lithium ion cell of claim 29 wherein the lithium cobalt oxide is coated. 
     
     
       38. The lithium ion cell of claim 29 having a specific energy of at least about 320 Wh/kg. 
     
     
       39. The lithium ion cell of claim 29 having an energy density of at least about 780 Wh/L. 
     
     
       40. The lithium ion cell of claim 29 wherein the electrolyte comprises fluoroethylene carbonate. 
     
     
       41. The lithium ion cell of claim 29 where in the lithium ion cell can be cycled for at least 375 cycles between 4.47V and 3V at a discharge rate of C/3 without a drop of more than 20% of the capacity from the 5th cycle capacity.