High voltage lithium ion positive electrode material
A positive electrode material having a nominal stoichiometry Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2 where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10 and x is within a range of 0≤x≤0.2. The use of double compositional modification to LiCoPO 4 increases the discharge capacity from ˜100 mAh/g to about 130 mAh/g while retaining the discharge capacity retention of the singly Fe-substituted LiCoPO 4 . Additional compositional modification to include Si increases the cycle life and greatly improved the coulombic efficiency to between 97-100% at a C/3 cycle rate.
1. A positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a covalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10, x is within a range of 0<x≤0.20, z is within a range of 0≤z≤0.10 and d is within a range of 0≤d≤0.20;
said Li-ion positive electrode material having an initial capacity of at least 120 mAh/g.
2. The positive electrode material of claim 1 , wherein x within the range of 0.08≤x≤0.12.
3. The positive electrode material of claim 1 , wherein 0.02≤y≤0.08.
4. The positive electrode material of claim 1 , wherein d=0.
5. The positive electrode material of claim 1 , wherein z=0.
6. The positive electrode material of claim 1 , wherein z is within a range of 0<z≤0.1.
7. The positive electrode material of claim 6 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.
8. A high voltage lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10, x is within a range of 0.08≤x≤0.12, z is within a range of 0≤z≤0.10 and d is within a range of 0≤d≤0.20;
said Li-ion positive electrode material having a discharge capacity of at least 100 mAhg −1 after 500 cycles.
9. The positive electrode material of claim 8 , wherein 0.02≤y≤0.08.
10. The positive electrode material of claim 8 , wherein d=0.
11. The positive electrode material of claim 8 , wherein z=0.
12. The positive electrode material of claim 8 , wherein z is within a range of 0<z≤0.1.
13. The positive electrode material of claim 12 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.
14. A lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10, x is within a range of 0≤x≤0.20, z is within a range of 0<z≤0.10 and d is within a range of 0≤d≤0.20;
said Li-ion positive electrode material having a discharge capacity of at least 80% of its initial discharge capacity after 500 cycles.
15. The positive electrode material of claim 14 , wherein x within the range of 0.08≤x≤0.12.
16. The positive electrode material of claim 14 , wherein 0.02≤y≤0.08.
17. The positive electrode material of claim 14 , wherein d=0.
18. The positive electrode material of claim 14 , wherein z=0.
19. The positive electrode material of claim 14 , wherein z is within a range of 0<z≤0.1.
20. The positive electrode material of claim 19 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.
21. A high voltage lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10, x is within a range of 0≤x≤0.20, z is within a range of 0≤z≤0.10and d is within a range of 0≤d≤0.20;
said Li-ion positive electrode material having a discharge capacity of at least 100 mAhg −1 after 500 cycles.
22. The positive electrode material of claim 21 , wherein 0.02≤y≤0.08.
23. The positive electrode material of claim 21 , wherein d=0.
24. The positive electrode material of claim 21 , wherein z=0.
25. The positive electrode material of claim 21 , wherein z is within a range of 0<z≤0.1.
26. The positive electrode material of claim 25 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.
27. A high voltage lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0.02≤y≤0.08, x is within a range of 0≤x≤0.20, z is within a range of 0≤z ≤0.10 and d is within a range of 0≤d≤0.20;
said Li-ion positive electrode material having a discharge capacity of at least 100 mAhg −1 after 500 cycles.
28. The positive electrode material of claim 27 , wherein x within the range of 0.08≤x≤0.12.
29. The positive electrode material of claim 27 , wherein d=0.
30. The positive electrode material of claim 27 , wherein z=0.
31. The positive electrode material of claim 27 , wherein z is within a range of 0<z≤0.1.
32. The positive electrode material of claim 31 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.
33. A high voltage lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, y is within a range of 0<y≤0.10, x is within a range of 0≤x≤0.20, and z is within a range of 0≤z≤0.10;
said Li-ion positive electrode material having a discharge capacity of at least 100 mAhg −1 after 500 cycles.
34. The positive electrode material of claim 33 , wherein x within the range of 0.08≤x≤0.12.
35. The positive electrode material of claim 33 , wherein 0.02≤y≤0.08.
36. The positive electrode material of claim 33 , wherein z=0.
37. The positive electrode material of claim 33 , wherein z is within a range of 0<z≤0.1.
38. The positive electrode material of claim 36 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.
39. A high voltage lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10, x is within a range of 0≤x≤0.20, and d is within a range of 0≤d ≤0.20;
said Li-ion positive electrode material having a discharge capacity of at least 100 mAhg −1 after 500 cycles.
40. The positive electrode material of claim 39 , wherein x within the range of 0.08≤x≤0.12.
41. The positive electrode material of claim 39 , wherein 0.02≤y≤0.08.
42. The positive electrode material of claim 39 , wherein d=0.
43. A high voltage lithium ion positive electrode material comprising:
a Li-ion positive electrode material having a nominal stoichiometry of:
Li 1+y/2 Co 1−x−y−z−d Si z Fe x M y M′ d (PO 4 ) 1+y/2
where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10, x is within a range of 0≤x≤0.20, z is within a range of 0<z≤0.1 and d is within a range of 0≤d≤0.20;
said Li-ion positive electrode material having a discharge capacity of at least 100 mAhg −1 after 500 cycles.
44. The positive electrode material of claim 43 , wherein x within the range of 0.08≤x≤0.12.
45. The positive electrode material of claim 43 , wherein 0.02≤y≤0.08.
46. The positive electrode material of claim 43 , wherein d=0.
47. The positive electrode material of claim 43 , wherein said Li-ion positive electrode material has a coulombic efficiency between 97-100% at a C/3 cycle rate.