Process for preparing electroactive insertion compounds and electrode materials obtained therefrom
View Patent ↗A process for preparing an at least partially lithiated transition metal oxyanion-based lithium-ion reversible electrode material, which includes providing a precursor of said lithium-ion reversible electrode material, heating said precursor, melting same at a temperature sufficient to produce a melt including an oxyanion containing liquid phase, cooling said melt under conditions to induce solidification thereof and obtain a solid electrode that is capable of reversible lithium ion deinsertion/insertion cycles for use in a lithium battery. Also, lithiated or partially lithiated oxyanion-based-lithium-ion reversible electrode materials obtained by the aforesaid process.
1. A lithium-ion reversible electrode material, said material said material having a particle size distribution comprising micron size particles and submicron size particles, wherein said particles have an about 1.23 wt % pyrolytic carbon deposit on at least a part of the surface thereof, said micron size particles and submicron size particles having the nominal formula AB(XO 4 )H in which:
A is lithium, which may be partially substituted with another alkali metal representing less than 20% at. of said A;
B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, which may be partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0;
XO 4 is any oxyanion wherein X is selected from the group consisting of P, S, V, Si, Nb, Mo and any combination thereof; and
H is a fluoride, hydroxide or chloride anion representing less that 35% at. of the XO 4 oxyanion, including 0.
2. The electrode material according to claim 1 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
3. The electrode material according to claim 2 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0.
4. The electrode material according to claim 1 , wherein said micron size particles have a particle size distribution that includes a plurality of micron sizes.
5. The electrode material according to claim 1 , wherein said submicron size particles have a particle size distribution that includes a plurality of submicron sizes.
6. The electrode material according to claim 1 , wherein said micron size particles have a particle size distribution that includes a plurality of micron sizes and said submicron size particles have a particle size distribution that includes a plurality of submicron sizes.
7. The electrode material according to claim 1 , wherein said electrode material has the nominal formula LiFePO 4 .
8. The electrode material according to claim 6 , wherein said electrode material has the nominal formula LiFePO 4 .
9. The electrode material according to claim 1 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
10. The electrode material according to claim 6 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
11. The electrode material according to claim 8 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
12. The electrode material according to claim 1 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
13. The electrode material according to claim 6 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
14. The electrode material according to claim 8 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
15. The electrode material according to claim 1 , wherein said particles have a mean size of about 1.5 μm.
16. The electrode material according to claim 1 , wherein said particles have a mean size of about 1 μm to about 5 μm.
17. A lithium-ion reversible electrode material, comprising particles having a mean size of about 1 nm to about 5 nm, and having an about 1.23 wt % pyrolytic carbon deposit on at least a part of the surface thereof, said particles having the nominal formula AB(XO 4 )H in which:
A is lithium, which may be partially substituted with another alkali metal representing less than 20% at. of said A;
B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, which may be partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0;
XO 4 is any oxyanion wherein X is selected from the group consisting of P, S, V, Si, Nb, Mo and any combination thereof; and
H is a fluoride, hydroxide or chloride anion representing less that 35% at. of the XO 4 oxyanion, including 0.
18. The electrode material according to claim 17 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
19. The electrode material according to claim 18 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0.
20. The electrode material according to claim 17 , wherein said particles have a particle size distribution that includes a plurality of micron sizes.
21. The electrode material according to claim 17 , wherein said particles have a particle size distribution that includes a plurality of submicron sizes.
22. The electrode material according to claim 17 , wherein said particles have a particle size distribution that includes a plurality of micron sizes and a plurality of submicron sizes.
23. The electrode material according to claim 17 , wherein said electrode material has the nominal formula LiFePO 4 .
24. The electrode material according to claim 22 , wherein said electrode material has the nominal formula LiFePO 4 .
25. The electrode material according to claim 17 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
26. The electrode material according to claim 22 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
27. The electrode material according to claim 24 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
28. The electrode material according to claim 17 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
29. The electrode material according to claim 22 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
30. The electrode material according to claim 24 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
31. The electrode material according to claim 17 , wherein said particles have a mean size of about 1.5 μm.
32. A lithium-ion reversible electrode material, comprising particles having an about 1.5 μm mean size, and an about 1.23 wt % pyrolytic carbon deposit on at least a part of the surface thereof, said particles having the nominal formula AB(XO 4 )H in which:
A is lithium, which may be partially substituted with another alkali metal representing less than 20% at. of said A;
B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, which may be partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0;
XO 4 is any oxyanion wherein X is selected from the group consisting of P, S, V, Si, Nb, Mo and any combination thereof; and
H is a fluoride, hydroxide or chloride anion representing less that 35% at. of the XO 4 oxyanion, including 0.
33. The electrode material according to claim 32 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
34. The electrode material according to claim 33 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0.
35. The electrode material according to claim 32 , wherein said particles have a particle size distribution that includes a plurality of micron sizes.
36. The electrode material according to claim 32 , wherein said particles have a particle size distribution that includes a plurality of submicron sizes.
37. The electrode material according to claim 32 , wherein said particles have a particle size distribution that includes a plurality of micron sizes and a plurality of submicron sizes.
38. The electrode material according to claim 32 , wherein said electrode material has the nominal formula LiFePO 4 .
39. The electrode material according to claim 37 , wherein said electrode material has the nominal formula LiFePO 4 .
40. The electrode material according to claim 32 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
41. The electrode material according to claim 37 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
42. The electrode material according to claim 39 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
43. The electrode material according to claim 32 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
44. The electrode material according to claim 37 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
45. The electrode material according to claim 39 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
46. A composition comprising a conductive agent, a binder and a lithium-ion reversible electrode material, said material comprising particles having an about 1.23 wt % pyrolytic carbon deposit on at least a part of the surface thereof, wherein said composition has a density of at least about 1.7 g/cm 3 , said particles having the nominal formula AB(XO 4 )H in which:
A is lithium, which may be partially substituted with another alkali metal representing less than 20% at. of said A;
B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, which may be partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0;
XO 4 is any oxyanion wherein X is selected from the group consisting of P, S, V, Si, Nb, Mo and any combination thereof; and
H is a fluoride, hydroxide or chloride anion representing less that 35% at. of the XO 4 oxyanion, including 0.
47. The composition according to claim 46 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
48. The composition according to claim 47 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni and any mixture thereof, partially substituted by one or more additional metal at oxidation level between +1 and +5 and representing less than 35% at. of said main +2 redox metal, including 0.
49. The composition according to claim 46 , wherein said particles have a particle size distribution that includes a plurality of micron sizes.
50. The composition according to claim 46 , wherein said particles have a particle size distribution that includes a plurality of submicron sizes.
51. The composition according to claim 46 , wherein said particles have a particle size distribution that includes a plurality of micron sizes and a plurality of submicron sizes.
52. The composition according to claim 46 , wherein said electrode material has the nominal formula LiFePO 4 .
53. The composition according to claim 51 , wherein said electrode material has the nominal formula LiFePO 4 .
54. The composition according to claim 46 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
55. The composition according to claim 51 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
56. The composition according to claim 53 , wherein said material has a particle size distribution comprising up to 40% of submicron size particles.
57. The composition according to claim 46 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
58. The composition according to claim 51 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.
59. The composition according to claim 53 , wherein said material has a particle size distribution comprising up to 60% of micron size particles.