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 pure, partially substituted or doped lithium-ion reversible electrode material 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 mixtures 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 combinations thereof; and
H is a fluoride, hydroxide or chloride anion representing less that 35% at. of the XO 4 oxyanion, including 0,
wherein said material comprises less than about 7% (wt./wt.), excluding 0, of a compound selected from the group consisting of Li 3 PO 4 , Li 4 P 2 O 7 , Li 8 P 8 O 24 , Li 6 P 6 O 18 , LiFeP 2 O 7 , LiFe 5 O 8 , Fe 2 O 3 and any combinations thereof.
2. The electrode material according to claim 1 , wherein said material comprises less than about 5% of a compound selected from the group consisting of Li 3 PO 4 , Li 4 P 2 O 7 , Li 8 P 8 O 24 , Li 6 P 6 O 18 , LiFeP 2 O 7 , LiFe 5 O 8 , Fe 2 O 3 and any combinations thereof.
3. The electrode material according to claim 1 , wherein said material comprises less than about 2% of a compound selected from the group consisting of Li 3 PO 4 , Li 4 P 2 O 7 , Li 8 P 8 O 24 , Li 6 P 6 O 18 , LiFeP 2 O 7 , LiFe 5 O 8 , Fe 2 O 3 and any combinations thereof.
4. The electrode material according to claim 1 , wherein said material comprises less than about 1% of Li 3 PO 4 .
5. The electrode material according to claim 1 , wherein said material comprises less than about 1.7% of Li 4 P 2 O 7 .
6. The electrode material according to claim 1 , wherein said material comprises less than about 1% of Li 4 P 2 O 7 .
7. 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.
8. The electrode material according to claim 1 , wherein A is lithium.
9. The electrode material according to claim 1 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni, and any mixtures 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.
10. The electrode material according to claim 1 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni, and any mixtures thereof.
11. The electrode material according to claim 1 , wherein XO 4 is PO 4 .
12. The electrode material according to claim 1 having the nominal formula LiFePO 4 .
13. The electrode material according to claim 1 , having the nominal formula AB(XO 4 ).
14. The electrode material according to claim 1 , having the nominal formula AB(PO 4 ).
15. The electrode material according to claim 1 , having the nominal formula AB(XO 4 ), wherein B comprises at least 65% at. of a transition metal selected from Fe, Mn and mixtures thereof.
16. The electrode material according to claim 1 , having the nominal formula AB(PO 4 ) wherein B comprises at least 65% at. of a transition metal selected from Fe, Mn and mixtures thereof.
17. The electrode material according to claim 1 , having a pyrolytic carbon deposit.
18. The electrode material according to claim 12 , having a pyrolytic carbon deposit.
19. A cathode electrode comprising the electrode material according to claim 17 .
20. A cathode electrode comprising the electrode material according to claim 18 .
21. A pure, partially substituted or doped lithium-ion reversible electrode material 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 mixtures 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 combinations thereof; and
H is a fluoride, hydroxide or chloride anion representing less that 35% at. of the XO 4 oxyanion, including 0,
wherein said material comprises less than about 1500 ppm, excluding 0, of sulfur content.
22. The electrode material according to claim 21 , wherein said material comprises less than about 500 ppm of sulfur content.
23. The electrode material according to claim 21 , wherein said material comprises less than about 100 ppm of sulfur content.
24. The electrode material according to claim 21 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
25. The electrode material according to claim 21 , wherein A is lithium.
26. The electrode material according to claim 21 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni, and any mixtures 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.
27. The electrode material according to claim 21 , wherein B is a main redox metal at oxidation level of +2 selected from the group consisting of Fe, Mn, Ni, and any mixtures thereof.
28. The electrode material according to claim 21 , wherein XO 4 is PO 4 .
29. The electrode material according to claim 21 having the nominal formula LiFePO 4 .
30. The electrode material according to claim 21 , having the nominal formula AB(XO 4 ).
31. The electrode material according to claim 21 , having the nominal formula AB(PO 4 ).
32. The electrode material according to claim 21 , having the nominal formula AB(XO 4 ), wherein B comprises at least 65% at. of a transition metal selected from Fe, Mn and mixtures thereof.
33. The electrode material according to claim 21 , having the nominal formula AB(PO 4 ) wherein B comprises at least 65% at. of a transition metal selected from Fe, Mn and mixtures thereof.
34. The electrode material according to claim 21 , having a pyrolytic carbon deposit.
35. The electrode material according to claim 29 , having a pyrolytic carbon deposit.
36. A cathode electrode comprising the electrode material according to claim 34 .
37. A cathode electrode comprising the electrode material according to claim 35 .
38. A pure, partially substituted or doped lithium-ion reversible electrode material having the nominal formula AB(XO 4 )H in which:
A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A;
B is a mixture of redox metals at oxidation level of +2 comprising Fe, Mn, and another metal at oxidation level +2;)
XO 4 is any oxyanion wherein X is selected from the group consisting of P, S, V, Si, Nb, Mo, and any combinations thereof; and
H is a fluoride hydroxide or chloride anion representing less that 35% at. of XO 4 including 0.
39. The electrode material according to claim 38 , wherein XO 4 is PO 4 .
40. The electrode material according to claim 38 , having a pyrolytic carbon deposit.
41. A cathode electrode comprising the electrode material according to claim 40 .