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. Process for preparing an at least partially lithiated transition metal oxyanion-based lithium-ion reversible electrode material, which comprises
providing a precursor of said lithium-ion reversible electrode material,
heating said precursor,
melting same at a temperature sufficient to produce a liquid phase comprising an at least partially lithiated transition metal oxyanion, and
cooling said liquid phase under conditions to induce solidification of an at least partially lithiated transition metal oxyanion electrode material in a pure, partially substituted or doped form,
wherein said solid electrode material is reduced to powder form or agglomerate of particles by high-energy wet ball milling.
2. A process according to claim 1 , wherein prior to said high-energy milling, said process comprises pre-milling said solid electrode material to produce about millimeter size powder.
3. A process according to claim 1 , wherein said high-energy wet ball milling is performed with milling balls having a size of about 3 to about 20 mm.
4. A process according to claim 1 , wherein said high-energy wet ball milling is performed with zirconia milling balls.
5. A process according to claim 1 , wherein said high-energy wet ball milling is performed with milling balls, using a solid electrode material:balls ratio (wt./wt.) of about 0.4:1 to about 17:1.
6. A process according to claim 1 , wherein said high-energy wet ball milling is performed for a time duration of about 10 minutes to about 90 minutes.
7. A process according to claim 1 , wherein said solid electrode material is reduced to a powder having an individual mean particle size between 20 nanometers and 5 microns and agglomerate mean particle size between 100 nanometers and 15 microns.
8. A process according to claim 7 , which comprises externally treating the individual particles or agglomerates by chemically or mechanically applying carbon (C) or other chemical additive used in a battery.
9. A process according to claim 1 , wherein said lithium-ion reversible electrode material has the nominal formula AB(XO 4 )H, wherein
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.
10. A process according to claim 9 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
11. A process according to claim 9 , wherein A is lithium.
12. A process according to claim 9 , 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.
13. A process according to claim 9 , 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.
14. A process according to claim 9 , wherein XO 4 is PO 4 .
15. A process according to claim 9 , wherein said lithium-ion reversible electrode material has the nominal formula AB(XO 4 ).
16. A process according to claim 9 , wherein said lithium-ion reversible electrode material has the nominal formula AB(PO 4 ).
17. A process according to claim 9 , wherein said lithium-ion reversible electrode material has the nominal formula LiB(PO 4 ).
18. 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 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.
19. The electrode material according to claim 18 , wherein the other metal at oxidation level +2 is Mg.
20. The electrode material according to claim 19 , comprising about 2% of Mg (wt./total wt. of B).
21. The electrode material according to claim 18 , comprising at least about 70% of Fe (wt./total wt. of B).
22. The electrode material according to claim 18 , comprising at least about 20% of Mn (wt./total wt. of B).
23. The electrode material according to claim 18 , wherein A is lithium, partially substituted with another alkali metal representing less than 20% at. of said A.
24. The electrode material according to claim 18 , wherein A is lithium.
25. The electrode material according to claim 18 , wherein XO 4 is PO 4 .
26. The electrode material according to claim 18 , having the nominal formula Li(Fe,Mn,Mg)PO 4 .
27. A pure, partially substituted or doped lithium-ion reversible electrode material having the nominal formula LiB(PO 4 ) in which B is a mixture of redox metals at oxidation level of +2 comprising Fe, Mn and Mg.
28. The electrode material according to claim 18 , having a pyrolytic carbon deposit.
29. The electrode material according to claim 26 , having a pyrolytic carbon deposit.
30. The electrode material according to claim 27 , having a pyrolytic carbon deposit.
31. A cathode electrode comprising the electrode material according to claim 28 .
32. A cathode electrode comprising the electrode material according to claim 29 .
33. A cathode electrode comprising the electrode material according to claim 30 .