Carbon-deposited alkali metal oxyanion electrode material and process for preparing same
The present invention relates to a process for the synthesis of a carbon-deposited alkali metal oxyanion cathode material comprising particles, wherein said particles carry, on at least a portion of the particle surface, carbon deposited by pyrolysis, said process comprising a dry high-energy milling step performed on precursors of said carbon-deposited alkali metal oxyanion prior to a solid-state thermal reaction.
1. A process for the synthesis of phosphosilicate cathode material particles having a deposit of carbon on at least a portion of the surface thereof, said phosphosilicate material comprising lithium and Fe, said Fe being doped with a 4+ valence state metal M′, said process comprising:
a first dry high-energy milling step performed on precursors of said cathode material;
a first solid-state thermal reaction;
a second dry high-energy milling step; and
a second solid-state thermal reaction.
2. The process of claim 1 , wherein said first solid-state thermal reaction is operated at a temperature selected from the range of temperatures of from about 200° C. to about 600° C.
3. The process of claim 1 , wherein said second solid-state thermal reaction is operated at a temperature selected from the range of temperatures of from about 400° C. to about 800° C.
4. The process of claim 1 , wherein said first and/or second high-energy milling step is performed during a time period selected from the range of from about 5 minutes to about 4 hours.
5. The process of claim 1 , further comprising a subsequent flash thermal treatment which is operated at a temperature selected from the temperature range of from about 650° C. to about 900° C.
6. The process of claim 1 , wherein said precursors include a source compound of carbon for obtaining the deposit of carbon.
7. The process of claim 6 , wherein said source compound of carbon is a liquid, solid or gaseous hydrocarbon.
8. The process of claim 1 , wherein said Fe is doped with from 3 atomic % to 15 atomic % of the 4+ valence state M′.
9. The process of claim 1 , wherein said precursors comprise at least one source compound of lithium, at least one source compound of Fe; at least one source compound of said 4+ valence state metal M′; at least one source compound of phosphorus; at least one source compound of silicon; and at least one source of carbon.
10. The process of claim 9 , wherein said at least one source compound of Fe is selected from the group consisting of iron, iron(III) oxide, magnetite (Fe 3 O 4 ), trivalent iron phosphate, lithium iron hydroxyphosphate, trivalent iron nitrate, ferrous phosphate, vivianite Fe 3 (PO 4 ) 2 , iron acetate (CH 3 COO) 2 Fe, iron sulfate (FeSO 4 ), iron oxalate, iron(III) nitrate, iron(II) nitrate, FeCl 3 , FeCl 2 , FeO, ammonium iron phosphate (NH 4 FePO 4 ), Fe 2 P 2 O 7 , ferrocene, and any combinations thereof.
11. The process of claim 9 , wherein said at least one source compound of lithium is selected from the group consisting of lithium oxide, lithium hydroxide, lithium carbonate, Li 3 PO 4 , LiH 2 PO 4 , LiNaHPO 4 , LiKHPO 4 , Li 2 HPO 4 , lithium ortho-, meta- or polysilicates, lithium sulfate, lithium oxalate, lithium acetate, and any combinations thereof.
12. The process of claim 9 , wherein said at least one source compound of silicon is selected from the group consisting of organosilicon, silicon alkoxides, tetraalkyl orthosilicate, tetraethyl orthosilicate, nanosized SiO 2 , Li 2 SiO 3 , Li 4 SiO 4 , and any combinations thereof.
13. The process of claim 1 , wherein said M′ is selected from the group consisting of Zr 4+ , Ti 4+ , Nb 4+ , Mo 4+ , Ge 4+ , Ce 4+ and Sn 4+ .
14. The process of claim 1 , wherein said M′ is Zr 4+ .
15. The process of claim 14 , wherein said at least one source compound of M′ is selected from the group consisting of zirconium acetate hydroxide, zirconium alkoxide, n-butyl zirconate, zirconium(IV) acetylacetonate, zirconium(IV) ethoxide, zirconium(IV) hydrogenphosphate, zirconium(IV) silicate and any combinations thereof.
16. The process of claim 14 , wherein said source compounds are selected to provide a cathode material having a general element ratios Li:(Fe+Zr):PO 4 :SiO 4 of about 1:1:0.7 to less than 1: more than 0 to 0.3.
17. The process of claim 1 , wherein said second dry high-energy milling step produces a substantially amorphous material.
18. The process of claim 1 , wherein said first and/or second solid-state thermal reactions is performed under an inert or reductive atmosphere.
19. The process of claim 1 , wherein said precursors comprise at least FePO 4 and Li 2 CO 3 .
20. The process of claim 1 , said material further comprising Mn.