Prelithiated silicon particles for lithium ion batteries
A process for the facile prelithiation of silicon-containing materials for use in lithium ion batteries is disclosed. The process can include using a lithium additive comprising LiSt, Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , LATP, LAGP, LLTO, LLZO, Li 3 N, LiBF 4 , Li 2 CO 3 , Li 3 PO 4 , lithium-enriched variations thereof, or combinations thereof. The resulting prelithiated materials demonstrate enhanced physicochemical properties providing for high target capacity and excellent cycle stability for the batteries prepared with the materials.
1. A prelithiated silicon-containing material comprising:
(a) a silicon core particle comprising a silicon-containing material selected from the group consisting of:
(i) a silicon alloy, wherein the silicon alloy is selected from the group consisting of a silicon iron (SiFe) alloy and an alloy comprising silicon, iron and another element X, wherein X is selected from the group consisting of Mn, Cr, Sn, Ti, Ni, Co, Mo, Zr, Cu, and Al;
(ii) nanoparticulate silicon (SiNP) and/or microparticulate silicon (SiMP); and
(iii) a silicon suboxide (SiO x ); and
(b) a lithium coating layer comprising a lithium additive, wherein the lithium coating layer directly covers at least a portion of the silicon core particle, further comprising a carbon coating layer coating at least a portion of an outer surface of the lithium coating layer, wherein the carbon coating layer comprises a carbon-containing material.
2. The prelithiated silicon-containing material of claim 1 , wherein the carbon-containing material is selected from the group consisting of activated carbon, artificial graphite, natural graphite, carbon nanotubes, graphene, and combinations thereof.
3. The prelithiated silicon-containing material of claim 1 , wherein the silicon core particle comprises SiNP and/or SiMP.
4. The prelithiated silicon-containing material of claim 3 , wherein the lithium additive is a lithium-enriched additive comprising one or more of the group consisting of lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , lithium-enriched LATP, lithium-enriched LAGP, lithium-enriched LLTO, lithium-enriched LLZO, lithium-enriched Li 3 N, lithium-enriched LiBF 4 , lithium-enriched LiPO 4 , and combinations thereof.
5. The prelithiated silicon-containing material of claim 4 , wherein the lithium additive comprises one or more of the group consisting of a lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , a lithium-enriched LATP, a lithium-enriched LAGP, a lithium-enriched LLTO, and a lithium-enriched LLZO.
6. The prelithiated silicon-containing material of claim 1 , wherein the silicon core particle comprises a silicon alloy selected from the group consisting of a SiFe alloy and an alloy comprising silicon, iron and another element X, wherein X is selected from the group consisting of Mn, Cr, Sn, Ti, Ni, Co, Mo, Zr, Cu, and Al.
7. The prelithiated silicon of claim 6 , wherein the silicon alloy is selected from the group consisting of a silicon iron (SiFe) alloy and an alloy comprising silicon, iron and another element X, wherein X is selected from the group consisting of Mn, Cr, Ni, Co, Zr, and Al.
8. The prelithiated silicon of claim 7 , wherein the silicon alloy is a silicon iron (SiFe) alloy or an alloy comprising silicon, iron and manganese (Mn).
9. The prelithiated silicon-containing material of claim 6 , wherein the lithium additive is a lithium-enriched additive comprising one or more of the group consisting of lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , lithium-enriched LATP, lithium-enriched LAGP, lithium-enriched LLTO, lithium-enriched LLZO, lithium-enriched Li 3 N, lithium-enriched LiBF 4 , lithium-enriched LiPO 4 , and combinations thereof.
10. The prelithiated silicon-containing material of claim 9 , wherein the lithium additive comprises one or more of the group consisting of a lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , a lithium-enriched LATP, a lithium-enriched LAGP, a lithium-enriched LLTO, and a lithium-enriched LLZO.
11. The prelithiated silicon-containing material of claim 1 , wherein the lithium additive is a lithium-enriched additive comprising one or more of the group consisting of lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , lithium-enriched LATP, lithium-enriched LAGP, lithium-enriched LLTO, lithium-enriched LLZO, lithium-enriched Li 3 N, lithium-enriched LiBF 4 , lithium-enriched LiPO 4 , and combinations thereof.
12. The prelithiated silicon-containing material of claim 11 , wherein the lithium additive comprises one or more of the group consisting of a lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , a lithium-enriched LATP, a lithium-enriched LAGP, a lithium-enriched LLTO, and a lithium-enriched LLZO.
13. The prelithiated silicon-containing material of claim 1 , wherein the lithium additive comprises one or more of the group consisting of lithium stearate (LiSt), lithium oxide-silicon oxide-titanium oxide-phosphorus pentoxide (Li 2 O—SiO 2 —TiO 2 —P 2 O 5 ), lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium lanthanum titanium oxide (LLTO), lithium lanthanum zirconium oxide (LLZO), lithium nitride (Li 3 N), lithium tetrafluoroborate (LiBF 4 ), lithium carbonate (Li 2 CO 3 ), lithium phosphate (Li 3 PO 4 ), lithium-enriched variations thereof, and combinations thereof.
14. A process for the preparation of a prelithiated silicon-containing material, wherein the process comprises:
providing a silicon core particle comprising a silicon-containing material selected from the group consisting of: (i) a silicon alloy, wherein the silicon alloy is selected from the group consisting of a silicon iron (SiFe) alloy and an alloy comprising silicon, iron and another element X, wherein X is selected from the group consisting of Mn, Cr, Sn, Ti, Ni, Co, Mo, Zr, Cu, and Al; (ii) nanoparticulate silicon (SiNP) and/or microparticulate silicon (SiMP); and (iii) a silic on suboxide (SiO x );
milling the silicon core particle with one or more lithium additive, such that a lithium coating layer comprising the one or more lithium additive directly covers at a least a portion of the silicon core particle; and
milling the lithium-coated particle with a carbon-containing material, such that a carbon coating layer coats at least a portion of an outer surface of the lithium coating layer, wherein the carbon coating layer comprises the carbon-containing material.
15. The process of claim 14 , wherein the lithium additive is a lithium-enriched additive comprising one or more of the group consisting of lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , lithium-enriched LATP, lithium-enriched LAGP, lithium-enriched LLTO, lithium-enriched LLZO, lithium-enriched Li 3 N, lithium-enriched LiBF 4 , lithium-enriched LiPO 4 , and combinations thereof.
16. The process of claim 14 , wherein the one or more lithium additive is selected from the group consisting of lithium stearate (LiSt), lithium oxide-silicon oxide-titanium oxide-phosphorus pentoxide (Li 2 O—SiO 2 —TiO 2 —P 2 O 5 ), lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium lanthanum titanium oxide (LLTO), lithium lanthanum zirconium oxide (LLZO), lithium nitride (Li 3 N), lithium tetrafluoroborate (LiBF 4 ), lithium carbonate (Li 2 CO 3 ), lithium phosphate (Li 3 PO 4 ), lithium-enriched variations thereof, and combinations thereof to provide a lithium-coated particle.
17. An anode active material comprising a plurality of prelithiated silicon-containing particles, which individually can be the same or different, wherein each of the plurality of prelithiated silicon-containing particles comprises:
(a) a silicon core particle comprising a silicon-containing material selected from the group consisting of:
(i) a silicon alloy, wherein the silicon alloy is selected from the group consisting of a silicon iron (SiFe) alloy and an alloy comprising silicon, iron and another element X, wherein X is selected from the group consisting of Mn, Cr, Sn, Ti, Ni, Co, Mo, Zr, Cu, and Al;
(ii) nanoparticulate silicon (SiNP) and/or microparticulate silicon (SiMP); and
(iii) a silicon suboxide (SiO x ); and
(b) a lithium coating layer comprising a lithium additive, wherein the lithium coating layer directly covers a least a portion of the silicon core particle;
wherein one or more of the plurality of prelithiated silicon-containing particles further comprises (c) a carbon coating layer coating at least a portion of an outer surface of the lithium coating layer, wherein the carbon coating layer comprises a carbon-containing material.
18. The anode active material of claim 17 , wherein one or more of the plurality of prelithiated silicon-containing particles comprises a silicon core particle comprising SiNP and/or SiMP.
19. The anode active material of claim 17 , wherein one or more of the plurality of prelithiated silicon-containing particles comprises a silicon core particle comprising a silicon alloy selected from a SiFe alloy or an alloy comprising silicon, iron, and another element X, wherein X is selected from the group consisting of Mn, Cr, Sn, Ti, Ni, Co, Mo, Zr, Cu, and Al.
20. The anode active material of claim 19 , wherein the silicon alloy is selected from the group consisting of a silicon iron (SiFe) alloy and an alloy comprising silicon, iron and another element X, wherein X is selected from the group consisting of Mn, Cr, Ni, Co, Zr, and Al.
21. The anode active material of claim 17 , wherein the plurality of prelithiated silicon-containing particles comprise particles wherein the silicon core particles comprise SiNP and/or SiMP and particles wherein the silicon core particles comprise SiOx.
22. The anode active material of claim 17 , wherein the plurality of prelithiated silicon-containing particles comprise particles wherein the silicon core particles comprise SiNP and/or SiMP and particles wherein the silicon core particles comprise a SiFe alloy or an SiFeMn alloy.
23. The anode active material of claim 17 , wherein the lithium additive is a lithium-enriched additive comprising one or more of the group consisting of lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , lithium-enriched LATP, lithium-enriched LAGP, lithium-enriched LLTO, lithium-enriched LLZO, lithium-enriched Li 3 N, lithium-enriched LiBF 4 , lithium-enriched LiPO 4 , and combinations thereof.
24. The anode active material of claim 23 , wherein the lithium additive is one or more of the group consisting of a lithium enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , a lithium-enriched LATP, a lithium-enriched LAGP, a lithium-enriched LLTO, a lithium-enriched LLZO, and combinations thereof.
25. A battery comprising:
a negative electrode comprising the anode active material of claim 17 ;
a positive electrode; and
an electrolyte.
26. The battery of claim 25 , wherein the lithium additive is a lithium-enriched additive comprising one or more of the group consisting of lithium-enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , lithium-enriched LATP, lithium-enriched LAGP, lithium-enriched LLTO, lithium-enriched LLZO, lithium-enriched Li 3 N, lithium-enriched LiBF 4 , lithium-enriched LiPO 4 , and combinations thereof.
27. The battery of claim 26 , wherein the lithium additive is one or more of the group consisting of a lithium enriched Li 2 O—SiO 2 —TiO 2 —P 2 O 5 , a lithium-enriched LATP, a lithium-enriched LAGP, a lithium-enriched LLTO, a lithium-enriched LLZO, and combinations thereof.
28. The anode active material of claim 17 , wherein the lithium additive comprises one or more of the group consisting of lithium stearate (LiSt), lithium oxide-silicon oxide-titanium oxide-phosphorus pentoxide (Li 2 O—SiO 2 —TiO 2 —P 2 O 5 ), lithium aluminum titanium phosphate (LATP), lithium aluminum germanium phosphate (LAGP), lithium lanthanum titanium oxide (LLTO), lithium lanthanum zirconium oxide (LLZO), lithium nitride (Li 3 N), lithium tetrafluoroborate (LiBF 4 ), lithium carbonate (Li 2 CO 3 ), lithium phosphate Li 3 PO 4 , lithium-enriched variations thereof, and combinations thereof.
29. The anode active material of claim 17 , wherein the carbon coating layer comprises a carbon-containing material selected from the group consisting of activated carbon, artificial graphite, natural graphite, carbon nanotubes, graphene, and combinations thereof.