Composite negative electrode materials
Composite particles that include an electrochemically active metal phase, an insulating phase, and a conducting phase are provided that are useful active materials in negative electrodes for lithium-ion electrochemical cells. The electrochemically active phase includes silicon. Lithium-ion electrochemical cells are provided that include the provided composite composite particles as active materials in negative electrodes as well as methods of making the provided composite particles.
1. A composite particle comprising an electrochemically active metal phase, an insulating phase, and a conducting phase,
wherein the electrochemically active metal phase comprises silicon;
wherein each of the phases of the particle is amorphous or has crystalline grains,
wherein the largest grain size of the particle as determined by the Scherrer equation is 14.9 nm or less; and
wherein the phases are distributed substantially homogeneously throughout the particle.
2. A composite particle according to claim 1 , wherein the electrochemically active metal phase occupies less than 50 volume percent of the volume of the composite particle.
3. A composite particle according to claim 1 , wherein the insulating phase occupies less than 50 volume percent of the volume of the composite particle.
4. A composite particle according to claim 1 , wherein at least one of the phases is amorphous.
5. A composite particle according to claim 1 , wherein the insulating phase is selected from a borate, a phosphate, a carbonate, an oxide, a halide and combinations thereof.
6. A composite particle according to claim 5 , wherein the oxide comprises Li, Na, Mg, Ca, La, Ce, Ti, Zr, K, Al, Si, B, or combinations thereof.
7. A composite particle according to claim 5 , wherein the insulating phase is selected from Al 2 O 3 , MgAl 2 O 3 , LiAlO 2 , Li 2 CO 3 , SiO 2 , B 2 O 3 , and combinations thereof.
8. A composite particle according to claim 1 , wherein the insulating phase occupies more than about 10 volume percent of the volume of the composite particle.
9. A composite particle according to claim 1 , wherein the conducting phase is selected from a metal element, an alloy, a carbide, an aluminide, a silicide, a boride, a nitride, and combinations thereof.
10. A composite particle according to claim 9 , wherein the conducting phase is selected from TiSi 2 , TiC, FeSi 2 , SiC, an iron titanium silicide and combinations thereof.
11. A composite particle according to claim 1 , wherein the insulating phase is nonstoichiometric.
12. A composite particle according to claim 1 , wherein the conducting phase is nonstoichiometric.
13. A composite particle according to claim 1 , further comprising a coating at least partially surrounding the particle.
14. An electrode for a lithium-ion electrochemical cell comprising composite particles according to claim 1 .
15. An electrochemical cell comprising an electrode according to claim 14 .
16. An electronic device comprising an electrochemical cell according to claim 15 .
17. A composite particle according to claim 1 , formed after incorporating the particle into an electrode, incorporating the electrode into a lithium-ion electrochemical cell, and cycling the lithium-ion electrochemical cells through at least one charge-discharge cycle.
18. A method of forming composite particles comprising:
providing precursor materials; and
mechanically milling the precursor materials to form the composite particles,
wherein the composite particles include an electrochemically active metal phase, an insulating phase and a conducting phase; wherein the electrochemically active metal phase comprises silicon and each of the phases of the particle is amorphous or has crystalline grains,
wherein the largest grain size of the particles as determined by the Scherrer equation is 14.9 nm or less; and
wherein the phases are distributed substantially homogeneously throughout the particle.
19. A method of forming composite particles according to claim 18 , wherein the precursor materials comprise silicon and additionally comprise one or more of Al 2 O 3 , MgAl 2 O 3 , LiAlO 2 , Li 2 CO 3 , SiO 2 , B 2 O 3 , LiF, FeSi 2 , CrSi 2 , NiSi 2 , CoSi 2 , TiSi 2 , Cu 3 Si, ZrSi 2 , TiB 2 , TiN, FeAl 3 , TiAl 3 , or combinations thereof.
20. A method of forming composite particles according to claim 18 , wherein the precursor materials include materials that form an electrochemically active metal phase, insulating phase and conducting phase during mechanical milling.
21. A method of forming composite particles according to claim 20 wherein the precursor materials comprise silicon and additionally comprise one or more of Fe 2 O 3 , NiO, Co 3 O 4 , Cu 2 O, Mn 2 O 3 , and ZnO 2 , Al 2 O 3 , Ti, V, Cr, Mn, Fe, Co Ni, Cu, carbon, or combinations thereof.
22. A composite particle according to claim 1 , wherein the insulating phase comprises SiO 2 and the conducting phase comprises a metal silicide.
23. A composite particle according to claim 1 , wherein the conducting phase comprises an iron silicide.