Curved two-dimensional nanocomposites for battery electrodes
A battery electrode composition is provided that comprises a composite material comprising one or more nanocomposites. The nanocomposites may each comprise a planar substrate backbone having a curved geometrical structure, and an active material forming a continuous or substantially continuous film at least partially encasing the substrate backbone. To form an electrode from the electrode composition, a plurality of electrically-interconnected nanocomposites of this type may be aggregated into one or more three-dimensional agglomerations, such as substantially spherical or ellipsoidal granules.
1. A three-dimensional (3D) porous silicon (Si)-comprising and carbon (C)-comprising nanocomposite particle, comprising:
interconnected curved and defect-comprising graphene;
Si or Si-comprising active material in direct contact with the interconnected curved and defect-comprising graphene;
at least one more material distinct from the interconnected curved and defect-comprising graphene and the Si or Si-comprising active material; and
internal pores that at least partially accommodate volume changes in the Si or Si-comprising active material during insertion and extraction of lithium ions, at least some of the internal pores formed by the interconnected curved and defect-comprising graphene,
wherein:
the internal pores comprise one or more micropores; and
the interconnected curved and defect-comprising graphene is characterized by a radius of curvature in a range of about 0.3 nm to about 0.03 mm.
2. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein:
the at least one more material distinct from the interconnected curved and defect-comprising graphene and the Si or Si-comprising active material comprises amorphous carbon.
3. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein:
the at least one more material distinct from the interconnected curved and defect-comprising graphene and the Si or Si-comprising active material comprises one or more of the following: oxide, carbide, nitride, sulfide, fluoride or oxyfluoride.
4. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein:
the at least one more material distinct from the interconnected curved and defect-comprising graphene and the Si or Si-comprising active material comprises a polymer.
5. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein at least some of the carbon in the 3D porous Si-comprising and C-comprising nanocomposite particle is produced by a thermal annealing or a hydrothermal treatment of a polymeric material.
6. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 5 , wherein at least about 20 atomic percent of the polymeric material comprises carbon in a monomeric unit used to form a polymer.
7. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 5 , wherein the polymeric material comprises one or more of the following: sucrose, carbonate, petroleum pitch, polyether, polyester, methyl-group comprising polymer, methacrylate-comprising polymer, nitrile-comprising polymer, and conductive polymer.
8. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein at least some carbon in the 3D porous Si-comprising and C-comprising nanocomposite particle is produced by thermal decomposition of a hydrocarbon.
9. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein at least one of the internal pores in the 3D porous Si-comprising and C-comprising nanocomposite particle is produced during thermal annealing of a polymeric material.
10. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein the 3D porous Si-comprising and C-comprising nanocomposite particle comprises one or more Group III elements.
11. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 10 , wherein the Si or Si-comprising active material comprises from 3000 parts per million (ppm) to 700,000 ppm of the one or more Group III elements in the 3D porous Si-comprising and C-comprising nanocomposite particle.
12. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein the 3D porous Si-comprising and C-comprising nanocomposite particle comprises one or more Group V elements.
13. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 12 , wherein the Si or Si-comprising active material comprises 3000 parts per million (ppm) to 700,000 ppm of the one or more Group V elements in the 3D porous Si-comprising and C-comprising nanocomposite particle.
14. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein the 3D porous Si-comprising and C-comprising nanocomposite particle comprises one or more of the following metal elements: Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Sr, Y, Zr, Nb, Mo, W, Ta, and Ba.
15. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 14 , wherein the Si or Si-comprising active material comprise 3000 parts per million (ppm) to 800,000 ppm of the one or more of the following metal elements: Mg, Ca, Sc, Ti, V, Cr, Mn, Fe, Cu, Zn, Sr, Y, Zr, Nb, Mo, W, Ta, and Ba.
16. A Li-ion battery, comprising:
an anode comprising the 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 ,
wherein the 3D porous Si-comprising and C-comprising nanocomposite particle plastically deforms and expands during first lithiation to form an expanded lithiated nanocomposite particle.
17. The Li-ion battery of claim 16 , wherein de-lithiation of the expanded lithiated nanocomposite particle induces formation of additional internal pores.
18. A battery electrode composition, comprising:
a plurality of three-dimensional (3D) porous silicon (Si)-comprising and carbon (C)-comprising nanocomposite particles,
wherein each of the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles is configured as the 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 .
19. A Li-ion battery, comprising:
an anode comprising the battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a lithiation peak in a differential capacity curve dQ/dV at around 0.22 V vs. Li/Li + .
20. A Li-ion battery, comprising:
an anode comprising the battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a de-lithiation peak in a differential capacity curve dQ/dV at around 0.49 V vs. Li/Li + .
21. A Li-ion battery, comprising:
an anode comprising the battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a first de-lithiation peak in a differential capacity curve dQ/dV at around 0.49 V vs. Li/Li + and a second lithiation peak in the differential capacity curve dQ/dV at around 0.22 V vs. Li/Li + , and wherein a first intensity of the first de-lithiation peak is greater than a second intensity of the second lithiation peak.
22. The battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles adsorbs about 10 cc of nitrogen per gram of the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles at a relative pressure of around 0.99 during cryogenic nitrogen sorption measurements at 77 K.
23. A Li-ion battery, comprising:
an anode comprising the battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a specific reversible capacity in a range of about 1060 mAh/g to about 2300 mAh/g when the Li-ion battery is cycled at a current density from around 140 mA/g to about 1400 mA/g.
24. The battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a characteristic Raman spectroscopy peak at around 520 cm −1 .
25. The battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a first characteristic Raman spectroscopy peak at around 1350 cm −1 (carbon D band) and a second characteristic Raman spectroscopy peak at around 1580 cm −1 (carbon G band) and wherein a first intensity of the first characteristic Raman spectroscopy peak is equal to or greater than a second intensity of the second characteristic Raman spectroscopy peak.
26. The battery electrode composition of claim 18 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a first characteristic Raman spectroscopy peak at around 520 cm −1 (silicon band) and a second characteristic Raman spectroscopy peak at around 1350 cm −1 (carbon D band) and wherein a first intensity of the first characteristic Raman spectroscopy peak is greater than a second intensity of the second characteristic Raman spectroscopy peak.
27. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 ,
wherein the 3D porous Si-comprising and C-comprising nanocomposite particle comprises Li-ion electrolyte and/or and a mixed conductor, and
wherein an ionic conductivity of the Li-ion electrolyte or an ionic conductivity of the mixed conductor is on the order of or higher than 10 −8 S cm −1 .
28. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 ,
wherein the internal pores further comprise one or more mesopores and/or one or more macropores.
29. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein a size of the 3D porous Si-comprising and C-comprising nanocomposite particle is approximately 10 micron.
30. The 3D porous Si-comprising and C-comprising nanocomposite particle of claim 1 , wherein a content of the Si in the 3D porous Si-comprising and C-comprising nanocomposite particle is about 60 wt. % of the 3D porous Si-comprising and C-comprising nanocomposite particle.
31. A Li-ion battery, comprising:
the battery electrode composition of claim 18 .
32. The Li-ion battery of claim 31 , further comprising:
an anode,
wherein the anode comprises the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles.
33. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits specific reversible capacity in a range of about 1060 mAh/g to about 2300 mAh/g when the Li-ion battery is cycled at a current density from around 140 mA/g to about 1400 mA/g.
34. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a characteristic Raman spectroscopy peak at around 520 cm −1 .
35. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a first characteristic Raman spectroscopy peak at around 1350 cm −1 (carbon D band) and a second characteristic Raman spectroscopy peak at around 1580 cm −1 (carbon G band) and wherein a first intensity of the first characteristic Raman spectroscopy peak is equal to or greater than a second intensity of the second characteristic Raman spectroscopy peak.
36. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a first characteristic Raman spectroscopy peak at around 520 cm −1 (silicon band) and a second characteristic Raman spectroscopy peak at around 1350 cm −1 (carbon D band) and wherein a first intensity of the first characteristic Raman spectroscopy peak is greater than a second intensity of the second characteristic Raman spectroscopy peak.
37. The Li-ion battery of claim 32 , wherein a size of the 3D porous Si-comprising and C-comprising nanocomposite particle is approximately 10 micron.
38. The Li-ion battery of claim 32 , wherein the anode is at least partially filled with a polymer-comprising and liquid-comprising electrolyte composition.
39. The Li-ion battery of claim 32 , further comprising:
a Li-ion battery electrolyte comprising a LiPF 6 salt and one or more carbonate solvents.
40. The Li-ion battery of claim 32 , wherein the Li-ion battery is a cylindrical Li-ion battery.
41. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a lithiation peak in a differential capacity curve dQ/dV at around 0.22 V vs. Li/Li + .
42. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibits a de-lithiation peak in a differential capacity curve dQ/dV at around 0.49 V vs. Li/Li + .
43. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles exhibit a first de-lithiation peak in a differential capacity curve dQ/dV at around 0.49 V vs. Li/Li + and a second lithiation peak in the differential capacity curve dQ/dV at around 0.22 V vs. Li/Li + , and wherein a first intensity of the first de-lithiation peak is greater than a second intensity of the second lithiation peak.
44. The Li-ion battery of claim 32 , wherein the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles adsorbs about 10 cc of nitrogen per gram of the plurality of 3D porous Si-comprising and C-comprising nanocomposite particles at a relative pressure of around 0.99 during cryogenic nitrogen sorption measurements at 77 K.