Materials with extremely durable intercalation of lithium and manufacturing methods thereof
Composites of silicon and various porous scaffold materials, such as carbon material comprising micro-, meso- and/or macropores, and methods for manufacturing the same are provided. The compositions find utility in various applications, including electrical energy storage electrodes and devices comprising the same.
1. A composite comprising a porous carbon scaffold and silicon, wherein the composite comprises from 15 to 85% silicon by weight and a nitrogen-inaccessible volume ranging from 0.05 to 0.5 cm 3 /g, and wherein the composite comprises a plurality of particles having a particle skeletal density ranging from 1.5 to 2.2 g/cm 3 , as measured by helium pycnometry.
2. The composite of claim 1 , wherein the nitrogen-inaccessible volume ranges from 0.2 to 0.4 cm 3 /g.
3. The composite of claim 1 , wherein the nitrogen-inaccessible volume ranges from 0.1 to 0.3 cm 3 /g.
4. The composite of claim 1 , wherein the particle skeletal density ranges from 1.9 to 2.2 g/cm 3 .
5. The composite of claim 1 , wherein the particle skeletal density ranges from 1.5 to 1.8 g/cm 3 .
6. The composite of claim 1 , having a pellet density ranging from 1.0 to 1.5 g/cm 3 .
7. The composite of claim 1 , wherein the composite has a pore structure comprising less than 10% micropores, greater than 30% mesopores, greater than 30% macropores and a total pore volume less than 0.1 cm 3 /g, as determined by nitrogen sorption.
8. The composite of claim 1 , wherein the composite has a pore structure comprising 30-60% micropores, 30-60% mesopores, less than 10% macropores and a total pore volume less than 0.1 cm 3 /g, as determined by nitrogen sorption.
9. The composite of claim 1 , wherein the composite has a pore structure comprising less than 20% micropores, greater than 60% mesopores, less than 30% macropores and a total pore volume less than 0.1 cm 3 /g, as determined by nitrogen sorption.
10. The composite of claim 1 , wherein the porous carbon scaffold has a pore structure comprising 30-60% micropores, 30-60% mesopores, less than 10% macropores and a total pore volume between 0.1 and 0.5 cm 3 /g, as determined by nitrogen sorption.
11. The composite of claim 1 , wherein the porous carbon scaffold has a pore structure comprising 40-60% micropores, 40-60% mesopores, less than 1% macropores and a total pore volume between 0.1 and 0.5 cm 3 /g, as determined by nitrogen sorption.
12. The composite of claim 1 , wherein the porous carbon scaffold comprises 10-50% of pores having a diameter from 50-200 Å and greater than 90% of pores having a diameter less than 200 Å.
13. The composite of claim 1 , wherein the silicon content ranges from 25% to 65%.
14. The composite of claim 1 , having a ratio of pore volume of the carbon scaffold to silicon volume between 0.3:1 and 1:1.
15. The composite of claim 1 , having a ratio of nitrogen-inaccessible pore volume to silicon volume between 0.3:1 and 1:1.
16. The composite of claim 1 , wherein the particles have an average particle size of less than 5 microns.
17. The composite of claim 1 , wherein the plurality of particles comprises particles having a surface layer of carbon.
18. The composite of claim 17 , wherein each surface layer of carbon comprises from 1 to 20% of the total mass each particle.
19. The composite of claim 17 , wherein the surface layer of carbon comprises a pyrolyzed or partially pyrolyzed conductive polymer.
20. The composite of claim 19 , wherein the conductive polymer comprises polyacrylonitrile or poly(3,4-ethylenedioxythiophene).
21. The composite of claim 17 , wherein the surface layer of carbon comprises a graphitizable carbon.
22. The composite of claim 1 , further comprising a metal.
23. The composite of claim 22 , wherein the metal is aluminum, nickel or manganese.
24. The composite of claim 1 , wherein particles of composite have an average expansion upon litiation ranging from 10 to 100% as determined by in situ TEM.
25. The composite of claim 24 , wherein the average expansion ranges from 10 to 50%.
26. The composite of claim 1 , wherein the composite comprises a plurality of particles, the particles having an average diameter less than 50 nm as determined by ex-situ TEM.
27. The composite of claim 1 , wherein the porous carbon scaffold has a surface area of greater than 750 m 2 /g.
28. The composite of claim 1 , wherein the porous carbon scaffold has a total pore volume of greater than 0.5 cm 3 /g.
29. An electrode comprising a composite according to claim 1 .
30. An energy storage device comprising an electrode according to claim 29 .