NOVEL MATERIALS WITH EXTREMELY DURABLE INTERCALATION OF LITHIUM AND MANUFACTURING METHODS THEREOF

• US 20170170477A1
• Filed: 08/26/2016
• Published: 06/15/2017
• Est. Priority Date: 08/28/2015
• Status: Active Grant

• Current Assignee: Group14 Technologies Inc.
• Original Assignee: EnerG2 Technologies, Incorporated
• Inventors: Costantino, Henry R., Feaver, Aaron M., Thompkins, Leah A., Geramita, Katharine, Sakshaug, Avery, Fredrick, Sarah, Kron, Benjamin E., Afkami, Farshid, Strong, Adam
• Granted Patent: US 10,147,950 B2
• Time in Patent Office: Days
• CPC Class Codes: C04B 2111/00853 in electrochemical cells or batteries, e.g. fuel cells
• CPC Class Codes: C04B 2235/428 Silicon
• CPC Class Codes: C04B 2235/616 Liquid infiltration of green bodies or pre-forms
• CPC Class Codes: C04B 2235/6581 Total pressure below 1 atmosphere, e.g. vacuum
• CPC Class Codes: C04B 35/522 Graphite C04B35/536 takes precedence
• CPC Class Codes: C04B 35/524 obtained from polymer precursors, e.g. glass-like carbon material
• CPC Class Codes: C04B 38/0051 characterised by the pore size, pore shape or kind of porosity
• CPC Class Codes: C04B 38/0054 the pores being microsized or nanosized
• CPC Class Codes: C04B 38/0064 Multimodal pore size distribution
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4529 applied from the gas phase
• CPC Class Codes: C04B 41/5096 Silicon C04B35/573 takes precedence
• CPC Class Codes: C04B 41/85 with inorganic materials
• CPC Class Codes: H01B 1/04 mainly consisting of carbon-silicon compounds, carbon or silicon
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2220/20 Batteries in motive systems, e.g. vehicle, ship, plane
• CPC Class Codes: H01M 4/0416 involving impregnation with a solution, dispersion, paste or dry powder H01M4/0438 takes precedence
• CPC Class Codes: H01M 4/133 Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/362 : Composites
• CPC Class Codes: H01M 4/364 : as mixtures
• CPC Class Codes: H01M 4/366 : as layered products
• CPC Class Codes: H01M 4/386 : Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/587 : for inserting or intercalating light metals
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

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.

Claims

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 cm³/g, and wherein the composite comprises a plurality of particles having a particle skeletal density ranging from 1.5 to 2.2 g/cm³, as measured by helium pycnometry.

2. The composite of claim 1, wherein the nitrogen-inaccessible volume ranges from 0.2 to 0.4 cm³/g.

3. The composite of claim 1, wherein the nitrogen-inaccessible volume ranges from 0.1 to 0.3 cm³/g.

4. The composite of claim 1, wherein the skeletal density ranges from 1.9 to 2.2 g/cm³.

5. The composite of claim 1, wherein the skeletal density ranges from 1.5 to 1.8 g/cm³.

6. The composite of claim 1, having a pellet density ranging from 1.0 to 1.5 g/cm³.

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 cm³/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%% mesoporesless than 10% macropores and a total pore volume less than 0.1 cm³/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 cm³/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 cm³/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 cm³/g, as determined by nitrogen sorption.

12. The composite of claim 1, wherein the particle skeletal density ranges from 1.5 to 1.8 g/cm³.

13. The composite of claim 1, wherein the porous carbon scaffold comprises 10-50% of pores having a diameter from 50-200 A and greater than 90% of pores having a diameter less than 200 A.

14. The composite of claim 1, wherein the silicon content ranges from 25% to 65%.

16. 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.

17. The composite of claim 1, having a ratio of nitrogen-inaccessible pore volume to silicon volume between 0.3:

1 and 1;

1.

18. The composite of claim 1, wherein the average particle size less than 5 microns.

20. The composite of claim 1, comprising a plurality of particles, wherein each particle comprises a surface layer of carbon.

21. The composite of claim 20, wherein the surface layer of carbon comprises from 1 to 20% of the total mass of the particle.

23. The composite of claim 20, wherein the surface layer of carbon comprises a pyrolyzed or partially pyrolyzed conductive polymer.

24. The composite of claim 23, wherein the conductive polymer comprises polyacrylonitrile or poly(3,4-ethylenedioxythiophene).

25. The composite of claim 20, wherein the surface layer of carbon comprises a graphitizable carbon.

26. The composite of claim 1, further comprising a metal.

27. The composite of claim 26, wherein the metal is aluminum, nickel or manganese.

28. 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.

29. The composite of claim 28, wherein the average expansion ranges from 10 to 50%.

31. 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.

32. An electrode comprising a composite according to claim 1.

34. An energy storage device comprising an electrode according to claim 32.

15. (canceled)

19. (canceled)

22. (canceled)

30. (canceled)

33. (canceled)

35-60. -60. (canceled)

61. A carbon material having a surface area of 100 to 2000 m²/g and a total pore volume, wherein less than 10% of the pore volume resides in micropores greater than 80% of the pore volume resides in mesopores volume and less than 5% of the pore volume resides in macropores.

62-66. -66. (canceled)

67. A method for producing a composite a material comprising a porous scaffold material and silicon comprising the following steps:

a) providing a porous scaffold material, wherein the said porous scaffold material comprises 10-50% of pores having a diameter from 50-200 A and greater than 90% of pores having a diameter less than 200 A; and

b) impregnating silicon within the porous scaffold material, thereby producing a silicon-impregnated scaffold material.

68-82. -82. (canceled)