Method of fabricating fibres composed of silicon or a silicon-based material and their use in lithium rechargeable batteries

• US 9,583,762 B2
• Filed: 10/16/2013
• Issued: 02/28/2017
• Est. Priority Date: 01/23/2006
• Status: Active Grant

• Current Assignee: Nexeon Limited
• Original Assignee: Nexeon Limited
• Inventors: Green, Mino, Liu, Feng-Ming
• Primary Examiner(s): Gatewood, Daniel
• Application Number:
  US14/055,371
• Publication Number:
  US 20140045062A1
• Time in Patent Office: 1,231 Days
• Field of Search: 429/211, 429/218.1, 296/235
• US Class Current: 1/1
• CPC Class Codes: C30B 29/06 Silicon
• CPC Class Codes: C30B 29/60 characterised by shape
• CPC Class Codes: C30B 33/08 Etching
• 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 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• 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 4/1393 of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/1395 of electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/386 Silicon or alloys based on silicon
• CPC Class Codes: H01M 4/5825 Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

An electrically interconnected mass includes elongated structures. The elongated structures are electrochemically active and at least some of the elongated structures cross over each other to provide intersections and a porous structure. The elongated structures include doped silicon.

Claims

1. A method of forming a porous structure for a lithium-ion battery electrode, wherein the porous structure comprises a plurality of silicon-comprising elongated elements, the elongated elements being capable of lithium insertion and removal, the method comprising:

arranging a plurality of silicon-comprising elongated elements, wherein at least some of the elongated elements cross over other elongated elements many times along their length to provide multiple intersections thereby defining the porous structure; and

charging the porous structure, wherein the charging welds the elongated elements to one another at the intersections by forming amorphous silicon-containing structures between disrupted crystalline structures of the silicon-comprising elongated elements at the intersections.

2. A method of forming a porous structure as claimed in claim 1, the method further comprising:

etching a silicon or silicon-based substrate to form silicon comprising elongated elements; and

detaching the elongated elements from the substrate to provide the plurality of silicon-comprising elongated elements.

3. A method of forming a porous structure as claimed in claim 1 wherein the porous structure has a percentage pore volume of about 10-30 percent.

4. A method of forming a porous structure as claimed in claim 1 wherein the elongated elements have a resistivity of 100 to 0.001 Ohm cm.

5. A method of forming a porous structure as claimed in claim 1 wherein the elongated elements have an aspect ratio of greater than 40:

1.

6. A method of forming a porous structure as claimed in claim 1 wherein the elongated elements have a transverse dimension in the range of 0.08 to 0.5 microns and/or a length in the range of 20 to 300 microns.

7. A method of forming a porous structure as claimed in claim 1, the method further comprising:

before arranging the plurality of silicon-comprising elongated elements, mixing the plurality of silicon-comprising elongated elements with at least one of a binder and an electronic additive,

wherein after the charging the silicon-comprising elongated structures and the at least one of the binder and the electronic additive cooperate to define a porous composite electrode layer.

8. A method of forming a lithium-ion battery electrode, the method comprising the method of forming a porous structure as claimed in claim 1 and further comprising:

at least partially filling the porous structure with electrolyte.

9. A method of making a lithium-ion battery comprising the steps of claim 1.

18. A method of forming a porous structure as claimed in claim 1, wherein the porous structure is a felt or felt-like structure.

20. A method of forming a porous structure as claimed in claim 1 wherein the elongated elements have a transverse dimension in the range of 0.08 to 5 microns.

21. A method of forming a porous structure as claimed in claim 20 wherein the elongated elements have a length in the range of 20 to 300 microns.

22. A method of forming a porous structure as claimed in claim 20 wherein the elongated elements have an aspect ratio of greater than 40:

1.

23. A method of forming a porous structure as claimed in claim 20 wherein the porous structure has a percentage pore volume of about 10-30 percent.

24. A method of forming the porous structure as claimed in claim 20, wherein the elongated elements are formed from doped silicon or pure silicon.

25. A method of forming a porous structure as claimed in claim 1, wherein the elongated elements are provided to the arranging step as fibers not attached to a substrate.

26. A method of forming a porous structure as claimed in claim 1, wherein the elongated elements are substantially straight.

27. A method of forming a porous structure as claimed in claim 1, wherein each of the elongated elements is a single crystal, and extends in a direction parallel to a crystalline plane of the single crystal.

28. A method of forming a porous structure as claimed in claim 1, wherein the mass of silicon fibers in the porous structure is between 70 percent and 95 percent of the mass of the porous structure.

29. A method of forming the porous structure as claimed in claim 1, wherein the elongated elements are formed from doped silicon or pure silicon.

30. A method of forming the porous structure as claimed in claim 1, wherein the elongated elements are formed from doped silicon, pure silicon, or an alloy of silicon.

31. A method of forming the porous structure as claimed in claim 1, wherein the arranging comprises depositing a slurry of the elongated elements in a solvent on a substrate;

and allowing the solvent to evaporate.

32. A method of forming a porous structure as claimed in claim 7 wherein the porous structure has a percentage pore volume of about 10-30 percent.

10. A porous structure for a lithium-ion battery electrode, wherein the porous structure comprises a plurality of silicon-comprising elongated elements, the elongated elements being capable of lithium insertion and removal,

wherein at least some of the elongated elements cross over other elongated elements many times along their length to provide multiple intersections;

and

wherein the intersections comprise a disrupted crystalline or amorphous structure, formed by charging the porous structure, which welds elongated elements to one another.

11. A porous structure as claimed in claim 10 having a percentage pore volume of about 10-30 percent.

12. A porous structure as claimed in claim 10 wherein the elongated elements have an aspect ratio of greater than 40:

1.

13. A porous structure as claimed in claim 10 wherein the elongated elements comprise n-type and/or p-type silicon.

14. A porous structure as claimed in claim 10 wherein the elongated elements have a transverse dimension in the range of 0.08 to 0.5 microns and/or a length in the range of 20 to 300 microns.

15. A porous structure as claimed in claim 10 further comprising at least one of a binder and an electronic additive, wherein the elongated structures and the at least one of the binder and the electronic additive cooperate to define a porous composite electrode layer.

16. A lithium-ion battery electrode comprising the porous structure of claim 10.

33. A porous structure as claimed in claim 10 wherein the elongated elements have a transverse dimension in the range of 0.08 to 5 microns.

35. A porous structure as claimed in claim 33 wherein the elongated elements have an aspect ratio of greater than 40:

1.

36. A porous structure as claimed in claim 33, wherein the elongated elements are formed from doped silicon or pure silicon.

37. A porous structure as claimed in claim 33 wherein the porous structure has a percentage pore volume of about 10-30 percent.

38. A porous structure as claimed in claim 10, wherein the elongated elements are formed from doped silicon, pure silicon, or an alloy of silicon.

39. A porous structure as claimed in claim 10, wherein the elongated elements are substantially straight.

40. A porous structure as claimed in claim 10, wherein each of the elongated elements is a single crystal, and extends in a direction parallel to a crystalline plane of the single crystal.

41. A porous structure as claimed in claim 10, wherein the mass of the elongated elements in the porous structure is between 70 percent and 95 percent of the mass of the porous structure.

42. A porous structure as claimed in claim 15 wherein the porous structure has a percentage pore volume of about 10-30 percent.

17. A method of forming a lithium-ion battery electrode, the method comprising:

depositing a plurality of crystalline silicon-comprising elongated elements, the elongated elements being capable of lithium insertion and removal, wherein when deposited at least some of the elongated elements cross over other elongated elements many times along their length to form multiple intersections thereby forming a porous structure; and

charging the porous structure, wherein the charging welds the elongated elements to one another at the intersections by forming amorphous silicon-containing structures between disrupted crystalline structures of the silicon-comprising elongated elements at the intersections.

19. A method of forming a lithium-ion battery electrode as claimed in claim 17, further comprising:

recharging the lithium-ion battery electrode a plurality of times;

wherein each of the recharging operations increases the structural strength of the electrode.

34. A porous structure as claimed in 33, wherein the elongated elements have a length in the range of 20 to 300 microns.