High capacity anodes

Patent metadata

Field	Value
Publication number	US-9054372-B2
Application number	US-200913056745-A
Country	US
Kind code	B2
Filing date	Jul 31, 2009
Priority date	Aug 1, 2008
Publication date	Jun 9, 2015
Grant date	Jun 9, 2015

Abstract

A novel anode for a lithium battery cell is provided. The anode contains silicon nanoparticles embedded in a solid polymer electrolyte. The electrolyte can also act as a binder for the silicon nanoparticles. A plurality of voids is dispersed throughout the solid polymer electrolyte. The anode may also contain electronically conductive carbon particles. Upon charging of the cell, the silicon nanoparticles expand as take up lithium ions. The solid polymer electrolyte can deform reversibly in response to the expansion of the nanoparticles and transfer the volume expansion to the voids.

First claim

We claim:

1. An electrode for an electrochemical cell comprising:
a solid polymer electrolyte comprising a plurality of voids; and nanostructures comprising electrode active material, the nanostructures distributed within and throughout the solid polymer electrolyte,
wherein the plurality of voids is compressible such that upon incorporation of the electrode active material into the nanostructures, the solid polymer electrolyte expands into the plurality of voids.

2. The electrode of claim 1 , further comprising a binder to bind the nanostructures within the electrode.

3. The electrode of claim 2 wherein the binder comprises PVDF.

4. The electrode of claim 1 wherein the electrode contains no additional electrolytes.

5. The electrode of claim 1 wherein the solid polymer electrolyte has a yield strain of 50-500% and an elastic modulus of greater than 1×10 5 Pa.

6. The electrode of claim 1 wherein the nanostructures are selected from the group consisting of nanorods, nanowires, nanotubes, and nanoparticles.

7. The electrode of claim 1 wherein the nanostructures comprise carbon, aluminum, silicon, germanium, tin, lead, antimony, magnesium, copper, nickel or alloys or mixtures thereof.

8. The electrode of claim 1 wherein the nanostructures comprise silicon.

9. The electrode of claim 1 wherein the nanostructures comprise silicon alloys of tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium (Ti), germanium (Ge), bismuth (Bi), antimony (Sb), and chromium (Cr) or mixtures thereof.

10. The electrode of claim 1 wherein the nanostructures comprise silicon oxides or silicon carbides.

11. The electrode of claim 1 wherein the nanostructures comprise a metal oxide.

12. The electrode of claim 1 wherein the nanostructures have no dimension larger than their critical fracture length.

13. The electrode of claim 1 wherein the nanostructures have no more than one dimension larger than their critical fracture length.

14. The electrode of claim 1 wherein the nanostructures are approximately equiaxed and have a diameter between about 5 nm and 1 μm.

15. The electrode of claim 1 wherein the nanostructures are approximately equiaxed and have a diameter between about 5 nm and 500 nm.

16. The electrode of claim 1 wherein the nanostructures are approximately equiaxed and have a diameter between about 5 nm and 100 nm.

17. The electrode of claim 1 wherein the nanostructures are approximately equiaxed and have a diameter between about 5 nm and 50 nm.

18. The electrode of claim 1 wherein the nanostructures are linear and have a diameter between about 1 nm and 1 μm.

19. The electrode of claim 1 wherein the nanostructures are linear and have a diameter between about 1 nm and 500 nm.

20. The electrode of claim 1 wherein the nanostructures are linear and have a diameter between about 1 nm and 100 nm.

21. The electrode of claim 1 wherein the plurality of voids has a total volume no smaller than four times the total volume of the nanostructures before lithiation.

22. The electrode of claim 1 wherein the plurality of voids has a total volume no smaller than three times the total volume of the nanostructures before lithiation.

23. The electrode of claim 1 wherein the plurality of voids has a total volume no smaller than two and a half times the total volume of the nanostructures before lithiation.

24. The electrode of claim 1 wherein the plurality of voids has a total volume no smaller than twice the total volume of the nanostructures before lithiation.

25. The electrode of claim 1 wherein the voids have a volume that is between about 10% and 60% of the electrode.

26. The electrode of claim 1 , further comprising between about 0 and 10 weight percent conductive carbon particles.

27. The electrode of claim 1 wherein the solid polymer electrolyte comprises one or more polymers selected from the group consisting of the following optionally cross-linked polymers: polyethylene oxide, polysulfone, polyacrylonitrile, siloxane, polyether, polyamine, linear copolymers containing ethers or amines, ethylene carbonate, Nafion®, and polysiloxane grafted with small molecules or oligomers that include polyethers and/or alkylcarbonates.

28. The electrode of claim 1 wherein the solid polymer electrolyte comprises a block copolymer.

29. The electrode of claim 28 wherein the solid polymer electrolyte further comprises at least one lithium salt.

30. The electrode of claim 28 wherein the block copolymer is either a diblock copolymer or a triblock copolymer.

31. The electrode of claim 30 wherein a first block of the block copolymer is ionically conductive and is selected from the group consisting of polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, polysiloxanes, polyphosphazines, polyolefins, polydienes, and combinations thereof.

32. The electrode of claim 30 wherein a first block of the block copolymer comprises an ionically-conductive comb polymer, which comb polymer comprises a backbone and pendant groups.

33. The electrode of claim 32 wherein the backbone comprises one or more selected from the group consisting of polysiloxanes, polyphosphazines, polyethers, polydienes, polyolefins, polyacrylates, polymethacrylates, and combinations thereof.

34. The electrode of claim 32 wherein the pendants comprise one or more selected from the group consisting of oligoethers, substituted oligoethers, nitrile groups, sulfones, thiols, polyethers, polyamines, polyimides, polyamides, alkyl carbonates, polynitriles, other polar groups, and combinations thereof.

35. The electrode of claim 30 wherein a second block of the block copolymer is selected from the group consisting of polystyrene, polymethacrylate, poly(methyl methacrylate), polyvinylpyridine, polyvinylcyclohexane, polyimide, polyamide, polypropylene, polyolefins, poly(t-butyl vinyl ether), poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), poly(t-butyl vinyl ether), polyethylene, fluorocarbons, polyvinylidene fluoride, and copolymers that contain styrene, methacrylate, and/or vinylpyridine.

36. A lithium battery cell, comprising:
a negative electrode according to the electrode of claim 1 ;
a positive electrode;
a solid polymer electrolyte layer between the negative electrode and the positive electrode, the electrolyte layer in ionic communication with both the negative electrode and the positive electrode.

37. The electrode of claim 1 wherein the plurality of voids does not contain the nanostructures.

38. The electrode of claim 28 wherein the block copolymer is nanostructured.

39. The electrode of claim 28 wherein one or more blocks of the block copolymer are cross-linked.

Assignees

• Singh Mohit
• Hudson William
• Seeo Inc

Inventors

• Singh Mohit
• Hudson William

Classifications

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/623

  fluorinated polymers · CPC title

• H01M4/131 Primary

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M4/36 Primary

  Selection of substances as active materials, active masses, active liquids · CPC title