Electrolytes for rechargeable batteries

• US 10,038,219 B2
• Filed: 08/20/2015
• Issued: 07/31/2018
• Est. Priority Date: 11/15/2010
• Status: Active Grant

• Current Assignee: Amprius Technologies Incorporated (Amprius, Inc.)
• Original Assignee: Amprius, Inc.
• Inventors: Roberts, Gregory Alan, Fasching, Rainer J., Stefan, Constantin I.
• Primary Examiner(s): Walls, Cynthia K
• Application Number:
  US14/831,697
• Publication Number:
  US 20160049693A1
• Time in Patent Office: 1,076 Days
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0034 Fluorinated solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 4/0428 Chemical vapour deposition
• CPC Class Codes: H01M 4/134 Electrodes based on metals, Si or alloys
• 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 4/483 for non-aqueous cells H01M4/485 takes precedence
• CPC Class Codes: H01M 4/75 Wires, rods or strips
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

Provided are novel electrolytes for use in rechargeable lithium ion cells containing high capacity active materials, such as silicon, germanium, tin, and/or aluminum. These novel electrolytes include one or more pyrocarbonates and, in certain embodiments, one or more fluorinated carbonates. For example, dimethyl pyrocarbonate (DMPC) may be combine with mono-fluoroethylene carbonate (FEC). Alternatively, DMPC or other pyrocarbonates may be used without any fluorinated carbonates. A weight ratio of pyrocarbonates may be between about 0% and 50%, for example, about 10%. Pyrocarbonates may be combined with other solvents, such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and/or ethyl-methyl carbonate (EMC). Alternatively, pyrocarbonates may be used without such solvents. Experimental results conducted using electrochemical cells with silicon based electrodes demonstrated substantial improvements in cycle life when pyrocarbonate containing electrolytes were used in comparison with pyrocarbonate free electrolytes.

Claims

1. A lithium ion battery comprising:

an electrode comprising an electrochemically active material selected from the group consisting of a silicon containing material, a tin containing material, a germanium containing material, and an aluminum containing material; and

an electrolyte comprising a lithium containing salt and a one or more fluorinated carbonate solvents; and

a solid electrolyte interphase (SEI) layer that includes fluorine, wherein the electrode comprising the electrochemically active material includes core-shell nanostructures that include an inner shell and an outer shell; and

wherein the SEI layer is formed on the outer shell, the nanostructures having at least one cross-sectional dimension between 1 and 1000 nm.

2. The lithium ion battery of claim 1, wherein the electrochemically active material comprises elemental silicon.

3. The lithium ion battery of claim 1, wherein the electrochemically active material comprises a silicon alloy.

4. The lithium ion battery of claim 1, wherein the nanostructures comprise nanowires.

5. The lithium ion battery of claim 4, wherein an outer surface of the nanowires comprise elemental silicon, silicon oxide, silicon alloy, or silicide.

6. The lithium ion battery of claim 1, wherein the electrochemically active material comprises silicon, wherein the lithium ion battery exhibits an average Coulombic efficiency of at least 99.8% after about 100 cycles during a cycling test;

and

wherein the cycling test comprises charging the lithium ion battery to at least about 1050 mAh/g at a rate of at least about C/2 and discharging to 900 mV versus lithium metal at a rate of at least about C/2 in each cycle.

7. The lithium ion battery of claim 1, wherein the one or more fluorinated carbonate solvents are selected from the group consisting of mono-fluoroethylene carbonate, fluoropropylene carbonate, difluoroethylene carbonate, and fluoromethylethylene carbonate.

8. The lithium ion battery of claim 1, wherein the one or more fluorinated carbonate solvents comprises mono-fluoroethylene carbonate (FEC).

9. The lithium ion battery of claim 1, wherein the one or more fluorinated carbonate solvents have a total concentration in the electrolyte of less than about 50% by weight.

10. The lithium ion battery of claim 9, wherein the one or more fluorinated carbonate solvents have a total concentration of less than about 10% by weight.

11. The lithium ion battery electrolyte of claim 1, wherein the one or more fluorinated carbonates includes a fluorinated pyrocarbonate.

12. The lithium ion battery of claim 1, wherein the nanostructures comprise a silicide.

13. The lithium ion battery of claim 1, wherein the nanostructures comprise silicon oxide.

14. The lithium ion battery of claim 1, wherein the thickness of the outer shell is between 1 and 100 nanometers.

15. The lithium ion battery of claim 1, wherein the inner shell comprises elemental silicon.

16. The lithium ion battery of claim 1, wherein the one or more fluorinated carbonate solvents have a total concentration in the electrolyte of less than about 50% by weight.

17. The lithium ion battery of claim 1, wherein the one or more fluorinated carbonate solvents have a total concentration in the electrolyte of less than about 10% by weight.

18. The lithium ion battery of claim 1, wherein the electrolyte further comprises a cyclic carbonate.

19. The lithium ion battery of claim 1, wherein the core-shell nanostructures have solid cores.

20. The lithium ion battery of claim 1, wherein the core-shell nanostructures are tapered along their lengths.