Electrolytes for rechargeable batteries

• US 9,142,864 B2
• Filed: 11/15/2011
• Issued: 09/22/2015
• 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:
  US13/296,753
• Publication Number:
  US 20120121989A1
• Time in Patent Office: 1,407 Days
• Field of Search: None
• US Class Current: 1/1
• 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;

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

and a solid electrolyte interphase (SEI) layer that includes fluorine, wherein the electrode comprising an 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 pyrocarbonate is selected from the group consisting of dimethyl pyrocarbonate, diethyl pyrocarbonate, dipropyl pyrocarbonate, dibutyl pyrocarbonate, and ethylmethyl pyrocarbonate.

3. The lithium ion battery of claim 1, wherein the pyrocarbonate is dimethyl pyrocarbonate.

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

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

6. The lithium ion battery of claim 1, wherein the electrode comprises nanostructures, the nanostructures comprising the electrochemically active material.

7. The lithium ion battery of claim 6, wherein the nanostructures comprise nanowires.

8. The lithium ion battery of claim 7, wherein an outer surface of the nanowires comprise elemental silicon, silicon oxide, silicon alloy, or silicide.

9. 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.

12. 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.

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

14. 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.

15. The lithium ion battery of claim 14, wherein the one or more fluorinated carbonate solvents have a total concentration of less than about 10% by weight.

21. The lithium ion battery electrode of claim 1, wherein the electrolyte consists of one or more carbonate solvents, one or more lithium-containing salts, and one or more additives, the one or more additives including the pyrocarbonate.

22. The lithium ion battery electrode of claim 1, wherein the electrolyte comprises one or more pyrocarbonates that have a total concentration in the electrolyte of between 5% and 10% by weight.

23. The lithium ion battery of claim 1, wherein the solvent is substantially free from linear carbonates.

10. The lithium ion battery 1, wherein the electrolyte comprises one or more pyrocarbonates that have a total concentration in the electrolyte of less than about 50% by weight.

11. The lithium ion battery 1, wherein the electrolyte comprises one or more pyrocarbonates that have a total concentration in the electrolyte of between about 1% and 10% by weight.

16. A lithium ion battery electrolyte for use in a lithium ion battery containing high capacity active materials, the lithium ion battery electrolyte comprising:

a lithium containing salt;

a solvent substantially free from linear carbonates;

dimethyl pyrocarbonate (DMPC);

and one or more fluorinated carbonate solvents substantially free from linear carbonates, wherein the DMPC is present in the lithium battery electrolyte at a concentration between 5% and 10% by weight and wherein the one or more fluorinated carbonates are present in the lithium ion battery electrolyte at a concentration of between about 1% and 10% by weight.

17. The lithium ion battery electrolyte of claim 16, wherein at least one of the one or more fluorinated carbonate solvents is selected from the group consisting of mono-fluoroethylene carbonate, fluoropropylene carbonate, difluoroethylene carbonate, and fluoromethylethylene carbonate.

18. The lithium ion battery electrolyte of claim 17, wherein the one or more fluorinated carbonate solvents comprise mono-fluoroethylene carbonate (FEC).

19. The lithium ion battery electrolyte of claim 16, wherein the solvent is selected from the group consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DMC), and/or ethyl-methyl carbonate (EMC).

20. The lithium ion battery electrolyte of claim 16, wherein the lithium containing salt is selected from the group consisting of lithium hexafluorophosphate (LiPF₆), lithium hexafluoroarsenate monohydrate (LiAsF₆), lithium perchlorate (LiClO₄), lithium tetrafluoroborate (LiBF₄), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiODFB), LiPF₃(CF₂CF₃)₃ (LiFAP), and LiBF₃(CF₂CF₃)₃ (LiFAB).