Electrolyte including silane for use in electrochemical devices

• US 8,765,295 B2
• Filed: 12/12/2011
• Issued: 07/01/2014
• Est. Priority Date: 02/04/2004
• Status: Active Grant

• Current Assignee: Hiroshi Nakahara, Khalil Amine, Nicholas A.A. Rossi, Qingzheng Wang, Robert C. West, Sang Young Yoon, Zhengcheng Zhang
• Original Assignee: Hiroshi Nakahara, Khalil Amine, Nicholas A.A. Rossi, Qingzheng Wang, Robert C. West, Sang Young Yoon, Zhengcheng Zhang
• Inventors: West, Robert C., Amine, Khalil, Zhang, Zhengcheng, Wang, Qingzheng, Rossi, Nicholas A. A., Yoon, Sang Young, Nakahara, Hiroshi
• Primary Examiner(s): Ruddock, Ula C
• Assistant Examiner(s): PARK, LISA S
• Application Number:
  US13/323,602
• Publication Number:
  US 20120135313A1
• Time in Patent Office: 932 Days
• Field of Search: 429/188, 429/313, 556/470
• US Class Current: 429/188
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/0568 characterised by the solutes
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

The electrolyte includes one or more salts and a silane. The silane has a silicon linked to one or more first substituents that each include a poly(alkylene oxide) moiety or a cyclic carbonate moiety. The silane can be linked to four of the first substituents. Alternately, the silane can be linked to the one or more first substituents and one or more second substituents that each exclude both a poly(alkylene oxide) moiety and a cyclic carbonate moiety.

Claims

1. An electrochemical device, comprising:

a liquid electrolyte including one or more salts and a silane, wherein the silane is represented by;

2. The device of claim 1, wherein the electrolyte consists of the silane and the one or more salts.

3. The device of claim 1, wherein the silane is one of a plurality of silanes included in the electrolyte.

4. The device of claim 1, wherein the electrolyte further includes one or more secondary silanes represented by:

SiR_4-zR′

_xSiR_4-zR′

_z, wherein z is 1 to 3, R′

is an alkyl, a halogenated alkyl, aryl, halogenated aryl, an alkoxy, a halogenated alkoxy or is represented by formula III-D;

R is an alkoxy, a halogenated alkoxy, or is represented by formula III-D or is represented by formula III-F;

z is the number of R′

substituents included in the secondary silane and is 1 to 3; and

(4-z) is the number of R substituents included in the secondary silane;

5. The device of claim 1, wherein at least one of the one or more salts is a lithium salt.

6. The device of claim 1, wherein the molar concentration of the one or more salts is 0.1 to 3.0 M.

7. The device of claim 1, wherein at least one of the one or more salts is an organoborate salt.

8. The device of claim 1, wherein at least one of the one or more salts is chosen from the group consisting of LiClO₄, LiBF₄, LiAsF₆, LiPF₆, LiCF₃SO₃, Li(CF₃SO₂)₂N, Li(CF₃SO₂)₃C, LiN(SO₂C₂F₅)₂, lithium alkyl fluorophosphates and lithium bis(chelato)borates.

9. The device of claim 1, wherein the electrochemical device includes an anode and the electrolyte includes an additive selected to form a passivation layer on the anode.

10. The device of claim 1, wherein the electrochemical device includes an anode and the electrolyte includes an additive selected such that the additive is reduced at the surface of the anode so as to form a passivation layer on the anode.

11. The device of claim 1, wherein the electrochemical device includes an anode and the electrolyte includes an additive selected so as to polymerize at the surface of the anode such that a passivation layer is formed on the anode.

12. The device of claim 1, wherein the electrolyte further includes:

one or more additives selected from the group consisting of vinyl carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite, 1,3-dimethylbutadiene, styrene carbonate, aromatic carbonates, vinyl pyrrole, vinyl piperazine, vinyl piperadine, vinyl pyridine, and mixtures thereof.

13. The device of claim 1, wherein the electrolyte includes a lithium bis(oxalato)borate (LiBOB) salt and one or more additives selected from the group consisting of VC and VEC.

14. The device of claim 1, wherein the device is a lithium secondary battery wherein the electrolyte activates one or more lithium metal oxide cathodes and one or more anodes.

15. The device of claim 14, wherein at least one of the one or more cathodes includes a material chosen from the group consisting of:

Li_XVO_Y, LiCoO₂, LiNi_1-xCo_yMe_xO₂, LiMn_0.5Ni_0.5O₂, LiMn_0.3Co_0.3Ni_0.3O₂, LiFePO₄, LiMn₂O₄, LiFeO₂, LiMc_0.5Mn_1.5O₄, and mixtures thereof, wherein Me is Al, Mg, Ti, B, or Si, and Mc is a divalent metal.

16. The device of claim 14, wherein at least one of the one or more anodes include a material chosen from the group consisting of graphite, carbon, Li₄Ti₅O₁₂, tin alloys, silicon alloys, intermetallic compounds, lithium metal, and mixtures thereof.

17. An electrochemical device, comprising:

a liquid electrolyte including one or more salts and a silane, wherein the silane is represented by;

18. The device of claim 17, wherein the electrolyte consists of the silane and the one or more salts.

19. The device of claim 17, wherein the silane is one of a plurality of silanes included in the electrolyte.

20. The device of claim 17, wherein the electrolyte further includes one or more secondary silanes represented by:

SiR_4-zR′

_z, wherein z is 1 to 3, R′

is an alkyl, a halogenated alkyl, aryl, halogenated aryl, an alkoxy, a halogenated alkoxy or is represented by formula III-D;

R is an alkoxy, a halogenated alkoxy, or is represented by formula III-D or is represented by formula III-F;

z is the number of R′

substituents included in the secondary silane and is 1 to 3; and

(4-z) is the number of R substituents included in the secondary silane;

formula III-D;

21. The device of claim 17, wherein at least one of the one or more salts is a lithium salt.

22. The device of claim 17, wherein the molar concentration of the one or more salts is 0.1 to 3.0 M.

23. The device of claim 17, wherein at least one of the one or more salts is an organoborate salt.

24. The device of claim 17, wherein at least one of the one or more salts is chosen from the group consisting of LiClO₄, LiBF₄, LiAsF₆, LiPF₆, LiCF₃SO₃, Li(CF₃SO₂)₂N, Li(CF₃SO₂)₃C, LiN(SO₂C₂F₅)₂, lithium alkyl fluorophosphates and lithium bis(chelato)borates.

25. The device of claim 17, wherein the electrochemical device includes an anode and the electrolyte includes an additive selected to form a passivation layer on the anode.

26. The device of claim 17, wherein the electrochemical device includes an anode and the electrolyte includes an additive selected such that the additive is reduced at the surface of the anode so as to form a passivation layer on the anode.

27. The device of claim 17, wherein the electrochemical device includes an anode and the electrolyte includes an additive selected so as to polymerize at the surface of the anode such that a passivation layer is formed on the anode.

28. The device of claim 17, wherein the electrolyte further includes:

one or more additives selected from the group consisting of vinyl carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite, 1,3-dimethylbutadiene, styrene carbonate, aromatic carbonates, vinyl pyrrole, vinyl piperazine, vinyl piperadine, vinyl pyridine, and mixtures thereof.

29. The device of claim 17, wherein the electrolyte includes a lithium bis(oxalato)borate (LiBOB) salt and one or more additives selected from the group consisting of VC and VEC.

30. The device of claim 17, wherein the device is a lithium secondary battery wherein the electrolyte activates one or more lithium metal oxide cathodes and one or more anodes.

31. The device of claim 30, wherein at least one of the one or more cathodes includes a material chosen from the group consisting of:

Li_XVO_Y, LiCoO₂, LiNiO₂, LiNi_1-xCo_yMe_xO₂, LiMn_0.5Ni_0.5O₂, LiMn_0.3Co_0.3Ni_0.3O₂, LiFePO₄, LiMn₂O₄, LiFeO₂, LiMc_0.5Mn_1.5O₄, and mixtures thereof, wherein Me is Al, Mg, Ti, B, or Si, and Mc is a divalent metal.

32. The device of claim 30, wherein at least one of the one or more anodes include a material chosen from the group consisting of graphite, carbon, Li₄Ti₅O₁₂, tin alloys, silicon alloys, intermetallic compounds, lithium metal, and mixtures thereof.