Protected active metal electrode and battery cell structures with non-aqueous interlayer architecture

• US 7,829,212 B2
• Filed: 06/28/2007
• Issued: 11/09/2010
• Est. Priority Date: 02/06/2004
• Status: Active Grant

• Current Assignee: PolyPlus Battery Company
• Original Assignee: PolyPlus Battery Company
• Inventors: Visco, Steven J., Katz, Bruce D., De Jonghe, Lutgard C., Nimon, Yevgeniy S.
• Primary Examiner(s): DOVE, TRACY MAE
• Application Number:
  US11/824,597
• Publication Number:
  US 20080038641A1
• Time in Patent Office: 1,230 Days
• Field of Search: 429/117, 429/126, 429/142, 429/300, 429/303, 429337-339, 429/231.95
• US Class Current: 429/126
• CPC Class Codes: H01G 11/06 with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
• CPC Class Codes: H01G 11/52 Separators
• CPC Class Codes: H01G 11/58 Liquid electrolytes
• 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 10/0562 Solid materials
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0002 Aqueous electrolytes
• CPC Class Codes: H01M 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 4/13 Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 50/451 comprising layers of only organic material and layers containing inorganic material
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• 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

Abstract

Active metal and active metal intercalation electrode structures and battery cells having ionically conductive protective architecture including an active metal (e.g., lithium) conductive impervious layer separated from the electrode (anode) by a porous separator impregnated with a non-aqueous electrolyte (anolyte). This protective architecture prevents the active metal from deleterious reaction with the environment on the other (cathode) side of the impervious layer, which may include aqueous or non-aqueous liquid electrolytes (catholytes) and/or a variety electrochemically active materials, including liquid, solid and gaseous oxidizers. Safety additives and designs that facilitate manufacture are also provided.

Claims

1. An electrochemical cell structure, comprising:

an anode comprising a material selected from the group consisting of active metal, active metal-ion, active metal alloying metal, and active metal intercalating material; and

an ionically conductive protective architecture on a first surface of the anode, the architecture comprising,

an active metal ion conducting separator layer comprising a micro-porous polymer semi-permeable membrane impregnated with a non-aqueous anolyte, the separator layer being chemically compatible with the active metal, and in contact with the anode, and

a substantially impervious ionically conductive layer chemically compatible with the separator layer and with aqueous environments, and in contact with the separator layer.

2. The structure of claim 1, wherein the anolyte is in the liquid phase.

3. The structure of claim 2, wherein the anolyte comprises a solvent selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, sulfolane and combinations thereof.

4. The structure of claim 3, wherein the anolyte comprises a solvent selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME or higher glymes, sufolane, methyl formate, methyl acetate, and combinations thereof and a supporting salt selected from the group consisting of LiPF₆, LiBF₄, LiAsF₆, LiClO₄, LiSO₃CF₃, LiN(CF₃SO₂)₂ and LiN(SO₂C₂F₅)₂.

5. The structure of claim 4, wherein the anolyte further comprises 1,3-dioxolane.

6. The structure of claim 1, wherein the anolyte is in the gel phase.

7. The structure of claim 6, wherein the anolyte comprises a gelling agent selected from the group consisting of PVdF, PVdF-HFP copolymer, PAN, PEO and mixtures thereof;

a plasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC, THF, 2MeTHF, 1,2-DME and mixtures thereof; and

a Li salt selected from the group consisting of LiPF₆, LiBF₄, LiAsF₆, LiClO₄, LiSO₃CF₃, LiN(CF₃SO₂)₂ and LiN(SO₂C₂F₅)₂.

8. The structure of claim 1, wherein the substantially impervious ionically conductive layer comprises a material selected from the group consisting of glassy or amorphous active metal ion conductors, ceramic active metal ion conductors, and glass-ceramic active metal ion conductors.

9. The structure of claim 8, wherein the active metal is lithium.

10. The structure of claim 9, wherein substantially impervious ionically conductive layer is an ion conductive glass-ceramic having the following composition:

11. The structure of claim 1, wherein the substantially impervious ionically conductive layer has an ionic conductivity of at least 10⁻

5 S/cm.

12. The structure of claim 1, wherein non-aqueous electrolyte separator layer has an ionic conductivity of at least 10⁻

5 S/cm.

13. The structure of claim 1, wherein the anode comprises active metal.

14. The structure of claim 1, wherein the anode comprises active metal-ions.

15. The structure of claim 1, wherein the anode comprises active metal alloying metal.

16. The structure of claim 15, wherein the active metal alloying metal is selected from the group consisting of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In and Sb.

17. The structure of claim 1, wherein the anode comprises active metal intercalating material.

18. The structure of claim 17, wherein the active metal intercalating material comprises carbon.

19. The structure of claim 1, wherein the anode is lithium metal.

20. The structure of claim 1, wherein the anode is a lithium metal alloy.