Method of making an electrolyte activatable lithium-ion rechargeable battery cell

• US 5,456,000 A
• Filed: 01/05/1995
• Issued: 10/10/1995
• Est. Priority Date: 03/05/1993
• Status: Expired due to Term

• Current Assignee: Valence Technology Incorporated (Lithium Werks B.V.)
• Original Assignee: Bell Communications Research, Inc. (Telefonaktiebolaget LM Ericsson)
• Inventors: Gozdz, Antoni S., Tarascon, Jean-Marie, Warren, Paul C., Schmutz, Caroline N.
• Primary Examiner(s): Maples, John S.
• Application Number:
  US08/369,191
• Time in Patent Office: 278 Days
• Field of Search: 29/623.4, 29/623.2, 429/192
• US Class Current: 29/623.2
• CPC Class Codes: C08J 2327/16 Homopolymers or copolymers of vinylidene fluoride
• CPC Class Codes: C08J 9/28 by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• CPC Class Codes: H01M 10/0431 Cells with wound or folded electrodes H01M10/045 takes precedence
• CPC Class Codes: H01M 10/05 Accumulators with non-aqueous electrolyte H01M10/39 takes precedence
• 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 2300/0085 Immobilising or gelification of electrolyte
• CPC Class Codes: H01M 50/426 Fluorocarbon polymers
• CPC Class Codes: H01M 50/489 Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
• CPC Class Codes: H01M 50/497 Ionic conductivity
• CPC Class Codes: H01M 6/181 with polymeric electrolytes
• CPC Class Codes: H01M 6/30 Deferred-action cells
• CPC Class Codes: H01M 6/32 activated through external addition of electrolyte or of electrolyte components
• CPC Class Codes: H01M 6/42 Grouping of primary cells into batteries H01M6/40 takes precedence
• CPC Class Codes: H01M 6/46 of flat cells
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10T 29/4911 including sealing
• CPC Class Codes: Y10T 29/49114 including adhesively bonding

Abstract

Li-ion rechargeable battery cell electrode and electrolyte/separator elements formulated as layers of plasticized polymeric matrix compositions are laminated to form a unitary battery cell structure. The structure may be stored indefinitely, since it is essentially devoid of electrolyte solution which typically comprises a moisture-sensitive lithium salt. Prior to the battery'"'"'s being put into service, at least a portion of the compatible polymeric composition plasticizer is displaced by contact with a lithium salt electrolyte solution or is removed by extraction with a selective solvent and replaced with the electrolyte solution by simple imbibition. The battery thus activated may then be charged and recharged in the usual manner.

Claims

1. A method of making a rechargeable battery structure which comprises arranging, in sequence, a positive electrode element, a separator element, and a negative electrode element characterized in that

a) each of said electrode and separator elements comprises a flexible, polymeric matrix composition substantially devoid of electrolyte salt, and

b) said method further comprises bonding each said element to contiguous elements at its respective interface to form a unitary flexible laminate structure.

2. A method according to claim 1 wherein the polymeric matrix composition of at least said separator element comprises a compatible plasticizer and said method further comprises removing at least a portion of said plasticizer from said laminate structure.

3. A method according to claim 2 wherein the polymeric matrix composition of each said element comprises a compatible plasticizer and said method comprises removing at least a portion of said plasticizer from each said composition.

4. A method according to claim 2 wherein said portion of plasticizer is removed by displacement with a solution of electrolyte salt.

5. A method according to claim 2 wherein said portion of plasticizer is removed by extraction with a solvent to which the polymer of said composition is substantially inert.

6. A method according to claim 5 which further comprises substantially replacing the extracted plasticizer with a solution of electrolyte salt.

7. A method according to claim 2 wherein said matrix composition comprises a copolymer of vinylidene fluoride with 8 to 25% by weight hexafluoropropylene and has homogeneously distributed therein 20 to 70% by weight of an organic plasticizer compatible with said copolymer.

19. A method according to claim 1 wherein

a) said matrix composition comprises a copolymer of vinylidene fluoride with 8 to 25% by weight hexafluoropropylene and has homogeneously distributed therein 20 to 70% by weight of an organic plasticizer compatible with said copolymer;

b) said positive electrode element composition comprises a lithium intercalation compound homogeneously distributed in a matrix of said separator element composition;

c) said negative electrode element composition comprises a carbon intercalation compound homogeneously distributed in a matrix of said separator element composition; and

d) said laminate structure is contacted with a lithium battery electrolyte solution.

8. A method of making a rechargeable battery structure which comprises arranging, in sequence, a positive current collector element, a positive electrode element, a separator element, a negative electrode element, and a negative current collector element characterized in that

a) each of said collector elements comprises a flexible electrically-conductive foil,

b) each of said electrode and separator elements comprises a flexible, polymeric matrix composition substantially devoid of electrolyte salt, and

c) said method further comprises bonding each said element to contiguous elements at its respective interface to form a unitary flexible laminate structure.

9. A method according to claim 8 wherein each of said electrode and separator elements comprises a self-supporting film and said method further comprises bonding at least one of said positive and negative collector elements to its respective positive or negative electrode element prior to bonding said electrode elements to said separator element.

10. A method according to claim 8 wherein:

a) at least one of said collector element foils comprises an open-mesh grid;

b) the polymeric matrix composition of at least said separator element comprises a compatible plasticizer; and

c) said method further comprises removing at least a portion of said plasticizer from said laminate structure.

11. A method according to claim 10 wherein the polymeric matrix composition of each said element comprises a compatible plasticizer and said method comprises removing at least a portion of said plasticizer from each said composition.

12. A method according to claim 10 wherein said portion of plasticizer is removed by displacement with a solution of electrolyte salt.

13. A method according to claim 12 wherein said laminate structure is contacted with said electrolyte solution for a time sufficient to effect such displacement.

14. A method according to claim 11 which further comprises hermetically sealing said rechargeable battery structure within a moisture-proof enclosure.

15. A method according to claim 13 wherein

a) said matrix composition comprises a copolymer of vinylidene fluoride with 8 to 25% by weight hexafluoropropylene and has homogeneously distributed therein 20 to 70% by weight of an organic plasticizer compatible with said copolymer;

b) said positive electrode element composition comprises a lithium intercalation compound homogeneously distributed in a matrix of said separator element composition;

c) said negative electrode element composition comprises a carbon intercalation compound homogeneously distributed in a matrix of said separator element composition; and

d) said laminate structure is contacted with a lithium battery electrolyte solution.

16. A method according to claim 10 wherein said portion of plasticizer is removed by extraction with a solvent to which the polymer of said composition is substantially inert.

17. A method according to claim 16 which further comprises substantially replacing the extracted plasticizer with a solution of electrolyte salt.

18. A method according to claim 17 wherein said extracted laminate structure is contacted with said electrolyte solution for a time sufficient to effect the imbibing of said solution into said extracted structure.

20. A method according to claim 18 which further comprises hermetically sealing said rechargeable battery structure within a moisture-proof enclosure.

21. A method according to claim 20 wherein said laminate structure is sealed within said enclosure after contacting said solution.

22. A method according to claim 20 wherein, in either order:

a) an appropriate amount of electrolyte solution is introduced into said enclosure; and

b) said laminate structure is sealed within said enclosure after extraction of said plasticizing solvent.

23. A method according to claim 18 which further comprises:

a) hermetically sealing said rechargeable battery structure within a moisture-proof enclosure; and

b) providing means individually communicating electrically between the respective positive and negative current collector elements and the exterior of said enclosure.