Method for forming an electrode-electrolyte assembly

• US 5,437,692 A
• Filed: 11/02/1994
• Issued: 08/01/1995
• Est. Priority Date: 11/02/1994
• Status: Expired due to Term

• Current Assignee: Electrovaya Incorporated
• Original Assignee: James K. Jacobs, Sankar Dasgupta
• Inventors: Dasgupta, Sankar, Jacobs, James K.
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/332,796
• Time in Patent Office: 272 Days
• Field of Search: 29/623.1, 29/623.2, 29/623.3, 29/623.5, 429/192, 429/212
• US Class Current: 29/623.1
• 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 4/587 for inserting or intercalating light metals
• CPC Class Codes: H01M 50/46 Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: H01M 50/461 with adhesive layers between electrodes and separators
• CPC Class Codes: H01M 6/40 Printed batteries , e.g. thin film batteries
• CPC Class Codes: Y10T 29/49108 Electric battery cell making
• CPC Class Codes: Y10T 29/49115 including coating or impregnating

Abstract

The non-aqueous thin film rechargeable lithium battery described has a negative electrode comprising a polymer laminate having embedded therein carbon, and a layer of fine carbon agglomerated with a lithium compound containing organic binder carried by the polymer laminate. The positive electrode of the rechargeable lithium battery contains a layer of fine particles of vanadium oxide, manganese oxide, cobalt oxide, nickel oxide or silver vanadate, agglomerated with a lithium compound containing organic binder and the layer is supported on another polymer laminate embedding carbon. In one embodiment the lithium battery has a solid polymer electrolyte containing a lithium compound capable of releasing lithium ions, located between the positive and negative electrodes. In another embodiment a microporous polymer laminate separator which has been impregnated with an organic liquid electrolyte containing a lithium compound, is placed between the polymer laminate negative electrode and the polymer laminate positive electrode. In both embodiments the electrodes are rendered adherent to the mobile lithium ion carrying electrolyte with a coating of an organic adhesive containing a lithium compound in a concentration lower than in the electrolyte, disposed between them.

Claims

1. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery, comprising the steps of:

i) providing a first polymer laminate having embedded therein an electronically conductive carbonaceous substance, said first polymer laminate having parallel faces and being impervious to water, said first polymer laminate being permeable to electrons;

ii) agglomerating particles of fine carbon capable of intercalating lithium, with a lithium compound containing organic binder, and providing a continuous layer of the agglomerated particles of fine carbon so obtained on one of said parallel faces of said first polymer laminate, said continuous layer having thickness in excess of 0.5 mm, thereby forming a lithium containing negative electrode;

iii) providing a second polymer laminate having parallel faces, said second polymer laminate being non-conductive of electrons, said second polymer laminate having a lithium compound dissolved therein in a first concentration, said lithium compound being capable of releasing mobile lithium ions, thereby forming a lithium ion-conductive solid polymer laminate electrolyte;

iv) providing a lithium ion containing fluid adhesive mixture and disposing said fluid adhesive mixture to form a lithium ion containing adhesive coating on at least a portion of one of the parallel faces of said lithium ion-conductive solid polymer laminate electrolyte, said fluid adhesive mixture containing a lithium compound in a second concentration, said second lithium compound concentration being less than said first lithium compound concentration; and

v) bringing into contact said lithium ion containing adhesive coating disposed on one of said parallel faces of said lithium ion-conductive solid polymer laminate electrolyte with said continuous layer of fine carbon agglomerated with a lithium compound containing organic binder located on one of said parallel faces of said first polymer laminate comprised in said lithium bearing negative electrode, thereby forming a lithium containing electrode-electrolyte assembly adherent to one another.

3. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 1, wherein said second polymer laminate comprises a polymeric compound selected from the group consisting of a polyether derivative copolymerized with a di-epoxy compound, a polyethylene-oxide based compound, a polypropylene-oxide based compound, a polyether-based polymer, a poly(epichlorhydrine) derivative containing compound, a poly(vinylidene fluoride) containing compound and an elastomerized organic polymer incorporating fine particles of a zeolitic substance.

5. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 1, wherein said lithium compound dissolved in said second polymer laminate in said first concentration is selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium phosphofluoride, lithium arsenofluoride and a lithium compound capable of releasing mobile lithium ions chemically bonded to a solid organic polymer.

7. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 5, wherein said first concentration of said lithium compound in said second polymer laminate is less than 2 Molar.

9. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 1, wherein said lithium ion containing adhesive coating is disposed on the entire face of one of said parallel faces of said lithium ion-conductive solid polymer laminate electrolyte.

11. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 1, wherein said lithium ion containing fluid adhesive mixture comprises an organic polymer selected from the group consisting of ethylene propylene-diamine monomer, poly(vinyledene fluoride), polyethylene-oxide and polypropylene-oxide, a lithium compound selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride, said organic polymer and said lithium compound being dispersed in a matrix selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, said lithium compound being present in said second concentration.

13. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 1, wherein said organic binder agglomerating said particles of fine carbon in said continuous layer, is selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and said lithium compound contained in said organic binder is one member of the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride.

15. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 1, wherein said continuous layer of agglomerated particles of fine carbon is embedded in a fourth polymer laminate having parallel faces.

2. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery compring the steps of:

i) providing a first polymer laminate having embedded therein an electronically conductive carbonaceous substance, said first polymer laminate having parallel faces and being impervious to water, said first polymer laminate being permeable to electrons;

ii) agglomerating fine particles of an oxide capable of incorporating lithium, with a lithium compound containing organic binder, said oxide being selected from the group consisting of vanadium oxide, manganese oxide, cobalt oxide, nickel oxide and silver-vanadium oxide, and providing a continuous layer of the agglomerated fine particles of oxide so obtained on one of said parallel faces of said first polymer laminate, said continuous layer having thickness in excess of 0.5 mm, thereby forming a lithium containing positive electrode;

iii) providing a second polymer laminate having parallel faces, said second polymer laminate being non-conductive of electrons, said second polymer laminate having a lithium compound dissolved therein in a first concentration, said lithium compound being capable of releasing mobile lithium ions, thereby forming a lithium ion-conductive solid polymer laminate electrolyte;

iv) providing a lithium ion containing fluid adhesive mixture and disposing said fluid adhesive mixture to form a lithium ion containing adhesive coating on at least a portion of one of the parallel faces of said lithium ion-conductive solid polymer laminate electrolyte, said fluid adhesive mixture containing a lithium compound in a second concentration, said second lithium compound concentration being less than said first lithium compound concentration; and

v) bringing into contact said lithium ion containing adhesive coating disposed on one of said parallel faces of said lithium ion-conductive solid polymer laminate electrolyte with said continuous layer of fine particles of said oxide agglomerated with a lithium compound containing organic binder located on one of said parallel faces of said first polymer laminate comprised in said lithium containing positive electrode, thereby forming a lithium containing electrode-electrolyte assembly adherent to one another.

4. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 2, wherein said second polymer laminate comprises a polymeric compound selected from the group consisting of a polyether derivative copolymerized with a di-epoxy compound, a polyethylene-oxide based compound, a polypropylene-oxide based compound, a polyether-based polymer, a poly(epichlorhydrine) derivative containing compound, a poly(vinylidene fluoride) containing compound and an elastomerized organic polymer incorporating fine particles of a zeolitic substance.

6. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 2, wherein said lithium compound dissolved in said second polymer laminate in said first concentration is selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium phosphofluoride, lithium arsenofluoride and a lithium compound capable of releasing mobile lithium ions chemically bonded to a solid organic polymer.

8. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 6, wherein said first concentration of said lithium compound in said second polymer laminate is less than 2 Molar.

10. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 2, wherein said lithium ion containing adhesive coating is disposed on the entire face of one of said parallel faces of said lithium ion-conductive solid polymer laminate electrolyte.

12. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 2, wherein said lithium ion containing fluid adhesive mixture comprises an organic polymer selected from the group consisting of ethylene propylene-diamine monomer, poly(vinyledene fluoride), polyethylene-oxide and polypropylene-oxide, a lithium compound selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride, said organic polymer and said lithium compound being dispersed in a matrix selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, said lithium compound being present in said second concentration.

14. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 2, wherein said organic binder agglomerating said fine particles of said oxide in said continuous layer, is selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and said lithium compound contained in said organic binder is one member of the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride.

16. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 2, wherein said continuous layer of agglomerated fine particles of an oxide is embedded in a fourth polymer laminate having parallel faces.

17. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery, comprising the steps of:

i) providing a first polymer laminate having embedded therein an electronically conductive carbonaceous substance, said first polymer laminate having parallel faces and being impervious to water, said first polymer laminate being permeable to electrons;

ii) agglomerating particles of fine carbon capable of intercalating lithium, with a lithium compound containing organic binder, and providing a continuous layer of the agglomerated particles of fine carbon so obtained on one of said parallel faces of said first polymer laminate, said continuous layer having thickness in excess of 0.5 mm, thereby forming a lithium containing negative electrode;

iii) providing a microporous polymer laminate separator having a pair of parallel faces, and impregnating an area of said microporous polymer laminate separator with an organic liquid containing a lithium compound in a first concentration, said lithium compound being capable of releasing lithium ions, said impregnated area of said microporous polymer laminate separator substantially corresponding to said agglomerated layer of particles of fine carbon located on one of the parallel faces of said first polymer laminate comprised in said lithium containing negative electrode, said microporous polymer laminate separator being non-conductive of electrons and lithium ions;

iv) providing a lithium ion containing fluid adhesive mixture and disposing said mixture to form a lithium ion containing adhesive coating on at least a portion of one of the parallel faces of said impregnated area of said microporous polymer laminate separator, said fluid adhesive mixture containing a lithium compound in a second concentration, said second lithium compound concentration being less than said first lithium compound concentration; and

v) bringing into contact said lithium ion containing adhesive coating disposed on one of said parallel faces of said impregnated area of said microporous polymer laminate separator with said continuous layer of fine carbon agglomerated with a lithium compound containing organic binder located on one of said parallel faces of said first polymer laminate comprised in said lithium containing negative electrode, thereby forming a lithium containing electrode-electrolyte assembly adherent to one another.

19. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 17, wherein said microporous polymer laminate separator comprises a polymeric compound selected from the group consisting of polyethylene and polypropylene.

21. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 17, wherein said organic liquid impregnating said microporous polymer laminate separator is selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and said lithium compound contained in said organic liquid impregnating said microporous polymer laminate is selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium phosphofluoride and lithium arsenofluoride.

25. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 17, wherein said coating of said fluid adhesive mixture containing a lithium compound is disposed on the entire face of one of said parallel faces of said impregnated area of said microporous polymer laminate separator corresponding to the entire face of said first polymer laminate comprised in said lithium containing negative electrode.

27. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 17, wherein said fluid adhesive mixture containing a lithium compound comprises an organic polymer selected from the group consisting of ethylene propylene-diamine monomer, poly(vinylidene fluoride), polyethylene-oxide and polypropylene-oxide, a lithium compound selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride, said organic polymer and said lithium compound being dispersed in a matrix selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, said lithium compound being present in said second concentration.

29. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 17, wherein said organic binder for agglomerating said particles of fine carbon in said continuous layer, is selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and said lithium compound contained in said organic binder is one member of the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride.

31. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 17, wherein said continuous layer of agglomerated particles of fine carbon is embedded in a fourth polymer laminate having parallel faces.

18. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery, comprising the steps of:

i) providing a first polymer laminate having embedded therein an electronically conductive carbonaceous substance, said first polymer laminate having parallel faces and being impervious to water, said first polymer laminate being permeable to electrons;

ii) agglomerating fine particles of an oxide capable of incorporating lithium, with a lithium compound containing organic binder, said oxide being selected from the group consisting of vanadium oxide, manganese oxide, cobalt oxide, nickel oxide and silver-vanadium oxide, and providing a continuous layer of the agglomerated fine particles of oxide so obtained on one of said parallel faces of said first polymer laminate, said continuous layer having thickness in excess of 0.5 mm, thereby forming a lithium containing positive electrode;

iii) providing a microporous polymer laminate separator having a pair of parallel faces, and impregnating an area of said microporous polymer laminate separator with an organic liquid containing a lithium compound in a first concentration, said lithium compound being capable of releasing lithium ions, said impregnated area of said microporous polymer laminate separator substantially corresponding to said agglomerated layer of fine particles of said oxide located on one of the parallel faces of said first polymer laminate comprised in said lithium containing positive electrode, said microporous polymer laminate separator being non-conductive of electrons and lithium ions;

iv) providing a lithium ion containing fluid adhesive mixture and disposing said mixture to form a lithium ion containing adhesive coating on at least a portion of one of the parallel faces of said impregnated area of said microporous polymer laminate separator, said fluid adhesive mixture containing a lithium compound in a second concentration, said second lithium compound concentration being less than said first lithium compound concentration; and

v) bringing into contact said lithium ion containing adhesive coating disposed on one of said parallel faces of said impregnated area of said microporous polymer laminate separator with said continuous layer of fine particles of said oxide agglomerated with a lithium compound containing organic binder located on one of said parallel faces of said first polymer laminate comprised in said lithium containing positive electrode, thereby forming a lithium containing electrode-electrolyte assembly adherent to one another.

20. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 18, wherein said microporous polymer laminate separator comprises a polymeric compound selected from the group consisting of polyethylene and polypropylene.

22. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 18, wherein said organic liquid impregnating said microporous polymer laminate separator is selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and said lithium compound contained in said organic liquid impregnating said microporous polymer laminate separator is selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium phosphofluoride and lithium arsenofluoride.

26. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 18, wherein said coating of said fluid adhesive mixture containing a lithium compound is disposed on the entire face of one of said parallel faces of said impregnated area of said microporous polymer laminate separator corresponding to the entire face of said first polymer laminate comprised in said lithium containing positive electrode.

28. A method for forming an electrode-electrolyte assembly for incorporation in a rechargable lithium battery as claimed in claim 18, wherein said fluid adhesive mixture containing a lithium compound comprises an organic polymer selected from the group consisting of ethylene propylene-diamine monomer, poly(vinylidene fluoride), polyethylene-oxide and polypropylene-oxide, a lithium compound selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride, said organic polymer and said lithium compound being dispersed in a matrix selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, said lithium compound being present in said second concentration.

30. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 18, wherein said organic binder for agglomerating said fine particles of said oxide in said continuous layer, is selected from the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof, and said lithium compound contained in said organic binder is one member of the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride.

32. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed in claim 18, wherein said continuous layer of agglomerated fine particles of said oxide is embedded in a fourth polymer laminate having parallel faces.

23. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed 17, wherein said first concentration of said lithium compound in said organic liquid impregnating said microporous polymer laminate separator is less than 2 Molar.

24. A method for forming an electrode-electrolyte assembly for incorporation in a rechargeable lithium battery as claimed 18, wherein said first concentration of said lithium compound in said organic liquid impregnating said microporous polymer laminate separator is less than 2 Molar.