Rechargeable non-aqueous thin film lithium battery

• US 5,512,389 A
• Filed: 05/05/1995
• Issued: 04/30/1996
• Est. Priority Date: 11/02/1994
• Status: Expired due to Term

• Current Assignee: Electrovaya Incorporated
• Original Assignee: Electrofuel, Inc.
• Inventors: Jacobs, James K., Dasgupta, Sankar
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/437,126
• Time in Patent Office: 361 Days
• Field of Search: 429/192, 429/194, 429/218, 429/127, 429/212, 252/182.1
• US Class Current: 429/312
• 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 rechargeable non-aqueous lithium battery comprising:

i) a battery housing means;

ii) a lithium containing negative electrode further comprising a first polymer laminate having embedded therein an electronically conductive carbonaceous substance, said first polymer laminate having a pair of parallel faces and being impervious to water, said first polymer laminate being permeable to electrons, and a continuous layer of agglomerated particles of fine carbon capable of intercalating lithium, located on one of the parallel faces of said first polymer laminate, said particles of fine carbon having been agglomerated with an organic binder containing a lithium compound, said continuous layer of agglomerated particles of fine carbon having thickness in excess of 0.5 mm;

iii) a lithium-ion conductive solid polymer laminate electrolyte further comprising a second polymer laminate having a pair of parallel faces, and a lithium compound capable of releasing mobile lithium ions dissolved in said second polymer laminate, said lithium compound having a first concentration in said second polymer laminate and said second polymer laminate being non-conductive of electrons, one of said pair of parallel faces of said second polymer laminate opposing said continuous layer of agglomerated particles of fine carbon comprised in said lithium containing negative electrode;

iv) a lithium containing positive electrode, further comprising a third polymer laminate having embedded therein an electronically conductive carbonaceous substance, said third polymer laminate having a pair of parallel faces and being impervious to water, said third polymer laminate being permeable to electrons, and a continuous layer of agglomerated fine particles of an oxide capable of incorporating lithium, located on one of the pair of parallel faces of said third polymer laminate, said oxide being one member of the group consisting of vanadium oxide, manganese oxide, cobalt oxide, nickel oxide and silver-vanadium oxide, said oxide having been agglomerated with an organic binder containing a lithium compound, said continuous layer of agglomerated fine particles of said oxide having thickness in excess of 0.5 mm, said continuous layer of agglomerated fine particles of said oxide opposing the other one of said pair of parallel faces of said second polymer laminate;

v) a first coating of a lithium ion containing fluid adhesive mixture disposed between at least a portion of said continuous layer of agglomerated particles of fine carbon comprised in said lithium containing negative electrode opposing one of the parallel faces of said second polymer laminate comprised in said lithium ion-conductive solid polymer laminate electrolyte, and a second coating of said lithium ion containing fluid adhesive mixture disposed between at least a portion of said continuous layer of agglomerated fine particles of said oxide comprised in said lithium containing positive electrode opposing the other one of said parallel faces of said second polymer laminate comprised in said lithium ion-conductive solid polymer laminate electrolyte, said lithium containing negative electrode being adherent to one of the pair of parallel faces of said lithium ion-conductive solid polymer laminate electrolyte and said lithium containing positive electrode being adherent to the other one of the pair of parallel faces of said lithium ion-conductive solid polymer laminate electrolyte, said first and said second coatings containing a lithium compound in a second concentration, said second lithium compound concentration being less than said first lithium compound concentration; and

vi) a first metallic current collector means in contact with the other one of said parallel faces of said first polymer laminate comprised in said lithium containing negative electrode, and a second metallic current collector means in contact with the other one of said parallel faces of said third polymer laminate comprised in said lithium containing positive electrode, and said first and said second current collector means having external electrical leads for discharging and charging said rechargeable non-aqueous lithium battery.

2. A rechargeable non-aqueous 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.

3. A rechargeable non-aqueous lithium battery as claimed in claim 1, wherein said second polymer laminate comprised in said lithium ion-conductive solid polymer laminate electrolyte is made of 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.

4. A rechargeable non-aqueous lithium battery as claimed in claim 1, wherein said lithium compound contained in said organic binder and dissolved in said second polymer laminate is selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride.

5. A rechargeable non-aqueous lithium battery comprising:

i) a battery housing means;

ii) a lithium containing negative electrode further comprising a first polymer laminate having embedded therein an electronically conductive carbonaceous substance, said first polymer laminate having a pair of parallel faces and being impervious to water, said first polymer laminate being permeable to electrons, and a continuous layer of agglomerated particles of fine carbon capable of intercalating lithium, located on one of the parallel faces of said first polymer laminate, said particles of fine carbon having been agglomerated with an organic binder containing a lithium compound, said continuous layer of agglomerated particles of fine carbon having thickness in excess of 0.5 mm;

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

iv) a lithium containing positive electrode, further comprising a third polymer laminate having embedded therein an electronically conductive carbonaceous substance, said third polymer laminate having a pair of parallel faces and being impervious to water, said third polymer laminate being permeable to electrons, and a continuous layer of agglomerated fine particles of an oxide capable of incorporating lithium, located on one of the pair of parallel faces of said third polymer laminate, said oxide being one member of the group consisting of vanadium oxide, manganese oxide, cobalt oxide, nickel oxide and silver-vanadium oxide, said oxide having been agglomerated with an organic binder containing a lithium compound, said continuous layer of agglomerated fine particles of said oxide having thickness in excess of 0.5 mm, said continuous layer of agglomerated fine particles of said oxide opposing the other one of said pair of parallel faces of said impregnated microporous laminate separator;

v) a first coating of a lithium ion containing fluid adhesive mixture disposed between at least a portion of said continuous layer of agglomerated particles of fine carbon comprised in said lithium containing negative electrode opposing one of the parallel faces of said impregnated area of said microporous polymer laminate separator, and a second coating of said lithium ion containing fluid adhesive mixture disposed between at least a portion of one of said continuous layer of agglomerated fine particles of said oxide comprised in said lithium containing positive electrode opposing other one the parallel faces of said impregnated area of said microporous polymer laminate separator, said lithium containing negative electrode being adherent to one of the pair of parallel faces of said impregnated area of said microporous polymer laminate separator and said lithium containing positive electrode being adherent to the other one of the pair of parallel faces of said impregnated area of said microporous polymer laminate separator, said first and said second coatings containing a lithium compound in a second concentration, and said second lithium compound concentration being less than said first lithium compound concentration; and

vi) a first current collector means in contact with the other one of said parallel faces of said first polymer laminate comprised in said lithium containing negative electrode, and a second current collector means in contact with the other one of said parallel faces of said third polymer laminate comprised in said lithium containing positive electrode, and said first and said second current collector means having external electrical leads for discharging and charging said rechargeable non-aqueous lithium battery.

6. A rechargeable non-aqueous lithium battery as claimed in claim 5, 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.

7. A rechargeable non-aqueous lithium battery as claimed in claim 5, wherein said microporous polymer laminate separator is made of a polymeric compound selected from the group consisting of polyethylene and polypropylene, and the organic liquid impregnating the micropores of said microporous polymer laminate separator is one member of the group consisting of ethylene carbonate, propylene carbonate and mixtures thereof.

8. A rechargeable non-aqueous lithium battery as claimed in claim 5, wherein said lithium compound contained in said organic binder and in said organic liquid impregnating said micropores of said microporous polymer laminate separator, is selected from the group consisting of lithium triflate, lithium perchlorate, lithium borofluoride, lithium arsenofluoride and lithium phosphofluoride.