Secondary battery

• US 5,824,434 A
• Filed: 11/30/1993
• Issued: 10/20/1998
• Est. Priority Date: 11/30/1992
• Status: Expired due to Fees

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Kawakami, Soichiro, Kobayashi, Naoya, Mishina, Shinya
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Everhart, Caridad
• Application Number:
  US08/159,141
• Time in Patent Office: 1,785 Days
• Field of Search: 429/209, 429/245, 429/214, 429/215, 427/247, 427/144, 427/145
• US Class Current: 429/209
• 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 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 10/058 Construction or manufacture
• CPC Class Codes: H01M 10/0585 of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
• CPC Class Codes: H01M 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• CPC Class Codes: H01M 10/24 Alkaline accumulators
• CPC Class Codes: H01M 10/30 Nickel accumulators H01M10/34 takes precedence
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2004/027 Negative electrodes
• CPC Class Codes: H01M 4/02 Electrodes composed of, or comprising, active material
• CPC Class Codes: H01M 4/04 Processes of manufacture in general
• CPC Class Codes: H01M 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/0404 by coating on electrode collectors
• CPC Class Codes: H01M 4/0409 by a doctor blade method, slip-casting or roller coating
• CPC Class Codes: H01M 4/0414 by screen printing
• CPC Class Codes: H01M 4/0416 involving impregnation with a solution, dispersion, paste or dry powder H01M4/0438 takes precedence
• CPC Class Codes: H01M 4/0419 involving spraying
• CPC Class Codes: H01M 4/0421 involving vapour deposition
• CPC Class Codes: H01M 4/0426 Sputtering
• CPC Class Codes: H01M 4/0428 : Chemical vapour deposition
• CPC Class Codes: H01M 4/043 : involving compressing or compaction
• CPC Class Codes: H01M 4/0435 : Rolling or calendering
• CPC Class Codes: H01M 4/0438 : by electrochemical processing electroless electrochemical plating C23C18/54
• CPC Class Codes: H01M 4/045 : Electrochemical coating; Electrochemical impregnation
• CPC Class Codes: H01M 4/0452 : from solutions
• CPC Class Codes: H01M 4/0466 : Electrochemical polymerisation
• CPC Class Codes: H01M 4/0471 : involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• 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 4/131 : Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/133 : Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
• CPC Class Codes: H01M 4/134 : Electrodes based on metals, Si or alloys
• CPC Class Codes: H01M 4/139 : Processes of manufacture
• CPC Class Codes: H01M 4/1391 : of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/24 : Electrodes for alkaline accumulators
• CPC Class Codes: H01M 4/244 : Zinc electrodes
• CPC Class Codes: H01M 4/36 : Selection of substances as active materials, active masses, active liquids
• CPC Class Codes: H01M 4/366 : as layered products
• CPC Class Codes: H01M 4/38 : of elements or alloys
• CPC Class Codes: H01M 4/40 : Alloys based on alkali metals
• CPC Class Codes: H01M 4/42 : Alloys based on zinc
• CPC Class Codes: H01M 4/48 : of inorganic oxides or hydroxides
• CPC Class Codes: H01M 4/485 : of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 : of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 : of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: H01M 4/58 : of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
• CPC Class Codes: H01M 4/581 : Chalcogenides or intercalation compounds thereof
• CPC Class Codes: H01M 4/582 : Halogenides
• CPC Class Codes: H01M 4/62 : Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• CPC Class Codes: H01M 4/621 : Binders
• CPC Class Codes: H01M 4/622 : being polymers
• CPC Class Codes: H01M 4/623 : fluorinated polymers
• CPC Class Codes: H01M 4/625 : Carbon or graphite
• CPC Class Codes: H01M 4/74 : Meshes or woven material; Expanded metal
• CPC Class Codes: H01M 4/742 : perforated material
• CPC Class Codes: H01M 4/808 : Foamed, spongy materials
• CPC Class Codes: H01M 50/46 : Separators, membranes or diaphragms characterised by their combination with electrodes
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries
• CPC Class Codes: Y10T 29/49108 : Electric battery cell making

Abstract

A secondary battery exhibiting a long cycle life and comprising a negative pole activating material made of lithium or zinc is provided, the battery at least having a negative pole made of lithium or zinc serving as the negative pole activating material, an electrolyte (electrolytic solution), a separator, a positive pole made of a positive pole activating material, a collecting electrode and a battery case, wherein at least the surface of the negative pole is covered with a film having a structure which allows ions relating to the battery reactions to pass through. Since growth of dendrite of lithium or zinc at the time of the charge can be prevented, short circuit between the negative pole and the positive pole can be prevented. Therefore, the charge/discharge cycle life can significantly be lengthened. As a result, a lithium secondary battery, a nickel-zinc secondary battery, an air-zinc secondary battery, a bromine-zinc secondary battery and a silver oxide-zinc secondary battery of the long cycle life can be manufactured.

Claims

1. A secondary battery having a negative electrode made of a negative electrode active material and a positive electrode made of a positive electrode active material and arranged in such a manner that said negative electrode active material and said positive electrode active material are separated from each other by a separator, said secondary battery comprising:

a multi-layered metal oxide film disposed between said positive electrode and said negative electrode and having small apertures to pass therethrough ions generated during operation of said secondary battery and to inhibit growth of dendrites grown from said negative electrode or said positive electrode during said battery operation.

2. A secondary battery according to claim 1, wherein said multi-layered metal oxide film contains at least one material selected from the group consisting of alumina, titanium oxide, silica, selenium oxide, zirconia oxide, magnesium oxide, chrome oxide, calcium oxide, tin oxide, indium oxide and germanium oxide.

3. A secondary battery according to claim 1, wherein said multi-layered metal oxide film is formed employing a bimolecular film as a template to orient the metal oxide as a multi-layered film.

4. A secondary battery according to claim 3, wherein said bimolecular film is a compound of an amphipathic material having both a hydrophobic group and a hydrophilic group.

5. A secondary battery according to claim 3, wherein said bimolecular film is formed in a film shape combining an amphipathic material and a polymer compound.

6. A secondary battery according to claim 3, wherein said bimolecular film is a polyion reactant of an ionic amphipathic material and a polymer electrolyte.

7. A secondary battery according to claim 1, wherein said multi-layered metal oxide film is a composite of an organic polymer.

8. A secondary battery according to claim 1, wherein said separator comprises said multi-layered metal oxide film and at least one polymer sheet.

9. A secondary battery according to claim 1, wherein the surface of said positive pole made of said positive pole activating material and opposing said negative pole is covered with at least a film through which ions relating to battery reactions are able to pass.

10. A secondary battery according to claim 1, wherein the surface of said negative pole made of said negative pole activating material and opposing said positive pole is covered with at least a film through which ions relating to battery reactions are able to pass.

11. A secondary battery according to claim 9, wherein said film through which the ions relating to the battery reactions are able to pass is a multilayered metal oxide film prepared employing a bimolecular film as a template to orient the metal oxide in a multi-layer structure.

12. A secondary battery according to claim 1, wherein said negative pole activating material is lithium or lithium alloy.

13. A secondary battery according to claim 1, wherein said negative pole activating material is zinc or zinc alloy.

14. A secondary battery according to claim 1, wherein said multi-layered metal oxide film is subjected to lipophilic treatment.

15. A secondary battery according to claim 1, wherein said multi-layered metal oxide film has a conductor member on the surface thereof which opposes said negative electrode.

16. A secondary battery according to claim 1, wherein said negative electrode active material contains lithium.