Lithium ion secondary battery

• US 5,869,208 A
• Filed: 03/07/1997
• Issued: 02/09/1999
• Est. Priority Date: 03/08/1996
• Status: Expired due to Term

• Current Assignee: Furukawa Battery Company Limited (Furukawa Electric Company Limited)
• Original Assignee: Fuji Photo Film Co Limited (Fujifilm Holdings Corporation)
• Inventors: Miyasaka, Tsutomu
• Primary Examiner(s): Gorgos, Kathryn L.
• Assistant Examiner(s): Chaney, Carol
• Application Number:
  US08/812,548
• Time in Patent Office: 704 Days
• Field of Search: 429/48, 429/126, 429/215, 429/216, 429/224, 429/218, 429/194, 429/197, 429/198, 429/199, 429/137
• US Class Current: 429/224
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 4/134 Electrodes based on metals, Si or alloys
• 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 4/1395 of electrodes based on metals, Si or alloys
• 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 4/405 Alloys based on lithium
• 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: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

In a lithium ion secondary battery having a positive electrode, a negative electrode, a non-aqueous electrolyte, and a container, the positive electrode is made of a positive electrode active material having a spinel structure and the formula:

Li.sub.x Mn.sub.2-a M.sub.a/c O.sub.4+b

wherein M is cation of a metal other than Li and Mn; x, a and b are 0.1<x≦1.2, 0≦a<2.0 (preferably 0<a<2.0), 1≦c≦3, and 0≦b<0.3, during its charge-discharge cycle;

the positive electrode is coated with a non-electron conductive protective layer; and

the negative electrode is made of a negative electrode active material of a lithium alloy or an alloy into which a lithium ion can be intercalated.

Claims

1. A lithium ion secondary battery comprising a positive electrode, a negative electrode, a non-aqueous electrolyte, a container sealing the electrodes and electrolyte therein, wherein

the positive electrode comprises a positive electrode active material having a spinel structure and the formula:

space="preserve" listing-type="equation">Li.sub.x Mn.sub.2-a M.sub.a/c O.sub.4+b

Wherein M is cation of a metal other than Li and Mn;

x, a and b are numbers satisfying the conditions of 0.1<

x≦

1.2, 0≦

a<

2.0, 1≦

c≦

3, and 0≦

b<

0.3, respectively, during its charge-discharge cycle;

the positive electrode is coated with a non-electron conductive protective layer comprising particles of a metal oxide and a polymer binder; and

the negative electrode comprises a negative electrode active material of a lithium alloy or an alloy into which a lithium ion can be intercalated.

2. The lithium ion secondary battery of claim 1, wherein "a" of the formula satisfies the condition of 0<

a≦

0.1.

3. The lithium ion secondary battery of claim 1, wherein "x" and "a" of the formula satisfy the conditions of 0.1<

x<

1.0 and 0<

a≦

0.1, respectively.

4. The lithium ion secondary battery of claim 1, wherein "a" of the formula satisfies the condition of 0<

a≦

0.1, and "M" is cation of a transition metal selected from the group consisting of Co, Ni, Fe, Cr, Cu and Ti.

5. The lithium ion secondary battery of claim 1, wherein "a" of the formula satisfies the condition of 0<

a≦

0.1, and "M" is cation of a transition metal selected from the group consisting of Zr and Nb.

6. The lithium ion secondary battery of claim 1, wherein "a" of the formula satisfies the condition of 0<

a≦

0.1, and "M" is cation of a lanthanoid.

7. The lithium ion secondary battery of claim 1, wherein "a" of the formula satisfies the condition of 0<

a≦

0.1, and "M" is a cation of an alkali or alkaline earth metal selected from the group consisting of Na, K, Mg, Ca and Cs.

8. The lithium ion secondary battery of claim 1, wherein the non-electron conductive protective layer comprises particles of a metal oxide selected from the group consisting of aluminum oxide, titanium dioxide and zirconium oxide.

9. The lithium ion secondary battery of claim 1, wherein the negative electrode active material comprises a lithium-containing or non-lithium-containing metal alloy of elements selected from the group consisting of aluminum, magnesium, boron, antimony, bismuth, silicon, germanium, copper, titanium, gallium, and indium.

10. The lithium ion secondary battery of claim 1, wherein the negative electrode active material comprises a metal alloy of lithium and tin.

11. The lithium ion secondary battery of claim 1, wherein the negative electrode active material comprises an amorphous metal.

12. The lithium ion secondary battery of claim 1, wherein the non-aqueous electrolyte comprises a mixed solvent of ethylene carbonate and at least one other carbonate selected from the group consisting of diethyl carbonate and dimethyl carbonate, and a supporting salt comprising LiPF₆.

13. The lithium ion secondary battery of claim 1, wherein the container is in the form of a cylinder.

14. The lithium ion secondary battery of claim 1, wherein the metal oxide is present in the protective layer in an amount of not less than 70 weight % and not more than 99 weight %.

15. The lithium ion secondary battery of claim 1, wherein the protective layer has a thickness in the range of 1 to 20 μ

m.