Non-aqueous lithium ion secondary battery

• US 5,677,083 A
• Filed: 12/19/1996
• Issued: 10/14/1997
• Est. Priority Date: 12/19/1995
• 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: Tomiyama, Hideki
• Primary Examiner(s): Skapars, Anthony
• Application Number:
  US08/769,525
• Time in Patent Office: 299 Days
• Field of Search: 429/194, 429/218, 429/209, 429/232, 429/66, 429/94, 252/182.1
• US Class Current: 429/231.3
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• 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 4/485 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: Y02E 60/10 Energy storage using batteries

Abstract

In a non-aqueous lithium ion secondary battery comprising a positive electrode sheet which comprises a lithium-containing transition metal oxide film, a negative electrode sheet which has a film of material capable of receiving and releasing a lithium ion, a non-aqueous electrolyte which contains a lithium salt, and a container which seals the electrodes and electrolyte therein, the lithium-containing transition metal oxide film comprises at least two layers, one of which expands during discharging while shrinks during charging, and another of which shrinks during discharging while expands during charging.

Claims

1. A non-aqueous lithium ion secondary battery comprising a positive electrode sheet which comprises a lithium-containing transition metal oxide film, a negative electrode sheet which has a film of material capable of receiving and releasing a lithium ion, a non-aqueous electrolyte which contains a lithium salt, and a container which seals the electrodes and electrolyte therein, wherein the lithium-containing transition metal oxide film comprises at least two layers, one of which expands during discharging while shrinks during charging, and another of which shrinks during discharging while expands during charging.

2. The non-aqueous lithium ion secondary battery of claim 1, wherein one of the two layers comprises a lithium-containing manganese oxide of a spinel structure, while another comprises a lithium-containing cobalt oxide.

3. The non-aqueous lithium ion secondary battery of claim 1, wherein one of the two layers comprises a lithium-containing manganese oxide of a spinel structure which is represented by Li_2-x Mn₂ O₄ wherein x is a number satisfying the condition of 0≦

x≦

1, while another comprises a lithium-containing cobalt oxide represented by Li_1-y CoO₂ wherein y is a number satisfying the condition of 0≦

y≦

1.

4. The non-aqueous lithium ion secondary battery of claim 1, wherein the film of material capable of receiving and releasing a lithium ion comprises an oxide or a chalcogenide comprising at least one element selected from the group consisting of Al, Ca, Si, Sn, Ge, Pb, Sb, and Bi.

5. The non-aqueous lithium ion secondary battery of claim 1, wherein the film of material capable of receiving and releasing a lithium ion comprises a complex oxide having the formula:

space="preserve" listing-type="equation">SnM.sup.1.sub.a O.sub.t

in which M¹ comprises at least two elements selected from the group consisting of Al, B, P, Si, Ge, Pb, Li, Na, K, Rb, Cs, Mg, Ca, Ba, and F; and

"a" and "t" are numbers satisfying the conditions of 0.2≦

a≦

2 and 1≦

t≦

6, respectively.

6. The non-aqueous lithium ion secondary battery of claim 1, wherein the film of material capable of receiving and releasing a lithium ion comprises a complex oxide having the formula:

space="preserve" listing-type="equation">SnM.sup.3.sub.c M.sup.4.sub.d O.sub.t

in which M³ is at least one element selected from the group consisting of Al, B, P, Ge;

M⁴ is at least one element selected from the group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Ba, and F;

"c" and "d" are numbers satisfying the conditions of 0.2≦

c≦

2, 0.01≦

d≦

1, and 0.2≦

c+d≦

2; and

"t" is a number satisfying the condition of 1≦

t≦

6.

7. The non-aqueous lithium ion secondary battery of claim 1, wherein the lithium-containing transition metal oxide film comprising at least two layers is prepared by simultaneous double coating of at least two slurries containing lithium-containing transition metal oxides differing from each other.

8. A non-aqueous lithium ion secondary battery comprising a positive electrode sheet which comprises a lithium-containing transition metal oxide film, a negative electrode sheet which has a film of material capable of receiving and releasing a lithium ion, a non-aqueous electrolyte which contains a lithium salt, and a container which seals the electrodes and electrolyte therein, wherein the lithium-containing transition metal oxide film comprises three layers which are composed of two layers expanding during discharging while shrinking during charging, and one layer shrinking during discharging while expanding during charging, the last layer intervening between the former two layers.

9. A non-aqueous lithium ion secondary battery comprising a positive electrode sheet which comprises a lithium-containing transition metal oxide film, a negative electrode sheet which has a film of material capable of receiving and releasing a lithium ion, a non-aqueous electrolyte which contains a lithium salt, and a container which seals the electrodes and electrolyte therein, wherein the lithium-containing transition metal oxide film comprises three layers which are composed of two layers shrinking during discharging while expanding during charging, and one layer expanding during discharging while shrinking during charging, the last layer intervening between the former two layers.