Solid state rechargeable lithium battery, stacking battery, and charging method of the same

• US 6,022,640 A
• Filed: 09/08/1997
• Issued: 02/08/2000
• Est. Priority Date: 09/13/1996
• Status: Expired due to Term

• Current Assignee: Godo Kaisha IP Bridge 1 (IP Bridge, Inc.)
• Original Assignee: Matsushita Electric Industrial Company Limited (Panasonic Holdings Corporation)
• Inventors: Takada, Kazunori, Iwamoto, Kazuya, Fujino, Makoto, Kondo, Shigeo
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): Martin, Angela J.
• Application Number:
  US08/925,136
• Time in Patent Office: 883 Days
• Field of Search: 429/231.3, 429/312, 429/313, 429/231.95
• US Class Current: 429/231.95
• CPC Class Codes: H01M 10/052 Li-accumulators
• 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 10/0562 Solid materials
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 10/44 Methods for charging or discharging circuits for charging H02J7/00
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 2300/0025 Organic electrolyte
• 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 4/38 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: 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 4/5815 Sulfides
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A solid-state secondary lithium battery with excellent charge and discharge cycle characteristics, using a negative electrode active material which shows discontinuous change of potential caused by the lithium ion insertion and extraction reactions, wherein the amount of the lithium ion inserted, until discontinuous change of potential of the negative elctrode takes place, is equal to or smaller than the maximum amount of extraction of lithium ions within the range where lithium ions are inserted and extracted into or from the lithium transition metal oxide reversibly, and a battery assembly using these batteries.

Claims

1. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide.

2. The battery assembly according to claim 1, wherein the plural unit cells are housed in a single airtight battery container.

3. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide, and

wherein the material showing discontinuous change of potential consequent to the insertion and extraction reactions to lithium ions into or from the lithium ion sites in the crystal structure is at least one metal selected from the group consisting of indium, aluminum, lead, bismuth, antimony gallium, tin, silver, silicon, zinc, cadmium, arsenic and titanium, an alloy of the metals selected from the above group, or an alloy of lithium and at least one metal selected from the above group.

10. The battery assembly according to claim 3, wherein the plural unit cells are housed in a single airtight battery container.

4. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide, and

wherein the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure is indium, and the amount of the lithium ion inserted, until potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is the amount corresponding to the following reaction formula (1):

space="preserve" listing-type="equation">In+Li.sup.+ +e.sup.- →

In-Li (1).

11. The battery assembly according to claim 4, wherein the plural unit cells are housed in a single airtight battery container.

5. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide, and

wherein the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure is selected from the group consisting of transition metal oxides, lithium transition metal oxides, transition metal sulfides and lithium transition metal sulfides.

12. The battery assembly according to claim 5, wherein the plural unit cells are housed in a single airtight battery container.

6. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide, and

wherein the transition metal element of the lithium transition metal oxides is at least one element from the group consisting of cobalt, manganese and iron.

13. The battery assembly according to claim 6, wherein the plural unit cells are housed in a single airtight battery container.

7. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide, and

wherein the lithium ion conductive solid electrolyte is an inorganic compound.

14. The battery assembly according to claim 7, wherein the plural unit cells are housed in a single airtight battery container.

8. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted, until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide,

wherein the lithium ion conductive solid electrolyte is an inorganic compound, and

wherein the inorganic compound is an amorphous compound mainly composed of a sulfide.

15. The battery assembly according to claim 8, wherein the plural unit cells are housed in a single airtight battery container.

9. A battery assembly comprising plural electrically connected unit cells, which battery assembly has a structure of plural unit cells connected in series at a part of the battery assembly and a unit cell having at least the smallest capacity among the plural unit cells connected in series is a solid-state secondary lithium battery comprising (a) an electrolyte layer comprising mainly a lithium ion conductive solid electrolyte, (b) a positive electrode comprising a lithium transition metal oxide capable of inducing reversible electrochemical insertion and extraction reactions of lithium ions into or from lithium ion sites in a crystal structure, and (c) a negative electrode comprising a material showing discontinuous change of potential consequent to insertion and extraction reactions of lithium ions into or from the lithium ion sites in the crystal structure,

wherein an amount of the lithium ion inserted until a potential of the material showing discontinuous change of potential consequent to the insertion and extraction reactions of lithium ions discontinuously changes, is equal to or less than a maximum amount of an extracted amount of the lithium ions which is extracted by the reversible insertion and extraction reactions of the lithium transition metal oxide,

wherein the lithium ion conductive solid electrolyte is an inorganic compound, and

wherein the inorganic compound is synthesized from a material mainly composed of lithium sulfide and silicon sulfide.

16. The battery assembly according to claim 9, wherein the plural unit cells are housed in a single airtight battery container.