Non-aqueous electrolyte for secondary battery and non-aqueous electrolyte secondary battery

• US 8,945,781 B2
• Filed: 02/05/2008
• Issued: 02/03/2015
• Est. Priority Date: 02/20/2007
• Status: Active Grant

• Current Assignee: Kanto Denka Kogyo Co., Ltd., Panasonic Energy (Shanghai) Co., Ltd. (Panasonic Holdings Corporation)
• Original Assignee: Kanto Denka Kogyo Co., Ltd., Sanyo Electric Company Limited (Panasonic Holdings Corporation)
• Inventors: Chiga, Takanobu, Saisho, Keiji, Omae, Osamu, Mogi, Ryo
• Primary Examiner(s): WEINER, LAURA S
• Application Number:
  US12/522,231
• Publication Number:
  US 20100081062A1
• Time in Patent Office: 2,555 Days
• Field of Search: 429/343, 429/341, 429/199, 429/200, 429/330, 429/322, 429/317, 252/62.2
• US Class Current: 429/343
• 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 10/0567 characterised by the additives
• CPC Class Codes: H01M 10/0569 characterised by the solvents
• CPC Class Codes: H01M 2300/0028 characterised by the solvent
• CPC Class Codes: H01M 2300/0034 Fluorinated solvents
• CPC Class Codes: H01M 2300/0037 Mixture of solvents
• CPC Class Codes: H01M 2300/004 Three solvents
• 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: Y02E 60/10 Energy storage using batteries

Abstract

The present invention provides a non-aqueous electrolyte secondary battery wherein a reaction between a non-aqueous electrolyte and an electrode is suppressed and decrease in battery capacity under high temperature is restricted, so that long time excellent battery characteristics can be obtained. A non-aqueous solvent of the non-aqueous electrolyte contains: chain fluorinated carboxylic acid ester represented by the formula R1-CH₂—COO—R2 where R1 represents hydrogen or alkyl group and R2 represents alkyl group and the sum of the carbon numbers of R1 and R2 is 3 or less, and in the case that R1 is hydrogen, at least one part of hydrogen in R2 is replaced with fluorine, and, in the case that R1 is alkyl group, at least one part of hydrogen in R1 and/or R2 is replaced with fluorine; and a film forming chemical compound decomposed in the range of +1.0 to 3.0 V based on an equilibrium potential between metal lithium and lithium ion.

Claims

1. A non-aqueous electrolyte for secondary battery comprising a non-aqueous solvent dissolving lithium salt as an electrolyte,

wherein said non-aqueous solvent contains:

(A) methyl 3,3,3-trifluoropropionate represented by the below formula (1);

CF₃—

CH₂—

COO—

CH₃ 

 

(1)

and

(B) a film-forming chemical compound decomposed in the range of +1.0 to 3.0 V based on an equilibrium potential between metal lithium and lithium ion;

wherein said film-forming chemical compound is at least one selected from the group consisting of 4-fluoroethylene carbonate, ethylene sulfite, vinyl ethylene carbonate, LiB(C₂O₄)₂, and LiBF₂(C₂O₄);

wherein said non-aqueous solvent further contains at least one low viscosity solvent selected from a group of CH₃COOCH₃, C₂H₅COOCH₃, CH₃COOC₂H₅, and CH₃OCOOCH₃;

wherein the amount of said methyl 3,3,3-trifluoropropionate is in the range of 20 to 90 volume % to the whole amount of non-aqueous solvent; and

wherein the amount of said 4-fluoroethylene carbonate to the whole amount of non-aqueous solvent is 2-40 volume %, the amount of said ethylene sulfite and said vinyl ethylene carbonate to the whole amount of non-aqueous solvent is 0.1-10 wt %, and the amount of said LiB(C₂O₄)₂ and said LiBF₂(C₂O₄) to the whole amount of non-aqueous solvent is 0.01-0.4 mol/l.

2. The non-aqueous electrolyte for secondary battery as claimed in claim 1, wherein said film-forming chemical compound is 4-fluoroethylene carbonate.

3. The non-aqueous electrolyte for secondary battery as claimed in claim 1, wherein said film-forming chemical compound is 4-fluoroethylene carbonate and the amount of the 4-fluoroethylene carbonate is in the range of 5 to 30 volume % to the whole amount of non-aqueous solvent.

4. A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte,

wherein said non-aqueous electrolyte comprises a non-aqueous solvent dissolving lithium salt as an electrolyte;

wherein said non-aqueous solvent contains;

(A) methyl 3,3,3-trifluoropropionate represented by the below formula (1);

CF₃—

CH₂—

COO—

CH₃ 

 

(1)

and

(B) a film-forming chemical compound decomposed in the range of +1.0 to 3.0 V based on an equilibrium potential between metal lithium and lithium ion;

wherein said film-forming chemical compound is at least one selected from a group consisting of 4-fluoroethylene carbonate, ethylene sulfite, vinyl ethylene carbonate, LiB(C₂O₄)₂, and LiBF₂(C₂O₄); and

wherein said non-aqueous solvent further contains at least one low viscosity solvent selected from a group of CH₃COOCH₃, C₂H₅COOCH₃, CH₃COOC₂H₅, and CH₃OCOOCH₃;

wherein the amount of said methyl 3,3,3-trifluoropropionate is in the range of 20 to 90 volume % to the whole amount of non-aqueous solvent and

wherein the amount of said 4-fluoroethylene carbonate to the whole amount of non-aqueous solvent is 2-40 volume %, the amount of said ethylene sulfite and said vinyl ethylene carbonate to the whole amount of non-aqueous solvent is 0.1-10 wt %, and the amount of said LiB(C₂O₄)₂ and said LiBF₂(C₂O₄) to the whole amount of non-aqueous solvent is 0.01-0.4 mol/l.

5. The non-aqueous electrolyte secondary battery as claimed in claim 4, wherein said film-forming chemical compound is 4-fluoroethylene carbonate.

6. The non-aqueous electrolyte secondary battery as claimed in claim 4, wherein said film-forming chemical compound is 4-fluoroethylene carbonate and the amount of the 4-fluoroethylene carbonate is in the range of 5 to 30 volume % to the whole amount of non-aqueous solvent.

7. The non-aqueous electrolyte secondary battery as claimed in claim 4 which is charged until a potential of the positive electrode becomes 4.35 V or more based on metal lithium.

8. A non-aqueous electrolyte for secondary battery comprising a non-aqueous solvent dissolving lithium salt as an electrolyte,

wherein said non-aqueous solvent contains:

(A) methyl 3,3,3-trifluoropropionate represented by the below formula (1);

CF₃—

CH₂—

COO—

CH₃ 

 

(1)

and

(B) a film-forming chemical compound decomposed in the range of +1.0 to 3.0 V based on an equilibrium potential between metal lithium and lithium ion;

wherein said film-forming chemical compound is at least one selected from the group consisting of 4-fluoroethylene carbonate, ethylene sulfite, vinyl ethylene carbonate, LiB(C₂O₄)₂, and LiBF₂(C₂O₄); and

wherein the amount of said methyl 3,3,3-trifluoropropionate is in the range of 20 to 90 volume % to the whole amount of the non-aqueous solvent; and

wherein the amount of said 4-fluoroethylene carbonate to the whole amount of non-aqueous solvent is 2-40 volume %, the amount of said ethylene sulfite and said vinyl ethylene carbonate to the whole amount of non-aqueous solvent is 0.1-10 wt %, and the amount of said LiB(C₂O₄)₂ and said LiBF₂(C₂O₄) to the whole amount of non-aqueous solvent is 0.01-0.4 mol/l.

9. The non-aqueous electrolyte for secondary battery as claimed in claim 8, wherein the lithium salt main comprises LiPF₆.

10. The non-aqueous electrolyte for secondary battery as claimed in claim 8, wherein said film-forming chemical compound is 4-fluoroethylene carbonate.

11. The non-aqueous electrolyte for secondary battery as claimed in claim 8, wherein said film-forming chemical compound is 4-fluoroethylene carbonate and the amount of the 4-fluoroethylene carbonate is in the range of 5 to 30 volume % to the whole amount of non-aqueous solvent.

12. A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte,

wherein said non-aqueous electrolyte comprises a non-aqueous solvent dissolving lithium salt as an electrolyte;

wherein said non-aqueous solvent contains;

(A) methyl 3,3,3-trifluoropropionate represented by the below formula (1);

CF₃—

CH₂—

COO—

CH₃ 

 

(1)

and

(B) a film-forming chemical compound decomposed in the range of +1.0 to 3.0 V based on an equilibrium potential between metal lithium and lithium ion;

wherein said film-forming chemical compound is at least one selected from a group consisting of 4-fluoroethylene carbonate, ethylene sulfite, vinyl ethylene carbonate, LiB(C₂O₄)₂, and LiBF₂(C₂O₄); and

wherein the amount of said methyl 3,3,3-trifluoropropionate is in the range of 20 to 90 volume % to the whole amount of the non-aqueous solvent; and

wherein the amount of said 4-fluoroethylene carbonate to the whole amount of non-aqueous solvent is 2-40 volume %, the amount of said ethylene sulfite and said vinyl ethylene carbonate to the whole amount of non-aqueous solvent is 0.1-10 wt %, and the amount of said LiB(C₂O₄)₂ and said LiBF₂(C₂O₄) to the whole amount of non-aqueous solvent is 0.01-0.4 mol/l.

13. The non-aqueous electrolyte secondary battery as claimed in claim 12, wherein the lithium salt main comprises LiPF₆.

14. The non-aqueous electrolyte secondary battery as claimed in claim 12, wherein said film-forming chemical compound is 4-fluoroethylene carbonate.

15. The non-aqueous electrolyte secondary battery as claimed in claim 12, wherein said film-forming chemical compound is 4-fluoroethylene carbonate and the amount of the 4-fluoroethylene carbonate is in the range of 5 to 30 volume % to the whole amount of non-aqueous solvent.

16. The non-aqueous electrolyte secondary battery as claimed in claim 12 which is charged until a potential of the positive electrode becomes 4.35 V or more based on metal lithium.