Secondary battery including an electrolytic solution with an organic additive

• US 6,303,250 B1
• Filed: 04/09/1999
• Issued: 10/16/2001
• Est. Priority Date: 04/09/1999
• Status: Expired due to Fees

• Current Assignee: Matsushita Electric Industrial Company Limited (Panasonic Holdings Corporation)
• Original Assignee: Matsushita Electric Industrial Company Limited (Panasonic Holdings Corporation)
• Inventors: Iwamoto, Kazuya, Ueda, Atsushi, Nunome, Jun, Watanabe, Shoichiro, Koshina, Hizuru
• Primary Examiner(s): Brouillette, Gabrielle
• Assistant Examiner(s): Ruthkosky, Mark
• Application Number:
  US09/289,468
• Time in Patent Office: 921 Days
• Field of Search: 429/328, 429/303, 429/306
• US Class Current: 429/306
• 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 10/0587 of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
• 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: 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
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y02T 10/70 Energy storage systems for electromobility, e.g. batteries

Abstract

A battery excellent in high temperature storage characteristic is presented. It comprises a positive electrode containing a positive electrode active material, a negative electrode containing a negative electrode material, a nonaqueous solvent, and an electrolytic solution containing at least one of organic compounds expressed in formula 1 and formula 2. The positive electrode active material has an oxide compound containing a lithium atom, and the negative electrode material has a material capable of storing and releasing a lithium ion.

Formula 1

where R₁, R₂, R₃, R₄ are individually at least one selected from the group consisting of H, aryl group, and aryl group having a functional group containing a substituent having an electron attracting property, and the number of H is three or less.

Formula 2

Claims

1. A secondary battery comprising:

a positive electrode comprising a positive electrode active material;

a negative electrode comprising a negative electrode material; and

a electrolytic solution comprising a nonaqueous solvent and at least one organic compound selected from the group consisting of;

and compounds represented by formula 1;

in which;

R₁, R₂, R₃, and R₄ are each independently (i) hydrogen, (ii) an aryl group, or (iii) an aryl group having a functional group containing a substituent having an electron attracting property; and

at least one of R₁, R₂, R₃, and R₄ is either (ii) an aryl group, or (iii) an aryl group having a functional group containing a substituent having an electron attracting property;

in which;

the positive electrode active material comprises a transition metal complex oxide comprising lithium; and

the negative electrode material comprises a material capable of storing and releasing lithium ions.

2. The secondary battery of claim 1 in which:

the positive electrode active material comprises a transition metal complex oxide comprising lithium; and

the negative electrode material comprises a material capable of storing and releasing lithium ions.

3. The secondary battery of claim 1 in which the functional group containing a substituent having an electron attracting property is selected from the group consisting of halogen, alkoxy, halogenated alkyl, aryl, hydroxyl, amino, carboxyl, ester, cyano, and nitro.

4. The secondary battery of claim 1 in which the at least one organic compound is oxidized and polymerized.

5. The secondary battery of claim 1 in which the positive electrode comprises a protective film formed by oxidation or polymerization of the at least one organic compound.

16. The secondary battery of claim 1 in which:

the negative electrode material comprises at least one material selected from the group consisting of lithium, lithium alloys, alloys, intermetallic compounds, carbon, organic compounds, inorganic compounds, metal complexes, and organic high molecular weight compounds; and

the negative electrode material comprises a compound capable of storing and releasing lithium.

17. The secondary battery of claim 1 in which:

the nonaqueous solvent comprises (a) a cyclic carbonate, (b) a mixture of a cyclic carbonate and noncyclic carbonate, or (c) a mixture of a cyclic carbonate, noncyclic carbonate, and an aliphatic ester carbonate;

the cyclic carbonate comprises at least one carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate;

the noncyclic carbonate comprises at least one carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate; and

the aliphatic ester carbonate comprises at least one carbonate selected from the group consisting of methyl formate, methyl acetate, methyl propionate, and ethyl propionate.

18. The secondary battery of claim 1 in which the electrolytic solution comprises a lithium salt.

19. The secondary battery of claim 1 in which the at least one organic compound has formula 1.

20. The secondary battery of claim 19 in which the at least one organic compound is oxidized and polymerized.

21. The secondary battery of claim 19 in which the positive electrode comprises a protective film formed by oxidation or polymerization of the at least one organic compound.

22. The secondary battery of claim 19 in which the at least one organic compound comprises about 0.1 wt % to about 20 wt % of the electrolytic solution.

6. A secondary battery comprising:

a positive electrode comprising a positive electrode active material;

a negative electrode comprising a negative electrode material; and

a electrolytic solution comprising a nonaqueous solvent and at least one organic compound selected from the group consisting of;

7. The secondary battery of claim 6 in which the at least one organic compound is oxidized and polymerized.

8. The secondary battery of claim 6 in which the positive electrode comprises a protective film formed by oxidation or polymerization of the at least one organic compound.

9. The secondary battery of claim 6 in which the at least one organic compound is biphenylene or 9,10-dihydrophenanthrene.

10. The secondary battery of claim 6 in which the at least one organic compound comprises about 0.1 wt % to about 20 wt % of the electrolytic solution.

11. The secondary battery of claim 6 in which:

the negative electrode material comprises a compound capable of storing and releasing lithium; and

the electrolytic solution comprises a lithium salt.

12. The secondary battery of claim 11 in which the at least one organic compound comprises about 0.1 wt % to about 20 wt % of the electrolytic solution.

13. The secondary battery of claim 11 in which the at least one organic compound comprises about 0.1 wt % to about 20 wt % of the electrolytic solution.

15. The secondary battery of claim 11 in which:

the negative electrode material comprises at least one material selected from the group consisting of lithium, lithium alloys, alloys, intermetallic compounds, carbon, organic compounds, inorganic compounds, metal complexes, and organic high molecular weight compounds; and

the negative electrode material comprises a compound capable of storing and releasing lithium.

14. A secondary battery comprising:

a positive electrode comprising a positive electrode active material;

a negative electrode comprising a negative electrode material; and

a electrolytic solution comprising a nonaqueous solvent and at least one organic compound selected from the group consisting of;

and compounds represented by formula 1;

formula 1

in which;

R₁, R₂, R₃, and R₄ are each independently (i) hydrogen, (ii) an aryl group, or (iii) an aryl group having a functional group containing a substituent having an electron attracting property; and

at least one of R₁, R₂, R₃, and R₄ is either (ii) an aryl group, or (iii) an aryl group having a functional group containing a substituent having an electron attracting property;

in which;

the positive electrode active material comprises a transition metal complex oxide comprising lithium; and

the negative electrode material comprises a material capable of storing and releasing lithium ions;

the positive electrode active material comprises at least one material selected from the group consisting of Li_xCoO₂, Li_xNiO₂, Li_xMnO₂, Li_xCo_yNi<sub>1−

y</sub>O₂, Li_xCo_fV<sub>1−

f</sub>O_z, Li_xNi<sub>1−

y</sub>M¹_yO₂, Li_xCo_aNi_bM²_cO₂, Li_xMn₂O₄, and Li_xMn<sub>2−

y</sub>M³_yO₄;

in which;

x is 0 to 1.2;

y is 0 to 0.9;

f is 0.9 to 0.98;

z is 2.0 to 2.3;

a+b+c=1, 0≦

a≦

1, 0≦

b≦

1, and 0≦

c≦

1;

M¹ is Ti, V, Mn, or F;

M² is Ti, Mn, Al, Mg, Fe, or Zr;

M³ is Na, Mg, Sc, Y, Fe, Co, Ni, Ti, Zr, Cu, Zn, Al, Pb, or Sb; and

the value of x is the value before start of charging and discharging, and the value of x decreases or increases by charging and discharging.

23. A secondary battery comprising:

a positive electrode comprising a positive electrode active material;

a negative electrode comprising a negative electrode material; and

a electrolytic solution comprising a nonaqueous solvent and at least one organic compound selected from the group consisting of 1,2-diphenyl ethylene, cis-stilbene, trans-stilbene, triphenyl ethylene, tetraphenyl ethylene, and p-fluoro-cis-stilbene.

24. The secondary battery of claim 23 in which the at least one organic compound is oxidized and polymerized.

25. The secondary battery of claim 23 in which the positive electrode comprises a protective film formed by oxidation or polymerization of the at least one organic compound.

26. The secondary battery of claim 23 in which the at least one organic compound comprises about 0.1 wt % to about 20 wt % of the electrolytic solution.

27. The secondary battery of claim 23 in which:

the negative electrode material comprises a compound capable of storing and releasing lithium; and

the electrolytic solution comprises a lithium salt.

28. The secondary battery of claim 27 in which the at least one organic compound comprises about 0.1 wt % to about 20 wt % of the electrolytic solution.

29. The secondary battery of claim 28 in which the at least one organic compound comprises cis-stilbene.

30. A secondary battery comprising:

(a) a positive electrode active material comprising Li_xCoO₂, in which x is 0 to 1.2;

(b) a negative electrode material comprises graphite;

(c) an electrolytic solution comprising lithium hexafluorophosphate, a nonaqueous solvent, and an organic compound;

in which;

the nonaqueous solvent comprises ethylene carbonate and at least one noncyclic carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; and

the organic compound comprises cis-stilbene.

31. The secondary battery of claim 30 in which the cis-stilbene comprises about 0.1 wt. % to about 20 wt. % of the electrolyte solution.

32. The secondary battery of claim 30 in which the at least one organic compound is oxidized and polymerized.

33. The secondary battery of claim 30 in which the positive electrode comprises a protective film formed by oxidation or polymerization of the at least one organic compound.