IP Library › Granted Patent US 10,224,570
Granted Patent B2
US 10,224,570 · App. 14/785,049 · Granted Mar 5, 2019

Nonaqueous electrolyte secondary battery

Inventors: Takeshi Abe (Toyota, JP); Toshiyuki Kawai (Toyota, JP); Akira Kouyama (Toyota, JP)
Assignee: TOYOTA JIDOSHA KABUSHIKI KAISHA
H01M10/0569H01M4/505H01M4/525H01M4/587H01M10/052H01M10/0525H01M10/0567H01M10/0587H01M2004/027H01M2004/028H01M2220/20H01M2220/30H01M2300/002H01M2300/004H01M2300/0034H01M2300/0037
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Quick Facts
Patent No.
US 10,224,570
App. No.
14/785,049
Granted
Mar 5, 2019
Kind
B2
Abstract

The invention provides a lithium ion secondary battery which exhibits excellent output characteristics and in which decline in the power characteristics is suppressed for a long period of time even after charge-discharge cycling. The lithium ion secondary battery includes a positive electrode, a negative electrode and a nonaqueous electrolyte solution. The positive electrode has a maximum achievable potential of 4.5 V or more versus metallic lithium. The nonaqueous electrolyte solution includes (A) a nonfluorinated cyclic carbonate, (B) a fluorinated cyclic carbonate, and (C) a fluorinated acyclic carbonate. The nonfluorinated cyclic carbonate (A) accounts for more than 10% by volume of (A), (B) and (C) combined.

Claims (42)

1. A nonaqueous electrolyte secondary battery comprising:

a positive electrode having a maximum achievable potential of 4.5 V or more versus metallic lithium;

a negative electrode; and

a nonaqueous electrolyte solution comprising a supporting salt and a nonaqueous solvent;

wherein

the nonaqueous solvent comprises:

(A) a nonfluorinated cyclic carbonate containing 3 to 8 carbon atoms;

(B) a fluorinated cyclic carbonate; and

(C) a fluorinated acyclic carbonate; and wherein

the nonfluorinated cyclic carbonate (A), the fluorinated cyclic carbonate (B) and the fluorinated acyclic carbonate (C) are present in an amount of 90% by volume or more in total relative to 100% by volume of a total amount of the nonaqueous solvent,

the nonfluorinated cyclic carbonate (A) accounts for more than 10% by volume of (A), (B) and (C) combined,

a volumetric ratio A:B of the nonfluorinated cyclic carbonate (A) to the fluorinated cyclic carbonate (B) is 75:25 to 60:40, and

a volumetric ratio (A+B):C of the nonfluorinated cyclic carbonate (A) and the fluorinated cyclic carbonate (B) combined to the fluorinated acyclic carbonate (C) is 50:50 to 35:65.

2. The nonaqueous electrolyte secondary battery of claim 1 , wherein

the nonfluorinated cyclic carbonate (A) accounts for 40% by volume or less of the combined amount of the nonfluorinated cyclic carbonate (A), the fluorinated cyclic carbonate (B) and the fluorinated acyclic carbonate (C).

3. The nonaqueous electrolyte secondary battery of claim 1 , wherein the nonfluorinated cyclic carbonate (A) includes a compound of formula (C1)

where, R 11 , R 12 , R 13 and R 14 are each independently selected from among a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a haloalkyl group that does not include fluorine, and a halogen atom other than fluorine.

4. The nonaqueous electrolyte secondary battery of claim 3 , wherein

the nonfluorinated cyclic carbonate (A) includes ethylene carbonate.

5. The nonaqueous electrolyte secondary battery of claim 1 , wherein

the fluorinated cyclic carbonate (B) includes a compound of formula (C2)

where, R 21 , R 22 and R 23 are each independently selected from among a hydrogen atom, a fluorine atom, a halogen atom other than fluorine, an alkyl group of 1 to 4 carbon atoms and a haloalkyl group.

6. The nonaqueous electrolyte secondary battery of claim 5 , wherein the fluorinated cyclic carbonate (B) includes fluoroethylene carbonate.

7. The nonaqueous electrolyte secondary battery of claim 1 , wherein

the fluorinated acyclic carbonate (C) includes a compound of formula (C3)

where, at least one of R 31 and R 32 is an organic group containing fluorine.

8. The nonaqueous electrolyte secondary battery of claim 7 , wherein

the fluorinated acyclic carbonate (C) includes methyl 2,2,2-trifluoroethyl carbonate.

9. The nonaqueous electrolyte secondary battery of claim 1 , wherein

an oxidation potential of the nonaqueous electrolyte solution is higher than the maximum achievable potential of the positive electrode, wherein

the oxidation potential is determined as a potential when a current value I initially becomes larger than 0.1 mA, measured by: building a three-electrode electrochemical cell that uses the electrolyte solution to be measured and that has a working electrode of LiNi 0.5 Mn 1.5 O 4 , a counter electrode of metallic lithium and a reference electrode of metallic lithium;

constant-current charging the three-electrode electrochemical cell at a temperature of from 25° C. up to 4.5 V at a first current value that is ⅕ of a battery capacity (Ah) calculated from a theoretical capacity of the working electrode;

constant-voltage charging the three-electrode cell at 4.5 V until the current value becomes 1/50 of the first current value; and then

repeatedly measuring the current value I when constant-voltage charging is carried out for 10 hours at a voltage increased by 0.2 V.

10. The nonaqueous electrolyte secondary battery of claim 1 , wherein

the positive electrode includes, as a positive electrode active material, a lithium-transition metal composite oxide having a spinel structure, and

the lithium-transition metal composite oxide includes, as transition metal elements, at least nickel and manganese.

11. The nonaqueous electrolyte secondary battery of claim 10 , wherein

the lithium-transition metal composite oxide is represented by the general formula: Li x (Ni y Mn 2-y-z M 1 z )O 4+β ;

where, M 1 is one or two or more selected from the group consisting of any transition metal elements other than Ni and Mn, and typical metal elements; x, y and z are values that satisfy the conditions 0.9≤x≤1.2, 0<y, 0≤z and y+z<2; and β is a value that satisfy the conditions −0.2≤β≤0.2 and set to satisfy a charge neutrality condition.

12. The nonaqueous electrolyte secondary battery of claim 1 , wherein

the negative electrode comprises, as a negative electrode active material, a carbonaceous material.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Oct 16, 2015
From: ABE, TAKESHI; KAWAI, TOSHIYUKI; KOUYAMA, AKIRA
To: TOYOTA JIDOSHA KABUSHIKI KAISHA
Reel/Frame 036811/0536 →
Priority Claims (1)
JP 2013-086347 · Apr 17, 2013 · national
Continuity (1)
Related Publication 20160079629A1 · Mar 17, 2016