IP Library Granted Patent US 8,808,927
Granted Patent B2
US 8,808,927 · App. 12/740,491 · Granted Aug 19, 2014

Nonaqueous electrolyte lithium secondary battery

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Quick Facts
Patent No.
US 8,808,927
App. No.
12/740,491
Granted
Aug 19, 2014
Kind
B2
Abstract

A lithium secondary battery comprises an anode capable of intercalating or disintercalating lithium ions, a cathode configured with a lithium-containing oxide, and a nonaqueous electrolyte solution. The lithium-containing oxide comprises a lithium nickel based oxide. The nonaqueous electrolyte solution comprises vinyl ethylene carbonate (VEC) and a mono-nitrile compound. This lithium secondary battery solves the deterioration of charge/discharge cycle characteristics caused by a lithium nickel based oxide used for a cathode, and also controls the decomposition reaction of electrolyte to solve the swelling phenomenon even though the battery is stored at a high temperature or charged/discharged in a fully-charged state, thereby improving high-temperature life characteristics.

Claims (49)

1. A lithium secondary battery comprising an anode capable of intercalating or disintercalating lithium ions, a cathode configured with a lithium-containing oxide, and a nonaqueous electrolyte solution,

wherein the lithium-containing oxide comprises a lithium nickel based oxide, and

the nonaqueous electrolyte solution comprises vinyl ethylene carbonate (VEC) of the following chemistry figure 1 and a mono-nitrile compound of the following chemistry figure 2 at the same time:

wherein R11 is an alkyl group having 3 to 4 carbons,

wherein the amount of the vinyl ethylene carbonate is 3.0 parts by weight based on 100 parts by weight of the nonaqueous electrolyte solution, and the amount of the mono-nitrile compound is 2.0 parts by weight based on 100 parts by weight of the nonaqueous electrolyte solution.

2. The lithium secondary battery according to claim 1 ,

wherein the lithium nickel based oxide is any one selected from the group consisting of LiNiO 2 ; Li 1-x (Ni a Co b Mn c )O 2 , wherein −0.1≦x≦0.1, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1; LiNi 1-y Co y O 2 , wherein 0≦y<1; LiNi 1-y Mn y O 2 , wherein 0≦y<1; Li(Ni a Co b Mn c )O 4 , wherein 0<a<2, 0<b<2, 0<c<2, and a+b+c=2; LiMn 2-z Ni z O 4 , wherein 0<z<2, and mixtures thereof.

3. The lithium secondary battery according to claim 1 ,

wherein the lithium nickel based oxide is Li 1-x (Ni a Co b Mn c )O 2 , wherein −0.1≦x≦0.1, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1.

4. The lithium secondary battery according to claim 1 ,

wherein the lithium nickel based oxide is Li 1-x (Ni a Co b Mn c )O 2 , wherein −0.1≦x≦0.1, 0.5≦a≦0.8, 0.1≦b≦0.2, 0.1≦c≦0.3, and a+b+c=1.

5. The lithium secondary battery according to claim 1 ,

wherein the lithium-containing oxide is a mixture of the lithium nickel based oxide and LiCoO 2 .

6. The lithium secondary battery according to claim 5 ,

wherein the lithium nickel based oxide is any one selected from the group consisting of LiNiO 2 ; Li 1-x (Ni a Co b Mn c )O 2 , wherein −0.1≦x≦0.1, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1; LiNi 1-y Co y O 2 , wherein 0≦y<1; LiNi 1-y Mn y O 2 , wherein O≦y<1; Li(Ni a Co b Mn c )O 4 , wherein 0<a<2, 0<b<2, 0<c<2, and a+b+c=2; LiMn 2-z Ni 3 O 4 ,wherein 0<z<2, and mixtures thereof.

7. The lithium secondary battery according to claim 5 ,

wherein the lithium nickel based oxide is Li 1-x (Ni a Co b Mn c )O 2 , wherein −0.1≦x≦0.1, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1.

8. The lithium secondary battery according to claim 5 ,

wherein the lithium nickel based oxide is Li 1-x (Ni a Co b Mn c )O 2 ,

wherein −0.1≦x≦0.1, 0.5a0.8, 0.1≦b≦0.2, 0.1≦c≦0.3, and a+b+c=1.

9. The lithium secondary battery according to claim 1 ,

wherein the mono-nitrile compound is any one selected from the group consisting of butyronitrile, valeronitrile, and mixtures thereof.

10. The lithium secondary battery according to claim 1 ,

wherein the nonaqueous electrolyte solution comprises a mixed organic solvent comprising a cyclic carbonate compound of the following chemistry figure 3 and a linear carbonate compound of the following chemistry figure 4:

wherein R1 to R4 are independently selected from the group consisting of hydrogen atoms, fluorine and alkyl groups having 1 to 4 carbons, and

wherein R7 and R8 are independently alkyl groups having 1 to 4 carbons, wherein at least one hydrogen atom of the alkyl group is replaceable with fluorine.

11. The lithium secondary battery according to claim 10 ,

wherein the cyclic carbonate compound is ethylene carbonate or a mixture of ethylene carbonate and propylene carbonate.

12. The lithium secondary battery according to claim 10 ,

wherein the mixed organic solvent further comprises a linear ester compound of the following chemistry figure 5:

wherein R9 and R10 are independently alkyl groups having 1 to 4 carbons, wherein at least one hydrogen atom of the alkyl group is replaceable with fluorine.

13. The lithium secondary battery according to claim 12 ,

wherein the linear ester compound is ethyl propionate.

14. The lithium secondary battery according to claim 1 ,

wherein the nonaqueous electrolyte solution comprises a mixed organic solvent comprising a cyclic carbonate compound of the following chemistry figure 3 and a linear ester compound of the following chemistry figure 5:

wherein R1 to R4 are independently selected from the group consisting of hydrogen atoms, fluorine and alkyl groups having 1 to 4 carbons, and

wherein R9 and R10 are independently alkyl groups having 1 to 4 carbons, wherein at least one hydrogen atom of the alkyl group is replaceable with fluorine.

15. The lithium secondary battery according to claim 13 ,

wherein the linear ester compound is ethyl propionate.

16. The lithium secondary battery according to claim 1 , wherein the lithium secondary battery has an initial efficiency ranging from 87.5 percent to 90.7 percent, wherein the initial efficiency is a ratio of a charge capacity to a discharge capacity of the battery, wherein the charge capacity was determined by charging the battery at 0.2 C rate at a constant voltage and a constant current, and wherein the discharge capacity was determined by discharging the battery at 0.2 C rate to 3.0 Volts (V) under the constant current.

17. The lithium secondary battery according to claim 16 , wherein the lithium secondary battery has capacity retention rate at a 400 th charging/discharging ranging from 73.7 percent to 86.9 percent, wherein the capacity retention rate is a ratio of a charge capacity to a discharge capacity at the 400 th charging/discharging of the battery, wherein the charge capacity was determined by charging the battery at 1.0 C rate at the constant voltage and the constant current, and wherein the discharge capacity was determined by discharging the battery at 1.0 C rate to 3.0 Volts (V) under the constant current.

18. The lithium secondary battery according to claim 17 , wherein the lithium secondary battery has a thickness change at 90 degrees Celsius ranging from 0.28 millimeters (mm) to 2.04 mm, wherein the thickness change was determined by the following steps:

(1) charging at 1.0 C rate at the constant current and the constant voltage;

(2) discharging at 1.0 C rate to about 3.0 V under the constant current;

(3) repeating steps (1) and (2) four times;

(4) charging at 1.0 C rate to about 4.2 V;

(5) heating from a normal temperature to 90 degrees Celsius for 1 hour;

(6) maintaining the temperature of the battery at 90 degrees Celsius for 4 hours; and

(7) measuring the change in thickness from the normal temperature to 90 degrees Celsius.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 4, 2021
From: LG CHEM, LTD.
To: LG ENERGY SOLUTION, LTD.
Reel/Frame 058295/0068 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 16, 2012
From: JEON, JONG-HO; KIM, SOO-JIN; LEE, HO-CHUN
To: LG CHEM, LTD.
Reel/Frame 027890/0956 →