Non-aqueous electrolyte secondary battery

Preparation of Positive Electrode Active Material

A lithium-containing nickel-manganese oxide, which serves as the first lithium-containing transition metal oxide in the present invention, was prepared in the following manner. Li 2 Co 3 and (Ni 0.5 Mn 0.5 ) 3 O 4 were mixed together at a mole ratio of 1.1:1, and the resultant mixture was baked in an air atmosphere at 900° C. for 20 hours. The composition of the lithium-containing nickel-manganese oxide thus obtained was Li 1.1 Ni 0.5 Mn 0.5 O 2 .

A lithium-containing nickel-manganese-cobalt oxide, which serves as the second lithium-containing transition metal oxide in the present invention, was prepared in the following manner. Li 2 Co 3 and (Ni 0.4 Co 0.3 Mn 0.3 ) 3 O 4 were mixed together at a mole ratio of 1.15:1, and the resultant mixture was baked in an air atmosphere at 900° C. for 20 hours. The composition of the lithium-containing nickel-manganese-cobalt oxide thus obtained was Li 1.15 Ni 0.4 Co 0.3 Mn 0.3 O 2 .

The lithium-containing nickel-manganese oxide obtained in the above-described manner had a particle size of 10 μm and a BET specific surface area of 1.0 m 2 /g. The lithium-containing nickel-manganese-cobalt oxide obtained in the above-described manner also had a particle size of 10 μm and a BET specific surface area of 1.0 m 2 /g. It was confirmed by X-ray diffraction analysis that both of the materials had a crystal structure belonging to the space group R3m.

Preparation of Positive Electrode

The first and second lithium-containing transition metal oxides thus prepared were mixed together at a weight ratio of 8:2 (the first lithium-containing transition metal oxide:the second lithium-containing transition metal oxide). The resultant mixture was mixed with a carbon material as a conductive agent and an N-methyl-pyrrolidone solution in which polyvinylidene fluoride as a binder agent was dissolved, so that the weight ratio of the active material, the conductive agent, and the binder agent were 90:5:5 to prepare a positive electrode slurry. The slurry thus prepared was applied onto an aluminum foil serving as a current collector and then dried. Thereafter, the aluminum foil coated with the positive electrode slurry was pressure-rolled with pressure rollers, and a current collector tab was attached thereto. Thus, a positive electrode was prepared.

Preparation of Electrolyte Solution

LiPF 6 as a solute was dissolved at a concentration of 1 mole/liter into a mixed solvent of 3:7 volume ratio of ethylene carbonate (EC) and diethyl carbonate (DEC) to thus prepare an electrolyte solution.

Preparation of Three-electrode Beaker Cell

The positive electrode prepared in the above-described manner was used as a working electrode, and metallic lithium was used for a counter electrode and a reference electrode. The electrolyte solution prepared in the above-described manner was filled into a container into which three electrodes were arranged. Thus, a three-electrode beaker cell A1 was prepared.

A test cell A2 was prepared in the same manner as in Example 1, except that the mixture ratio of the first lithium-containing transition metal oxide and the second lithium-containing transition metal oxide was 6:4 (weight ratio).

A test cell A3 was prepared in the same manner as in Example 1, except that the mixture ratio of the first lithium-containing transition metal oxide and the second lithium-containing transition metal oxide was 4:6 (weight ratio).

A test cell A4 was prepared in the same manner as in Example 1, except that the mixture ratio of the first lithium-containing transition metal oxide and the second lithium-containing transition metal oxide was 2:8 (weight ratio).

COMPARATIVE EXAMPLE 1

A test cell B was prepared in the same manner as in Example 1, except that the first lithium-containing transition metal oxide alone was used as the positive electrode active material.

COMPARATIVE EXAMPLE 2

A test cell C was prepared in the same manner as in Example 1, except that the second lithium-containing transition metal oxide alone was used as the positive electrode active material.

COMPARATIVE EXAMPLE 3

A test cell D was prepared in the same manner as in Example 1, except that the positive electrode active material was an 8:2 weight ratio mixture of the first lithium-containing transition metal oxide and a lithium manganese oxide (Li 1.1 Mn 1.9 O 4 ) having a spinel structure.

The test cells prepared in the manners described in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to the following charge-discharge test and I-V resistance measurement test.

Charge-discharge Test

Each of the cells was charged at 1 mA to 4300 mV (vs. Li/Li + ) at room temperature, then rested for 10 minutes, and then discharged at 1 mA to 2000 mV (vs. Li/Li + ), to thus calculate the rated discharge capacity.

I-V Resistance Measurement Test

The cells were discharged to 2000 mV (vs. Li/Li + ) under the just-described charge-discharge test condition, and thereafter charged at 1 mA to 10% and 50% of the rated discharge capacity, and the following tests were carried out.

(1) 5 mA charge (10 seconds)→rest (10 minutes)→5 mA discharge (10 seconds)→rest (10 minutes)

(2) 10 mA charge (10 seconds)→rest (10 minutes)→10 mA discharge (10 seconds)→rest (10 minutes)

(3) 20 mA charge (10 seconds)→rest (10 minutes)→20 mA discharge (10 seconds)→rest (10 minutes)

The charge-discharge tests (1) to (3) were carried out in that order at room temperature. The highest potential reached in each charging was measured, and from the gradient of the potential values with respect to the current values, I-V resistances were calculated. From The I-V resistances obtained and the initial voltage Vo at the start of the above test (1), input power values were calculated using the following equation:

Input power ( W )=(4300 −Vo )/ I - V resistance×4300

The rated discharge capacity, the initial voltage Vo, the I-V resistance, and the input power of each of the test cells are shown in Table 1 (input power characteristics at 50% SOC) and Table 2 (input power characteristics at 10% SOC).

FIG. 1 shows the I-V resistances and the initial voltages of the test cells of Examples 1 to 4 and Comparative Examples 1 and 2. FIG. 2 shows the relationship between input power and the mixture ratios of the first lithium-containing transition metal oxide Li 1.1 Ni 0.5 Mn 0.5 O 2 . As clearly seen from FIGS. 1 and 2 , adding the second lithium-containing transition metal oxide to the first lithium-containing transition metal oxide according to the present invention caused the I-V resistance and the input power to differ from those expected from the weighted average of the mixture ratios, exceptionally improving the I-V resistance and input power. In addition, by adding the second lithium-containing transition metal oxide, the initial voltage Vo lowered, improving the input power characteristics. Comparative Example 3, in which the lithium manganese oxide having a spinel structure (Li 1.1 Mn 1.9 O 4 ) was added, did not yield sufficient input power characteristics because of the increase of initial voltage Vo originating from its high discharge potential.

In addition, as shown in Table 2, Comparative Example 2, which used the lithium-containing nickel-manganese-cobalt oxide alone, showed the greatest input power difference between the input power at 50% SOC and that at 10% SOC. In contrast, Examples 1 to 4, each of which used a mixture of a lithium-containing nickel-manganese oxide and a lithium-containing nickel-manganese-cobalt oxide according to the present invention, showed smaller differences between the input power at 50% SOC and the input power at 10% SOC than Comparative Example 2, and moreover, they yielded relatively high input power. Thus, it will be understood that the present invention makes it possible to obtain uniform and high input power over a wide range of charge depth.

Although the details of workings of the above-described advantageous effect achieved by the present invention have not yet been clearly understood, it is believed that adding a lithium-containing nickel-manganese-cobalt oxide to a lithium-containing nickel-manganese oxide improves the electrochemical activity of the lithium-containing nickel-manganese oxide, and moreover, reduces the dependence of the power characteristics on the depth of charge and discharge.

A test cell A5 was prepared in the same manner as in Example 1, except for the following. Li 2 Co 3 and (Ni 0.1 Mn 0.6 ) 3 O 4 were mixed together at a mole ratio of 1.3:0.7, and the resultant mixture was baked in an air atmosphere at 1000° C. for 20 hours, to thus prepare a lithium-containing nickel-manganese oxide Li 1.3 Ni 0.1 Mn 0.6 O 2 , which was used as the first positive electrode active material. The first positive electrode active material thus prepared was mixed with the second positive electrode active material Li 1.15 Ni 0.4 Co 0.3 Mn 0.3 O 2 at a weight ratio of 1:1.

A test cell A6 was prepared in the same manner as in Example 5, except that a lithium cobalt oxide containing other elements, LiCo 0.99 Zr 0.005 Mg 0.005 O 2 , was used as the second positive electrode active material.

COMPARATIVE EXAMPLE 4

A test cell E was prepared in the same manner as in Example 1, except that Li 1.3 Ni 0.1 Mn 0.6 O 2 alone was used as the positive electrode active material.

COMPARATIVE EXAMPLE 5

A test cell F was prepared in the same manner as in Example 1, except that a lithium cobalt oxide containing other elements LiCo 0.99 Zr 0.005 Mg 0.005 O 2 alone was used as the positive electrode active material.

Charge-discharge Test

Each of the cells was charged at 1 mA to 4600 mV (vs. Li/Li + ) at room temperature, then rested for 10 minutes, and then discharged at 1 mA to 2000 mV (vs. Li/Li + ), to thus calculate the discharge capacity.

I-V Resistance Measurement Test

The cells were discharged to 2000 mV (vs. Li/Li + ) under the just-described charge-discharge test condition, and thereafter charged at 1 mA to 30% and 70% of the discharge capacity, and the following tests were carried out.

(1) 5 mA charge (10 seconds)→rest (10 minutes)→5 mA discharge (10 seconds)→rest (10 minutes)

(2) 10 mA charge (10 seconds)→rest (10 minutes)→10 mA discharge (10 seconds)→rest (10 minutes)

(3) 20 mA charge (10 seconds)→rest (10 minutes)→20 mA discharge (10 seconds)→rest (10 minutes)

The charge-discharge tests (1) to (3) were carried out in that order at room temperature. The highest potential reached in each charging was measured, and from the gradient of the potential values with respect to the current values, I-V resistances were calculated. From The I-V resistances obtained and the initial voltage Vo at the start of the above test (1), input power values were calculated using the following equation.

Input power ( W )=(4300− Vo )/ I - V resistance×4300

The input power and input power difference for each of the cells are shown in Table 3.

The test results shown in Table 3 clearly demonstrate that mixing Li 1.3 Ni 0.1 Mn 0.6 O 2 with either Li 1.15 Ni 0.4 Co 0.3 Mn 0.3 O 2 or LiCo 0.99 Zr 0.005 Mg 0.005 O 2 makes it possible to reduce variations in input power with respect to changes in SOC considerably. Thus, it is possible to fabricate a battery that shows little dependence of power on the depth of charge and discharge.

Although the details of workings of the above-described advantageous effect achieved by the present invention have not yet been clearly understood, it is believed that the effects of improving the electrochemical activity of the lithium-containing nickel-manganese oxide and reducing the dependence of power on charge depth, which is achieved by the addition of another type of positive electrode active material, emerges more evidently because the positive electrode material comprising a lithium-containing nickel-manganese oxide having a large proportion of manganese shows a low electron conductivity.

Only selected embodiments have been chosen to illustrate the present invention. To those skilled in the art, however, it will be apparent from the foregoing disclosure that various changes and modifications can be made herein without departing from the scope of the invention as defined in the appended claims. Furthermore, the foregoing description of the embodiments according to the present invention is provided for illustration only, and not for limiting the invention as defined by the appended claims and their equivalents.

This application claims priority of Japanese Patent Application Nos. 2005-233528 and 2005-278108 filed Aug. 11 and Sep. 26, 2005, respectively, which are incorporated herein by reference.