Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the same
View Patent ↗[Object] Provided is a means for improving cycle characteristics by suppressing electrode deterioration resulting from non-uniformity of voltage across an electrode plane in a high-capacity and large-area non-aqueous electrolyte secondary battery that includes lithium nickel-based composite oxide as a positive electrode active substance. [Solving Means] Disclosed is a positive electrode for a non-aqueous electrolyte secondary battery used in a non-aqueous electrolyte secondary battery in which the ratio value of battery area (projected area of the battery including the battery outer casing body) to rated capacity is 5 cm 2 /Ah or more and the rated capacity is 3 Ah or more, the positive electrode comprising a positive electrode current collector and a positive electrode active substance layer that is formed on a surface of the positive electrode current collector and has a positive electrode active substance containing a lithium nickel-based composite oxide and a spinel type lithium manganese composite oxide, in which, when the average secondary particle diameter (D50) of the lithium nickel-based composite oxide is D50(A) [μm], the content ratio of the lithium nickel-based composite oxide in the positive electrode active substance layer is A [% by mass], the average secondary particle diameter (D50) of the spinel type lithium manganese composite oxide is D50(B) [μm], and the content ratio of the spinel type lithium manganese composite oxide in the positive electrode active substance layer is B [% by mass], the positive electrode satisfies the following Mathematical Formula 1 and Mathematical Formula 2: [Math. 1] 0.5≦ D 50( A )/ D 50( B )≦2.0 MathematicalFormula1: B /( A+B )≧0.2 MathematicalFormula2:
1. A positive electrode for a non-aqueous electrolyte secondary battery in which a ratio value of a battery area to a rated capacity is 89.8 cm 2 /Ah or more, the battery area being a projected area of the non-aqueous electrolyte secondary battery including a battery outer casing body and the rated capacity being 3 Ah or more, the positive electrode comprising:
a positive electrode current collector; and
a positive electrode active substance layer that is formed on a surface of the positive electrode current collector and has a positive electrode active substance containing a lithium nickel-based composite oxide and a spinel type lithium manganese composite oxide,
wherein, when an average secondary particle diameter of the lithium nickel-based composite oxide is D50(A), a content ratio of the lithium nickel-based composite oxide in the positive electrode active substance layer is A [% by mass], the average secondary particle diameter of the spinel type lithium manganese composite oxide is D50(B), and a content ratio of the spinel type lithium manganese composite oxide in the positive electrode active substance layer is B [% by mass], the positive electrode satisfies the following
0.5≦ D 50( A )/ D 50( B )≦2.0 and
0.3≦ B /( A+B )≦0.5.
2. The positive electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the lithium nickel-based composite oxide has a composition represented by a general formula: Li a Ni b Mn c Co d M x O 2 ,
wherein a, b, c, d, and x satisfy the following:
0.9≦ a≦ 1.2,
0≦ b≦ 1,
0≦ c≦ 0.5,
0≦ d≦ 0.5,
0≦ x≦ 0.3,
b+c+d= 1, and
wherein M represents at least one element selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr.
3. The positive electrode for a non-aqueous electrolyte secondary battery according to claim 2 , wherein b, c and d satisfy the following equations:
0.44≦ b≦ 0.51,
0.27≦ c≦ 0.31, and
0.19≦ d≦ 0.26.
4. The positive electrode for a non-aqueous electrolyte secondary battery according to claim 1 , wherein the positive electrode active substance layer has a rectangular shape and an aspect ratio of an electrode defined as a longitudinal/transversal ratio of a rectangular-shaped positive electrode active substance layer is 1 to 3.
5. A non-aqueous electrolyte secondary battery comprising:
a power generating element including a positive electrode, a negative electrode obtained by forming a negative electrode active substance layer on a surface of a negative electrode current collector, and a separator, the positive electrode comprising:
a positive electrode current collector; and
a positive electrode active substance layer that is formed on a surface of the positive electrode current collector and has a positive electrode active substance containing a lithium nickel-based composite oxide and a spinel type lithium manganese composite oxide,
wherein a ratio value of a battery area to a rated capacity is 89.8 cm 2 /Ah or more, the battery area being a projected area of the non-aqueous electrolyte secondary battery including a battery outer casing body and the rated capacity being 3 Ah or more, and
wherein, when an average secondary particle diameter of the lithium nickel-based composite oxide is D50(A), a content ratio of the lithium nickel-based composite oxide in the positive electrode active substance layer is A [% by mass], the average secondary particle diameter of the spinel type lithium manganese composite oxide is D50(B), and a content ratio of the spinel type lithium manganese composite oxide in the positive electrode active substance layer is B [% by mass], the positive electrode satisfies the following:
0.5≦ D 50( A )/ D 50( B )≦2.0, and
0.3≦ B /( A+B )≦0.5.
6. The non-aqueous electrolyte secondary battery according to claim 5 , wherein the separator has a heat resistant insulating layer.
7. The non-aqueous electrolyte secondary battery according to claim 5 , wherein the non-aqueous electrolyte secondary battery is a flat stack type laminate battery in which the power generating element is enclosed in the battery outer casing body which is formed of a laminate film containing aluminum.
8. The non-aqueous electrolyte secondary battery according to claim 5 , wherein the rated capacity is 3 Ah or more.
9. The non-aqueous electrolyte secondary battery according to claim 5 , wherein the lithium nickel-based composite oxide has a composition represented by a general formula:
Li a Ni b Mn c Co d M x O 2 ,
wherein a, b, c, d, and x satisfy the following:
0.9≦ a≦ 1.2,
0≦ b≦ 1,
0≦ c≦ 0.5,
0≦ d≦ 0.5,
0≦ x≦ 0.3,
b+c+d= 1, and
wherein M represents at least one element selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr.
10. The non-aqueous electrolyte secondary battery according to claim 5 , wherein b, c and d satisfy the following:
0.44≦ b≦ 0.51,
0.27≦ c≦ 0.31, and
0.19≦ d≦ 0.26.
11. The non-aqueous electrolyte secondary battery according to claim 5 , wherein the positive electrode active substance layer has a rectangular shape and an aspect ratio of an electrode defined as a longitudinal/transversal ratio of a rectangular-shaped positive electrode active substance layer is 1 to 3.