Positive electrode active substance, positive electrode material, positive electrode, and non-aqueous electrolyte secondary battery

• US 9,843,033 B2
• Filed: 02/27/2014
• Issued: 12/12/2017
• Est. Priority Date: 02/28/2013
• Status: Active Grant

• Current Assignee: Envision AESC Japan Co., Ltd.
• Original Assignee: Nissan Motor Co., Ltd.
• Inventors: Kaseda, Manabu, Ibuka, Shigeo, Tanizaki, Hiroaki, Nagano, Kodai, Uwai, Kenta
• Primary Examiner(s): Walls, Cynthia K
• Application Number:
  US14/771,000
• Publication Number:
  US 20160013471A1
• Time in Patent Office: 1,384 Days
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/60 Compounds characterised by their crystallite size
• CPC Class Codes: C01P 2002/74 by peak-intensities or a ratio thereof only
• CPC Class Codes: C01P 2004/50 Agglomerated particles
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/84 one phase coated with the other
• CPC Class Codes: C01P 2006/11 Powder tap density
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: H01M 2004/021 Physical characteristics, e.g. porosity, surface area
• CPC Class Codes: H01M 2004/028 Positive electrodes
• 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 4/366 as layered products
• 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

Abstract

[Object] Provided is a means which is capable, with respect to a non-aqueous electrolyte secondary battery, of suppressing a decrease in capacity when the battery is used for a long period of time, and improving cycle characteristics.

[Solving Means] Disclosed is a positive electrode active substance for a non-aqueous electrolyte secondary battery comprising a composite oxide containing lithium and nickel, in which the positive electrode active substance has a structure of secondary particles formed by aggregation of primary particles, the average particle diameter of the primary particles (D1) is 0.9 μm or less, and the ratio value (D2/D1)) of the average particle diameter of the secondary particles (D2) to the average particle diameter of the primary particles (D1) is 11 or more.

[Representative Drawing] None

Claims

1. A positive electrode active substance for a non-aqueous electrolyte secondary battery comprising a composite oxide containing lithium and nickel,

wherein the positive electrode active substance has a structure of secondary particles formed by aggregation of primary particles, the arithmetic average particle diameter of primary particles (D1) is 0.25 to 0.48 μ

m, the arithmetic average particle diameter of secondary particles (D2) is 5.8 to 8.5 μ

m, the ratio value (D2/D1)) of the arithmetic average particle diameter of the secondary particles (D2) to the arithmetic average particle diameter of the primary particles (D1) is 28.7 to 33.5, the tap density of the positive electrode active substance is 2.32 to 2.65 g/cm³, and the crystallite diameter of the positive electrode active substance is 0.10 to 0.15 μ

m.

2. The positive electrode active substance according to claim 1, wherein the composite oxide comprises a composition represented by General Formula:

Li_aNi_bMn_cCo_dM_xO₂with the proviso that, in the formula, a, b, c, d, and x satisfy 0.9≦

a≦

1.2, 0<

b<

1, 0<

c≦

0.5, 0<

d≦

0.5, 0≦

x≦

0.3, and b +c +d =1; and

M represents at least one selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr.

3. The positive electrode active substance according to claim 2, wherein b, c and d are as follows:

0.44≦

b≦

0.51, 0.27c≦

0.31, and 0.19≦

d≦

0.26.

4. The positive electrode active substance according to claim 1, wherein the BET specific surface area of the positive electrode active substance is 0.1 to 1.0m²/g.

5. The positive electrode active substance according to claim 1, wherein the diffraction peak of a (104) surface and the diffraction peak of a (003) surface of the positive electrode active substance obtained by powder X ray diffraction measurement have a diffraction peak intensity ratio ((003)/(104)) of 1.62 to 1.7 and a diffraction peak integrated intensity ratio ((003)/(104)) of 1.14 to 1.16.

6. A positive electrode material for a non-aqueous electrolyte secondary battery, the positive electrode material comprising:

a core part comprising the positive electrode active substance according to claim 1; and

a shell part comprising a lithium-containing composite oxide which is different from the positive electrode active substance.

7. A positive electrode material for a non-aqueous electrolyte secondary battery, the positive electrode material being formed by containing in a mixed state of the positive electrode active substance according to claim 1 and a spinel type manganese positive electrode active substance.

8. The positive electrode material according to claim 7, wherein the mixing weight ratio of the positive electrode active substance and the spinel type manganese positive electrode active substance is 50:

50 to 90;

10.

9. A positive electrode for a non-aqueous electrolyte secondary battery, the positive electrode being obtained by forming, on a surface of a positive electrode current collector, a positive electrode active substance layer containing at least one selected from the group consisting of the positive electrode active substance according to claim 1;

and

a positive electrode material comprising a core part comprising the positive electrode active substance, and a shell part comprising a lithium-containing composite oxide which is different from the positive electrode active substance.

10. A non-aqueous electrolyte secondary battery comprising a power generating element comprising:

the positive electrode according to claim 9,

a negative electrode obtained by forming a negative electrode active substance layer on a surface of a negative electrode current collector,

and a separator.

11. The non-aqueous electrolyte secondary battery according to claim 10, wherein the separator is a separator having a heat resistant insulating layer.

12. The non-aqueous electrolyte secondary battery according to claim 10, wherein the ratio value of a battery area (projected area of a battery including an outer casing body of a battery) to rated capacity is 5 to 13.0 cm²/Ah and the rated capacity is 3 to 56.6Ah.

13. The non-aqueous electrolyte secondary battery according to claim 10, wherein the aspect ratio of an electrode defined as a longitudinal/transversal ratio of a rectangular positive electrode active substance layer is 1 to 3.