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

• US 9,537,148 B2
• Filed: 02/27/2014
• Issued: 01/03/2017
• Est. Priority Date: 02/28/2013
• Status: Active Grant

• Current Assignee: Envision AESC Japan Co., Ltd.
• Original Assignee: Nissan Motor Co., Ltd.
• Inventors: Nagano, Kodai, Kaseda, Manabu, Ibuka, Shigeo, Tanizaki, Hiroaki, Uwai, Kenta
• Primary Examiner(s): Fraser, Stewart
• Application Number:
  US14/771,106
• Publication Number:
  US 20160006031A1
• Time in Patent Office: 1,041 Days
• US Class Current: 1/1
• 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 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/74 by peak-intensities or a ratio thereof only
• CPC Class Codes: C01P 2004/45 Aggregated particles or particles with an intergrown morphology
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2006/11 Powder tap density
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• 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 4/364 as mixtures
• 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
• CPC Class Codes: Y02T 10/70 : Energy storage systems for electromobility, e.g. batteries

Abstract

Disclosed is a positive electrode active substance for a non-aqueous electrolyte secondary battery including 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. The average particle diameter of the primary particles (D1) and the standard deviation (σ) of the average particle diameter of the primary particles (D1) meet the relationship of D1/σ²≧24.

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 average particle diameter of primary particles (D1) is 0.9 μ

m or less, the average particle diameter of the primary particles (D1) and the standard deviation (σ

) of the average particle diameter of the primary particles (D1) meet the relationship of D1/σ

²≧

24, and the tap density of the positive electrode active substance is 2.3g/cm³ or more.

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_xO₂, with 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, 0.27≦

c≦

0.31, and 0.19≦

d≦

0.26.

4. The positive electrode active substance according to claim 1, wherein the crystallite diameter of the positive electrode active substance is 0.4 μ

m or less.

5. 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 1.0 m²/g.

6. 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 1.28 or more and a diffraction peak integrated intensity ratio ((003)/(104)) of 1.05 or more.

7. 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.

8. A positive electrode material for a non-aqueous electrolyte secondary battery, the positive electrode material being formed as a mixture of the positive electrode active substance according to claim 1 and a spinel type manganese positive electrode active substance.

9. The positive electrode material according to claim 8, 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.

10. 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 being formed as a mixture of the positive electrode active substance and a spinel type manganese positive electrode active substance.

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

the positive electrode according to claim 10,

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

and a separator.

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

13. The non-aqueous electrolyte secondary battery according to claim 11, 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 cm²/Ah or more and the rated capacity is 3 Ah or more.

14. The non-aqueous electrolyte secondary battery according to claim 11, 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.