Positive electrode active substance particles and process for producing the same, and non-aqueous electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-9564634-B2
Application number	US-201314388931-A
Country	US
Kind code	B2
Filing date	Mar 14, 2013
Priority date	Mar 30, 2012
Publication date	Feb 7, 2017
Grant date	Feb 7, 2017

Abstract

The present invention relates to positive electrode active substance particles comprising a compound having at least a crystal system belonging to a space group of R-3m and a crystal system belonging to a space group of C2/m, the positive electrode active substance particles having a specific intensity ratio; a content of Mn in the positive electrode active substance particles being controlled such that a molar ratio of Mn/(Ni+Co+Mn) therein is not less than 0.55; and the positive electrode active substance particles comprising an element A (that is at least one element selected from the group consisting of Si, Zr and Y) in an amount of 0.03 to 5% by weight and having a tap density of 0.8 to 2.4 g/cc and a compressed density of 2.0 to 3.1 g/cc. The positive electrode active substance particles can be produced by calcining a mixture of precursor particles comprising the element A, Mn, Ni and/or Co, and a lithium compound.

First claim

The invention claimed is:

1. Positive electrode active substance particles comprising a compound having at least a crystal system belonging to a space group of R-3m and a crystal system belonging to a space group of C2/m,
the compound being in the form of a composite oxide comprising at least Li, Mn, an element A, and Co and/or Ni, wherein element A is at least one element selected from the group consisting of Si, Zr and Y;
a relative intensity ratio [(a)/(b)] of a maximum diffraction peak intensity (a) observed at 2θ=20.8±1° in a powder X-ray diffraction pattern of the positive electrode active substance particles as measured using a Cu—Kα ray to a maximum diffraction peak intensity (b) observed at 2θ=18.6±1° in the powder X-ray diffraction pattern being 0.02 to 0.2;
a content of Mn in the positive electrode active substance particles being a molar ratio of Mn/(Ni+Co+Mn) therein is not less than 0.55; and
the positive electrode active substance particles comprising the element A in an amount of 0.03 to 5% by weight and having a tap density of 1.63 to 2.4 g/cc and a compressed density of 2.0 to 3.1 g/cc,
wherein a molar ratio of Li/(Ni+Co+Mn) in the positive electrode active substance particles is 1.25 to 1.7.

2. The positive electrode active substance particles according to claim 1 , wherein the positive electrode active substance particles comprise LiM x Mn 1-x O 2 wherein M is Ni and/or Co; 0<x≦1, as the compound having a crystal system belonging to a space group of R-3m, and Li 2 M′ (1-y) Mn y O 3 wherein M′ is Ni and/or Co; 0<y≦1, as the compound having a crystal system belonging to a space group of C2/m.

3. The positive electrode active substance particles according to claim 1 , wherein the positive electrode active substance particles have a specific surface area of 0.1 to 20 m 2 /g as measured by a BET method.

4. The positive electrode active substance particles according to claim 1 , wherein the positive electrode active substance particles are in the form of secondary particles produced by aggregating primary particles thereof in which the secondary particles have an average secondary particle diameter of 1 to 50 μm.

5. Precursor particles to the positive electrode active substance particles according to claim 1 , the precursor particles comprising a composite hydroxide or a composite carbonate as a main component which comprises at least Mn, an element A, and Co and/or Ni, wherein element A is at least one element selected from the group consisting of Si, Zr and Y,
a content of Mn in the precursor particles being a molar ratio of Mn/(Ni+Co+Mn) therein is not less than 0.55; and the precursor particles comprising the element A in an amount of 0.025 to 5.5% by weight and having an average secondary particle diameter of 1 to 50 μm.

6. A process for producing the positive electrode active substance particles as claimed in claim 1 , comprising the step of calcining a mixture comprising the precursor particles, and a lithium compound at a temperature of 500 to 1500° C.

7. A non-aqueous electrolyte secondary battery using a positive electrode comprising the positive electrode active substance particles as claimed in claim 1 .

8. The positive electrode active substance particles according to claim 1 , wherein a content of Mn in the positive electrode active substance particles being controlled such that a molar ratio of Mn/(Ni+Co+Mn) therein is not less than 0.573.

9. The positive electrode active substance particles according to claim 1 , wherein the tap density is 1.76 to 2.4 g/cc.

10. Positive electrode active substance particles consisting of a compound having at least a crystal system belonging to a space group of R-3m and a crystal system belonging to a space group of C2/m,
the compound being in the form of a composite oxide consisting of Li, Mn, an element A, oxygen and Co and/or Ni, wherein element A is at least one element selected from the group consisting of Si, Zr and Y;
a relative intensity ratio [(a)/(b)] of a maximum diffraction peak intensity (a) observed at 2θ=20.8±1° in a powder X-ray diffraction pattern of the positive electrode active substance particles as measured using a Cu—Kα ray to a maximum diffraction peak intensity (b) observed at 2θ=18.6±1° in the powder X-ray diffraction pattern being 0.02 to 0.2;
a content of Mn in the positive electrode active substance particles being controlled such that a molar ratio of Mn/(Ni+Co+Mn) therein is not less than 0.55; and
the positive electrode active substance particles comprising the element A in an amount of 0.03 to 5% by weight and having a tap density of 1.63 to 2.4 g/cc and a compressed density of 2.0 to 3.1 g/cc,
wherein a molar ratio of Li/(Ni+Co+Mn) in the positive electrode active substance particles is 1.25 to 1.7.

11. The positive electrode active substance particles according to claim 10 , wherein the tap density is 1.76 to 2.4 g/cc.

Assignees

• Toda Kogyo Corp
• Toda Kogyo Corp

Inventors

• Yamamoto Manabu
• Nishikawa Daisuke
• Inoue Taisei
• Sasaki Osamu
• Sadamura Hideaki

Classifications

• C01P2006/12

  Surface area · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title

• C01P2002/50

  Solid solutions · CPC title

• C01G51/50 Primary

  of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2 · CPC title

• C01P2006/80

  Compositional purity · CPC title