Lithium-containing composite oxide, cathode active material, positive electrode for lithium ion secondary battery, and lithium ion secondary battery

Patent metadata

Field	Value
Publication number	US-11043695-B2
Application number	US-201716074031-A
Country	US
Kind code	B2
Filing date	Feb 3, 2017
Priority date	Jun 30, 2015
Publication date	Jun 22, 2021
Grant date	Jun 22, 2021

Abstract

To provide a lithium-containing composite oxide, a cathode active material and a positive electrode for a lithium ion secondary battery, with which a lithium ion secondary battery having favorable cycle characteristics even when charged at a high voltage can be obtained; and a lithium ion secondary battery having favorable cycle characteristics even when charged at a high voltage. A lithium-containing composite oxide which is represented by LiaNibCocMndMeO2 wherein M is Mg, Ca, Al, Ti, V, Nb, Mo, W or Zr, a+b+c+d+e=2, “a” is from 1.01 to 1.10, b is from 0.30 to 0.95, c is from 0 to 0.35, d is from 0 to 0.35, and e is from 0 to 0.05, wherein in an X-ray diffraction pattern obtained by reflection X-ray diffraction employing Cu-Kα rays, the ratio (I104/I110) of the integrated intensity (I104) of a peak of (104) plane to the integrated intensity (I110) of a peak of (110) plane is at least 4.20.

First claim

The invention claimed is:

1. A lithium-containing composite oxide which is represented by the following formula (I):
Li a Ni b Co c Mn d M e O 2   formula (I)

wherein M is at least one member selected from the group consisting of Ca, Al, Ti, Nb, Mo, W and Zr, a+b+c+d+e=2, a is from 1.01 to 1.10, b is from 0.30 to 0.95, c is from 0 to 0.35, d is from 0 to 0.35, and 0<e≤0.05,
wherein in an X-ray diffraction pattern obtained by reflection X-ray diffraction employing Cu-Kα rays, the ratio (I 104 /I 110 ) of the integrated intensity (I 104 ) of a peak of (104) plane assigned to a crystal structure with space group R-3m to the integrated intensity (I 110 ) of a peak of (110) plane assigned to a crystal structure with space group R-3m is at least 4.20.

2. The lithium-containing composite oxide according to claim 1 , wherein with respect to the ratio (I 003 /I 104 ) of the integrated intensity (I 003 ) of a peak of (003) plane assigned to a crystal structure with space group R-3m to the integrated intensity (I 104 ) of a peak of (104) plane assigned to a crystal structure with space group R-3m in an X-ray diffraction pattern of the lithium-containing composite oxide, the value obtained by dividing the above ratio obtained by reflection X-ray diffraction employing Cu-Kα rays, by the above ratio obtained by transmission X-ray diffraction employing synchrotron radiation, is at least 1.18.

3. The lithium-containing composite oxide according to claim 1 , wherein with respect to the ratio (I 003 /I 104 ) of the integrated intensity (I 003 ) of a peak of (003) plane assigned to a crystal structure with space group R-3m to the integrated intensity (I 104 ) of a peak of (104) plane assigned to a crystal structure with space group R-3m in an X-ray diffraction pattern of the lithium-containing composite oxide, the value obtained by subtracting the above ratio obtained by transmission X-ray diffraction employing synchrotron radiation, from the above ratio obtained by reflection X-ray diffraction employing Cu-Kα rays, is at least 0.18.

4. The lithium-containing composite oxide according to claim 1 , wherein in the formula (I), a+b+c+d+e=2, a is from 1.01 to 1.10, b is from 0.40 to 0.55, c is from 0.15 to 0.35, d is from 0.20 to 0.35, and 0<e≤0.05.

5. The lithium-containing composite oxide according to claim 1 , wherein in an X-ray diffraction pattern of the lithium-containing composite oxide obtained by reflection X-ray diffraction employing Cu-Kα rays, the crystallite size obtained in accordance with the Scherrer equation from a peak of (110) plane assigned to a crystal structure with space group R-3m is from 30 to 70 nm.

6. A cathode active material containing the lithium-containing composite oxide as defined in claim 1 .

7. The cathode active material according to claim 6 , wherein D 50 of the cathode active material is from 3 to 15 μm.

8. A positive electrode for a lithium ion secondary battery, which comprises the cathode active material as defined in claim 6 , an electrically conductive material and a binder.

9. A lithium ion secondary battery, which comprises the positive electrode for a lithium ion secondary battery as defined in claim 8 , a negative electrode, a separator and a non-aqueous electrolyte.

10. A lithium-containing composite oxide which is represented by the following formula (I):
Li a Ni b Co c Mn d M e O 2   formula (I)

wherein M is at least one member selected from the group consisting of Ca, Al, Ti, Nb, Mo, W and Zr, a+b+c+d+e=2, a is from 1.01 to 1.10, b is from 0.30 to 0.95, c is from 0 to 0.35, d is from 0 to 0.35, and 0<e≤0.05,
wherein in an X-ray diffraction pattern obtained by reflection X-ray diffraction employing Cu-Kα rays, the ratio (I 104 /I 110 ) of the integrated intensity (I 104 ) of a peak of (104) plane assigned to a crystal structure with space group R-3m to the integrated intensity (I 110 ) of a peak of (110) plane assigned to a crystal structure with space group R-3m is at least 4.20 and at most 5.00.

11. The lithium-containing composite oxide according to claim 1 , wherein c is from 0.25 to 0.35.

12. A lithium-containing composite oxide which is represented by the following formula (I):
Li a Ni b Co c Mn d M e O 2   formula (I)

wherein M is at least one member selected from the group consisting of Ca, Al, Ti, Nb, Mo, and Zr, a+b+c+d+e=2, a is from 1.01 to 1.10, b is from 0.30 to 0.95, c is from 0 to 0.35, d is from 0 to 0.35, and 0<e≤0.05,
wherein in an X-ray diffraction pattern obtained by reflection X-ray diffraction employing Cu-Kα rays, the ratio (I 104 /I 110 ) of the integrated intensity (I 104 ) of a peak of (104) plane assigned to a crystal structure with space group R-3m to the integrated intensity (I 110 ) of a peak of (110) plane assigned to a crystal structure with space group R-3m is at least 4.20.

Assignees

• Sumitomo Chemical Co

Inventors

• Tamura Masahiko
• Kato Tomoo
• Kawasato Takeshi
• Eguchi Ryo

Classifications

• C01P2002/60

  Compounds characterised by their crystallite size · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01G53/50 Primary

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title