5V-class spinel-type lithium-manganese-containing composite oxide

Patent metadata

Field	Value
Publication number	US-10276867-B2
Application number	US-201615512990-A
Country	US
Kind code	B2
Filing date	Apr 28, 2016
Priority date	Apr 30, 2015
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

Provided is a new 5 V-class spinel-type lithium-manganese-containing composite oxide capable of achieving both the expansion of a high potential capacity region and the suppression of gas generation. Proposed is the spinel-type lithium-manganese-containing composite oxide comprising Li, Mn, O and two or more other elements, and having an operating potential of 4.5 V or more at a metal Li reference potential, wherein a peak is present in a range of 14.0 to 16.5° at 2θ, in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray.

First claim

The invention claimed is:

1. A spinel-type lithium-manganese-containing composite oxide, comprising
Li, Mn, O and two or more other elements,
and having an operating potential of 4.5 V or more at a metal Li reference potential,
wherein, in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray,
a peak is present in a range of 14.0 to 16.5° at 2θ.

2. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
at least one element from the “two or more other elements” according to claim 1 is selected from the group consisting of Ni, Co and Fe, and
another element is selected from the group consisting of Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr and Nb.

3. The spinel-type lithium-manganese-containing composite oxide according to claim 2 , wherein
the spinel-type lithium-manganese-containing composite oxide is represented by formula (1): Li[Li a Mn 2-a-b-c M1 b M2 c ]O 4-δ (wherein M1 represents one or two or more elements selected from the group consisting of Ni, Co and Fe, M2 represents one or two or more elements selected from the group consisting of Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr and Nb, a is 0.00 to 0.20, b is 0.20 to 1.20, and c is 0.001 to 0.400).

4. The spinel-type lithium-manganese-containing composite oxide according to claim 2 , wherein
the spinel-type lithium-manganese-containing composite oxide is represented by formula (2): Li[Li a Mn 2-a-b-c Ni b M2 c ]O 4-δ (wherein M2 represents one or two or more elements selected from the group consisting of Co, Fe, Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr and Nb, a is 0.00 to 0.20, b is 0.20 to 0.70, and c is 0.001 to 0.400).

5. The spinel-type lithium-manganese-containing composite oxide according to claim 2 , wherein
the spinel-type lithium-manganese-containing composite oxide is represented by formula (2): Li[Li a Mn 2-a-b-c Ni b M2 c ]O 4-δ (wherein M2 represents one or two or more elements selected from the group consisting of Ti, Y, and Zr, a is 0.00 to 0.20, b is 0.20 to 0.70, and c is 0.001 to 0.400).

6. The spinel-type lithium-manganese-containing composite oxide according to claim 2 , wherein,
in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray,
a ratio of a peak intensity of the peak that is the highest in the peaks present in a range of 14.0 to 16.5° at 2θ with respect to a peak intensity of the peak that is the highest in the peaks present in a range of 18 to 19° at 2θ is more than 0.05%.

7. The spinel-type lithium-manganese-containing composite oxide according to claim 2 , wherein
a tap density is 1.2 g/cm 3 or more.

8. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
the spinel-type lithium-manganese-containing composite oxide is represented by formula (1): Li[Li a Mn 2-a-b-c M1 b M2 c ]O 4-δ (wherein M1 represents one or two or more elements selected from the group consisting of Ni, Co and Fe, M2 represents one or two or more elements selected from the group consisting of Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr and Nb, a is 0.00 to 0.20, b is 0.20 to 1.20, and c is 0.001 to 0.400).

9. The spinel-type lithium-manganese-containing composite oxide according to claim 8 , wherein,
in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray,
a ratio of a peak intensity of the peak that is the highest in the peaks present in a range of 14.0 to 16.5° at 2θ with respect to a peak intensity of the peak that is the highest in the peaks present in a range of 18 to 19° at 2θ is more than 0.05%.

10. The spinel-type lithium-manganese-containing composite oxide according to claim 8 , wherein
a tap density is 1.2 g/cm 3 or more.

11. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
the spinel-type lithium-manganese-containing composite oxide is represented by formula (2): Li[Li a Mn 2-a-b-c Ni b M2 c ]O 4-δ (wherein M2 represents one or two or more elements selected from the group consisting of Co, Fe, Mg, Ti, Al, Ba, Cr, W, Mo, Y, Zr and Nb, a is 0.00 to 0.20, b is 0.20 to 0.70, and c is 0.001 to 0.400).

12. The spinel-type lithium-manganese-containing composite oxide according to claim 11 , wherein,
in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray,
a ratio of a peak intensity of the peak that is the highest in the peaks present in a range of 14.0 to 16.5° at 2θ with respect to a peak intensity of the peak that is the highest in the peaks present in a range of 18 to 19° at 2θ is more than 0.05%.

13. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
the spinel-type lithium-manganese-containing composite oxide is represented by formula (2): Li[Li a Mn 2-a-b-c Ni b M2 c ]O 4-δ (wherein M2 represents one or two or more elements selected from the group consisting of Ti, Y, and Zr, a is 0.00 to 0.20, b is 0.20 to 0.70, and c is 0.001 to 0.400).

14. The spinel-type lithium-manganese-containing composite oxide according to claim 13 , wherein,
in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray,
a ratio of a peak intensity of the peak that is the highest in the peaks present in a range of 14.0 to 16.5° at 2θ with respect to a peak intensity of the peak that is the highest in the peaks present in a range of 18 to 19° at 2θ is more than 0.05%.

15. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein,
in an X-ray diffraction pattern measured by a powder X-ray diffractometer (XRD) using CuKα1 ray,
a ratio of a peak intensity of the peak that is the highest in the peaks present in a range of 14.0 to 16.5° at 2θ with respect to a peak intensity of the peak that is the highest in the peaks present in a range of 18 to 19° at 2θ is more than 0.05%.

16. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
a tap density is 1.2 g/cm 3 or more.

17. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
an average primary particle size is more than 0.5 μm.

18. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
a specific surface area (SSA) is 1.5 m 2 /g or less.

19. The spinel-type lithium-manganese-containing composite oxide according to claim 1 , wherein
a crystallite size is 100 nm or more.

20. A lithium secondary battery having the spinel-type lithium-manganese-containing composite oxide according to claim 1 as a positive electrode active material.

Assignees

• Mitsui Mining & Smelting Co

Inventors

• Mitsumoto Tetsuya
• Yamaguchi Kyohei
• Matsuyama Toshikazu
• Matsushima Hideaki
• Kagei Shinya

Classifications

• H01M2004/028

  Positive electrodes · CPC title

• C01P2006/82

  water content · CPC title

• C01G49/009

  Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements · CPC title

• C01G51/54

  of the type (Mn2O4)-, e.g. Li(CoxMn2-x)O4 or Li(MyCoxMn2-x-y)O4 · CPC title

• C01P2006/80

  Compositional purity · CPC title