Spinel-type lithium manganese transition metal oxide

Patent metadata

Field	Value
Publication number	US-9893355-B2
Application number	US-201214368635-A
Country	US
Kind code	B2
Filing date	Dec 27, 2012
Priority date	Dec 27, 2011
Publication date	Feb 13, 2018
Grant date	Feb 13, 2018

Abstract

Provided is a new spinel type lithium manganese transition metal oxide for use in lithium batteries, which can increase the capacity retention ratio during cycling, and can increase the power output retention ratio during cycling. Disclosed is a spinel type lithium manganese transition metal oxide having an angle of repose of 50° to 75°, and having an amount of moisture (25° C. to 300° C.) measured by the Karl Fischer method of more than 0 ppm and less than 400 ppm.

First claim

The invention claimed is:

1. A spinel type lithium manganese transition metal oxide, having an angle of repose of 50° to 75°, and having an amount of moisture (25° C. to 300° C.) measured by the Karl Fischer Method of more than 0 ppm and less than 400 ppm,
wherein the amount of moisture (200° C. to 300° C.) measured by the Karl Fischer Method is 0 ppm or more and less than 150 ppm, and the amount of moisture (200° C. to 300° C.) measured by the Karl Fischer Method is the moisture that is chemically adsorbed to the surface of the lithium manganese transition metal oxide.

2. The spinel type lithium manganese transition metal oxide according to claim 1 , which is represented by composition formula: Li 1+x M 2−x O 4 , wherein M in the composition formula represents metal elements including Mn, Al and Mg; and x represents 0.01 to 0.09.

3. The spinel type lithium manganese transition metal oxide according to claim 1 , which is represented by composition formula: Li 1+x M 2−x O 4 , wherein M in the composition formula represents metal elements including three elements of Mn, Al and Mg; and x represents 0.01 to 0.09.

4. The spinel type lithium manganese transition metal oxide according to claim 2 , wherein x in the composition formula represents 0.01 to 0.08.

5. The spinel type lithium manganese transition metal oxide according to claim 1 , comprising, as constituent elements, Mg at a proportion of more than 0 wt % and less than or equal to 0.3 wt %, and comprising Al at a proportion of 0.4 wt % to 1.8 wt %.

6. The spinel type lithium manganese transition metal oxide according to claim 5 , comprising Al at a proportion of 0.9 wt % to 1.8 wt %.

7. The spinel type lithium manganese transition metal oxide according to claim 1 , wherein an amount of magnetic substances measured by a measurement method described below is more than 0 ppb and less than 450 ppb:
Method for measuring the amount of magnetic substances:
a 500-cc resinous container with a lid is used, and 500 cc of ion-exchanged water and one cylindrical stirring bar type magnet coated with tetrafluoroethylene, the magnet having a magnetic force in the range of 100 mT to 150 mT when the magnetic force is measured using a TESLA METER Model TM-601 manufactured by Kanetec Co., Ltd., are added to 100 g of the raw material of a positive electrode active material (powder); the mixture is mounted on a rotary rack of a ball mill and is rotated to be slurrified; next, the magnet is taken out and immersed in ion-exchanged water, and any excess powder attached to the magnet is removed in an ultrasonic cleaner; subsequently, the magnet is taken out and immersed in aqua regia, and the magnet is heated at 80° C. for 30 minutes in the aqua regia to dissolve any magnetic substances; the aqua regia in which magnetic substances are dissolved is then analyzed for the amounts of iron, nickel, chromium, and zinc using an ICP emission analyzer, and by designating the total amounts thereof as the amount of magnetic substances, the amount of magnetic substances per weight of the raw material of the positive electrode active material is calculated.

8. The spinel type lithium manganese transition metal oxide according to claim 1 , which is represented by composition formula: Li[Li a Mn 2−a−b−c M1 b M2 c ]O 4-δ wherein M1 in the composition formula represents a metal element including Ni, Co or Fe; M2 in the composition formula represents a metal element including Mg, Ti, Al, Ba, Cr, or Nb; “a” in the composition formula represents 0.00 to 1.0; “b” represents 0.30 to 0.70; “c” is 0.00≦c; and “δ” is 0≦δ.

9. The spinel type lithium manganese transition metal oxide according to claim 8 , comprising a composite oxide phase containing Ni, Mn, and B.

10. The spinel type lithium manganese transition metal oxide according to claim 8 , wherein the amount of magnetic substances measured by a measurement method described below is more than 0 ppb and less than 450 ppb:
Method for measuring the amount of magnetic substances:
a 500-cc resinous container with a lid is used, and 500 cc of ion-exchanged water and one cylindrical stirring bar type magnet coated with tetrafluoroethylene, the magnet having a magnetic force in the range of 100 mT to 150 mT when the magnetic force is measured using a TESLA METER Model TM-601 manufactured by Kanetec Co., Ltd., are added to 100 g of a raw material of a positive electrode active material (powder); the mixture is mounted on a rotary rack of a ball mill and is rotated to be slurrified; next, the magnet is taken out and immersed in ion-exchanged water, and any excess powder attached to the magnet is removed in an ultrasonic cleaner; subsequently, the magnet is taken out and immersed in aqua regia, and the magnet is heated at 80° C. for 30 minutes in the aqua regia to dissolve any magnetic substances; the aqua regia in which magnetic substances are dissolved is then analyzed for the amounts of iron, chromium, and zinc using an ICP emission analyzer, and by designating the total amounts thereof as the amount of magnetic substances, the amount of magnetic substances per weight of the raw material of the positive electrode active material is calculated.

11. The spinel type lithium manganese transition metal oxide according to claim 1 , wherein the sulfur content is more than 0 wt % and less than 0.3 wt %.

12. The spinel type lithium manganese transition metal oxide according to claim 3 , wherein x in the composition formula represents 0.01 to 0.08.

13. The spinel type lithium manganese transition metal oxide according to claim 2 , comprising, as constituent elements, Mg at a proportion of more than 0 wt % and less than or equal to 0.3 wt %, and comprising Al at a proportion of 0.4 wt % to 1.8 wt %.

14. The spinel type lithium manganese transition metal oxide according to claim 3 , comprising, as constituent elements, Mg at a proportion of more than 0 wt % and less than or equal to 0.3 wt %, and comprising Al at a proportion of 0.4 wt % to 1.8 wt %.

15. The spinel type lithium manganese transition metal oxide according to claim 4 , comprising, as constituent elements, Mg at a proportion of more than 0 wt % and less than or equal to 0.3 wt %, and comprising Al at a proportion of 0.4 wt % to 1.8 wt %.

Assignees

• Mitsui Mining & Smelting Co

Inventors

• Mitsumoto Tetsuya
• Ide Hitohiko
• Kagei Shinya
• Hata Yoshimi
• Shibamura Natsumi

Classifications

• H01M4/505 Primary

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• C01G53/50

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

• C01G45/22

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

• Y02E60/10

  Energy storage using batteries · CPC title

• C01G45/00 Primary

  Compounds of manganese · CPC title