Metal-containing trimanganese tetraoxide composite particles and method for producing same

Patent metadata

Field	Value
Publication number	US-10109857-B2
Application number	US-201314389536-A
Country	US
Kind code	B2
Filing date	Mar 29, 2013
Priority date	Apr 5, 2012
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

Metal-containing trimanganese tetraoxide combined particles containing a metal element (excluding lithium and manganese). Such metal-containing trimanganese tetraoxide combined particles can be obtained by a production process comprising a crystallization step of crystalizing a metal-substituted trimanganese tetraoxide not by means of metal-substituted manganese hydroxide from a manganese salt aqueous solution containing manganese ions and metal ions other than manganese.

First claim

The invention claimed is:

1. Metal-containing trimanganese tetraoxide combined particles containing a metal element, said metal element being one other than lithium or manganese,
wherein
said particles are particles in which manganese in the crystal structure of trimanganese tetraoxide is substituted by the metal element;
said particles are continuously produced by a process comprising crystallizing trimanganese tetraoxide at a temperature of at least 60° C. and at most 95° C. from a manganese salt aqueous solution containing manganese ions and a metal element other than manganese and lithium, wherein the crystallizing is in the absence of a complexing agent and:
a) is not by a hydroxide of manganese, or
b) is under conditions where crystal growth of a hydroxide of manganese is suppressed;

said particles have an average particle size from 3 μm to 30 μm;
the coefficient of variation of the standard deviation of the particle size is at most 50%;
said particles have a tap density of at least 1.1 g/cm 3 ; and
said particles have a BET specific surface area of at most 2 m 2 /g.

2. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein the metal element is at least one member selected from the group consisting of Mg, Al, Si, Ca, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In and Sn.

3. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein the metal element is at least one of Al and Mg.

4. The metal-containing trimanganese tetraoxide combined particles according to claim 1 which are represented by the following formula (1):
A x Mn 3-x O 4   (1)

wherein A is the metal element excluding lithium and manganese, and x is at most 1.

5. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein the tap density is at least 1.5 g/cm 3 .

6. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein a hydroxide of manganese comprises manganese hydroxide and/or metal-containing manganese hydroxide.

7. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein the crystallizing excludes precipitating a hydroxide of manganese at a pH greater than 9.

8. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein crystallizing trimanganese tetraoxide occurs at a pH from 6 to 9.

9. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein the not by a hydroxide of manganese excludes crystallizing an oxide of manganese and wherein the process further excludes oxidizing the hydroxide of manganese by an oxidizing agent to produce a metal-containing trimanganese tetraoxide.

10. The metal-containing trimanganese tetraoxide combined particles according to claim 1 , wherein the conditions where crystal growth of a hydroxide of manganese is suppressed comprises precipitating fine crystals of hydroxide of trimanganese and oxidization to trimanganese tetraoxide, and wherein fine crystals of hydroxide of trimanganese excludes hexagonal plate-form crystals of a hydroxide of trimanganese.

11. A lithium manganese oxide, which is obtained from the metal-containing trimanganese tetraoxide combined particles as defined claim 1 .

12. A cathode active material, which comprises the lithium manganese oxide as defined in claim 11 .

13. A process for producing the metal-containing trimanganese tetraoxide combined particles as defined in claim 1 , the process comprising crystallizing the metal-substituted trimanganese tetraoxide under conditions which satisfy at least one of a pH of at least 6 and at most 9 and an oxidation-reduction potential of at least 0 mV and at most 300 mV.

14. A process for producing the metal-containing trimanganese tetraoxide combined particles as defined in claim 1 , the process comprising blowing an oxygen-containing gas into the manganese salt aqueous solution.

15. A process for producing a metal-substituted lithium manganese oxide, which comprises mixing the metal-containing trimanganese tetraoxide combined particles as defined in claim 1 with a lithium compound, and subjecting the mixture to heat treatment.

16. Metal-containing trimanganese tetraoxide combined particles comprising crystalline trimanganese tetraoxide in which some of the manganese in the crystal structure of trimanganese tetraoxide is substituted by a metal element other than lithium or manganese;
wherein said particles:
have a have a tap density of at least 1.1 g/cm 3 ,
have an average particle size from 3 μm to 30 μm,
have a BET specific surface area of at most 2 m 2 /g,
vary in size such that the coefficient of variation of the standard deviation of the particle size is at most 50%, and
are continuously produced by a process comprising crystallizing trimanganese tetraoxide at a temperature of at least 60° C. and at most 95° C. at a pH from 6 to 9 from a manganese salt aqueous solution containing manganese ions and a metal element other than manganese and lithium, wherein crystallizing trimanganese tetraoxide occurs:
in the absence of a complexing agent; and
in the absence of the formation of hexagonal plate-form crystals of manganese hydroxide and/or a metal-containing manganese hydroxide.

17. The metal-containing trimanganese tetraoxide combined particles according to claim 16 which are represented by the following formula (1):
A x Mn 3-x O 4   (1)

wherein A is the metal element excluding lithium and manganese, and x is at most 1.

18. The metal-containing trimanganese tetraoxide combined particles according to claim 16 , wherein the metal element is at least one metal element selected from Mg, Al, Si, Ca, Ti, V, Cr, Co, Ni, Cu, Zn, Ga, Ge, Y, Zr, Nb, Mo, Ag, In and Sn.

19. The metal-containing trimanganese tetraoxide combined particles according to claim 16 , wherein the continuously produced by a process excludes crystallizing a hydroxide of manganese and then oxidizing the hydroxide of manganese by an oxidizing agent to produce a metal-containing trimanganese tetraoxide.

Assignees

• Tosoh Corp

Inventors

• Iwata Eiichi
• Yamashita Miki
• Fujii Yasuhiro

Classifications

• C01G45/00

  Compounds of manganese · CPC title

• C01P2004/61

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

• C01P2002/76

  by a space-group or by other symmetry indications · CPC title

• H01M4/505 Primary

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

• C01P2004/45

  Aggregated particles or particles with an intergrown morphology · CPC title