Mixed oxide containing a lithium manganese spinel and process for its preparation

Patent metadata

Field	Value
Publication number	US-9281522-B2
Application number	US-99937609-A
Country	US
Kind code	B2
Filing date	Jun 23, 2009
Priority date	Jun 24, 2008
Publication date	Mar 8, 2016
Grant date	Mar 8, 2016

Abstract

A mixed oxide containing
a) a mixed-substituted lithium manganese spinel in which some of the manganese lattice sites are occupied by lithium ions and b) a boron-oxygen compound.

Furthermore, a process for its preparation and the use of the mixed oxide as electrode material for lithium ion batteries.

First claim

The invention claimed is:

1. Mixed oxide containing
a) a mixed-substituted lithium manganese spinel as a first constituent in which a first portion of the manganese lattice sites are occupied by lithium ions and
b) a boron-oxygen constituent as a second constituent,
wherein the mixed oxide is a single-phase homeotype mixed crystal comprising the two constituents wherein the second constituent is in the same phase as the first Constituent, and
wherein the mixed oxide has a composition satisfied by the following formula:
[(Li 1−a M a )(Mn 2−c−d Li c N d )O x ].b(B z O y H u X v )

 wherein
0≦a<0.1;
d ≦1.2
3.5<×<4.5;
0.01<c<0.06
z=1, 2 or 4
y=1, 2, 3 or 7
u=0, 1, 2 or 3
v=0, 1, 2 or 3
0.01<b<0.5
M is at least one element selected from the group of Zn, Mg, and Cu;
N is at least on element selected from the group of Al, Mg, Zn, Co, Ni, Cu and Cr; and
X is at least one element selected from the group Li, Na, K,
wherein in the mixed-substituted lithium manganese spinal, and second portion of the manganese lattice sites are occupied by mental ions of N selected from at least one of Ni and Co, wherein either “d” of Ni is 0.5+/−0.1 or “d”of Co is 1+/−0.2, and the size of the primary crystallites of the mixed oxide, measured as D 50 , is at least 0.5 μm.

2. Mixed oxide according to claim 1 , wherein in the mixed-substituted lithium manganese spinel further manganese lattice sites are occupied by metal ions of N selected from the group consisting of Al, Mg, Zn, Cu and Cr.

3. Mixed oxide according to claim 2 , wherein some of the lithium ions on the 8a tetrahedral sites are substituted by the metal ion M, selected from the group consisting of Zn, Mg and Cu.

4. Mixed oxide according to claim 1 , wherein the X-ray diffractogram of the mixed oxide has a signal at a diffraction angle 2θ in the range from 63.5 to 65°, in which the ratio of the line widths B 10 measured at 10% of the signal height to the line width B 50 measured at 50% of the signal height is less than 2.0, preferably less than 1.8.

5. Mixed oxide according to claim 4 with a BET surface area of less than 4 m 2 /g.

6. Mixed oxide according to claim 5 , wherein the size of the primary crystallites of the mixed oxide, measured as D 50 , is greater than 1 μm.

7. An electrode, comprising an electrically conductive support to which a mixed oxide according to claim 1 is applied.

8. Secondary battery with an electrode according to claim 7 .

Assignees

• Vogler Christian
• Nuspl Gerhard
• Wohlfahrt-Mehrens Margret
• Axmann Peter
• Arnold Gisela
• Johnson Matthey Plc

Inventors

• Vogler Christian
• Nuspl Gerhard
• Wohlfahrt-Mehrens Margret
• Axmann Peter
• Arnold Gisela

Classifications

• C01P2004/51

  Particles with a specific particle size distribution · CPC title

• C01G51/54

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

• H01M10/052

  Li-accumulators · CPC title

• C01P2006/13

  thermal stability thereof at high temperatures · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title