Manganese oxides production thereof, and use thereof

• US 5,672,329 A
• Filed: 01/11/1996
• Issued: 09/30/1997
• Est. Priority Date: 07/29/1992
• Status: Expired due to Term

• Current Assignee: Tosoh Corporation
• Original Assignee: Tosoh Corporation
• Inventors: Okada, Masaki, Mouri, Takashi
• Primary Examiner(s): BOS, STEVEN J
• Application Number:
  US08/584,094
• Time in Patent Office: 628 Days
• Field of Search: 423/594, 423/599, 423/205, 423/206, 429/224
• US Class Current: 423/599
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/1221 Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
• CPC Class Codes: C01G 45/1242 of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
• CPC Class Codes: C01G 51/52 of the type [Mn2O4]2-, e.g. Li2(CoxMn2-x)O4, Li2(MyCoxMn2-x-y)O4
• CPC Class Codes: C01P 2002/02 Amorphous compounds
• CPC Class Codes: C01P 2002/20 Two-dimensional structures
• CPC Class Codes: C01P 2002/22 layered hydroxide-type, e.g. of the hydrotalcite-type
• CPC Class Codes: C01P 2002/32 spinel-type (AB2O4)
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/74 by peak-intensities or a ratio thereof only
• CPC Class Codes: C01P 2002/78 by stacking-plane distances or stacking sequences
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/82 water content
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A manganeses oxide is provided which is represented by the general formula A_x Mn₂ O₄.nH₂ O, where A is Zn, Mg, Ca, or Co; and if A is Zn, 0<x<1 and n=0; if A is Mg or Ca, 0≦x≦1 and 0≦n≦20; and if A is Co 0<x≦1 and n=0. The manganese oxide has a spinel type, a layer type, or amorphous type both crystal structures of layer type and spinel type. The manganese oxide is produced by oxidizing a mixture of a hydroxide of A (where A is Zn, Mg, Ca, or Co) and manganese hydroxide in a molar ratio 1:2 in an alkali solution, and then removing A by oxidation treatment. A lithium secondary battery is provided by use of a kind of the above manganese oxide for the positive electrode, exhibiting high output with high energy density and with satisfactory reversibility in charge-discharge cycle.

Claims

1. A manganese oxide represented by the general formula A_x Mn₂ O₄.nH₂ O, where A is selected from the group consisting of Zn, Mg, Ca and Co;

and if A is Zn, 0.1<

x<

0.67, n=0 and said manganese oxide has a spinel crystal structure;

if A is Mg, 0<

x<

1, 0≦

n≦

20, said manganese oxide has a layer crystal structure having interplanar spacings

9.23±

0.05 angstrom

7.14±

0.05 angstrom

5.00±

0.05 angstrom

3.56±

0.05 angstrom

2.51±

0.05 angstrom and

2.48±

0.05 angstrom;

if A is Ca, x is 1 or 0.1<

x<

0.19, and 0≦

n≦

20, said manganese oxide has an amorphous crystal structure when x=1 having interplanar spacings

3. The manganese oxide of claim 1, wherein A is Ca, x=1, and the manganese oxide has an amorphous crystal structure.

4. The manganese oxide of claim 1, wherein A is Ca, 0.1<

x<

0.19, and the manganese oxide has a δ

crystal structure.

5. The manganese oxide of claim 1, wherein A is Zn and said manganese oxide has a BET specific surface area of not less than 100 m² /g.

6. The manganese oxide of claim 1, wherein A is Zn.

7. The manganese oxide of claim 1, wherein A is Mg.

8. The manganese oxide of claim 1, wherein said compound has a reduction capacity, when used as an electrode in a battery and subjected to repeated oxidation-reduction, within the range of from 7.2 to 16.9 mAh/g.

9. The manganese oxide of claim 1, wherein said compound has a peak current, when used as an electrode in a battery and subjected to repeated oxidation-reduction, within the range of from 7.1 to 16.0 mA/cm².

10. The manganese oxide of claim 1, wherein said compound has an average output, when used as an electrode in a battery and subjected to repeated oxidation-reduction, within the range of from 10.3 to 22.4 mWh/cm².

2. 8±

0.05 angstrom

3.1±

0.05 angstrom

and said manganese oxide has a δ

crystal structure when 0.1<

x<

0.19; and

if A is Co, 0.7<

x<

0.8, n=0 and said manganese oxide has a mixed crystal structure of both a layer and a spinel.