High-density precursor for manufacture of composite metal oxide cathodes for li-ion batteries

Patent metadata

Field	Value
Publication number	US-2016036043-A1
Application number	US-201414449987-A
Country	US
Kind code	A1
Filing date	Aug 1, 2014
Priority date	Aug 1, 2014
Publication date	Feb 4, 2016
Grant date	—

Abstract

The disclosed embodiments relate to the manufacture of a precursor co-precipitate material for a cathode active material composition. During manufacture of the precursor co-precipitate material, an aqueous solution containing at least one of a manganese sulfate and a cobalt sulfate is formed. Next, a NH 4 OH solution is added to the aqueous solution to form a particulate solution comprising irregular secondary particles of the precursor co-precipitate material. A constant pH in the range of 10-12 is also maintained in the particulate solution by adding a basic solution to the particulate solution.

First claim

What is claimed is:

1 . A method for manufacturing a precursor co-precipitate material for a cathode active material composition, comprising:
forming an aqueous solution comprising at least one of a manganese sulfate and a cobalt sulfate; adding a NH 4 OH solution to the aqueous solution to form a particulate solution comprising irregular secondary particles of the precursor co-precipitate material; and maintaining a constant pH in the range of 10-12 in the particulate solution by adding a basic solution to the particulate solution.

2 . The method of claim 1 , further comprising:
agitating the particulate solution to form spherical co-precipitate particles from the irregular secondary particles.

3 . The method of claim 2 , further comprising:
filtering the spherical co-precipitate particles from the particulate solution; washing the filtered spherical co-precipitate particles; and drying the spherical co-precipitate particles.

4 . The method of claim 2 , wherein the spherical co-precipitate particles have a median particle size of greater than 5 microns.

5 . The method of claim 2 , wherein the particulate solution is agitated for 3-72 hours or continuously.

6 . The method of claim 1 , wherein the particulate solution is maintained at a constant temperature in the range of 30-65° C.

7 . The method of claim 1 , wherein the basic solution comprises at least one of an alkali metal hydroxide, an alkali carbonate, and an alkali oxalate.

8 . The method of claim 7 , wherein a concentration of the alkali metal hydroxide in the basic solution ranges from 0.5 mol/L to 10 mol/L.

9 . The method of claim 1 , wherein the precursor co-precipitate material has a composition represented by Mn x M y Co z (OH) 2 .

10 . The method of claim 9 , wherein M comprises one or more metal cations selected from one or more monovalent, divalent, trivalent or tetravalent cations and Ru.

11 . The method of claim 9 , wherein a concentration of the manganese, M, and cobalt sulfates in the aqueous solution ranges from 0.5 mol/L to 5 mol/L.

12 . A precursor to a cathode active material composition, having a composition represented by Mn x M y Co z (OH) 2 .

13 . The precursor of claim 12 , wherein the cathode active material composition has a composition represented by xLi 2 MO 3 .(1−x)LiCo 2 M′ (1−y) O 2 .

14 . The precursor of claim 13 , wherein Mn, Co, M, and M′ possess an average oxidation state of three in the cathode active material composition.

15 . The precursor of claim 13 , wherein the cathode active material composition is created using a solid-state reaction of the precursor and a lithium salt.

16 . The precursor of claim 12 , wherein 0.01≦x<1.00, 0≦y<1.00, and 0.50≦z<1.00.

17 . The precursor of claim 12 , wherein the precursor is formed using a solution co-precipitation reaction.

18 . An apparatus for manufacturing a precursor co-precipitate material for a cathode active material composition, comprising:
a reactor maintained at a constant temperature and under an inert gas atmosphere; a first feeding mechanism configured to add an aqueous solution comprising at least one of a manganese sulfate and a cobalt sulfate to the reactor; a second feeding mechanism configured to add a NH 4 OH solution to the aqueous solution to form a particulate solution comprising irregular secondary particles of the precursor co-precipitate material; and a pH controller configured to maintain a constant pH in the range of 10-12 in the particulate solution by adding a basic solution to the particulate solution.

19 . The apparatus of claim 18 , further comprising:
an agitator in the reactor, configured to agitate the particulate solution to form spherical co-precipitate particles from the irregular secondary particles.

20 . The apparatus of claim 19 , wherein the particulate solution is agitated for 3-72 hours or continuously.

21 . The apparatus of claim 18 , wherein the constant temperature is in the range of 30-65° C.

22 . The apparatus of claim 18 , wherein the precursor co-precipitate material has a composition represented by Mn x M y Co z (OH) 2 .

23 . The apparatus of claim 18 , wherein the basic solution comprises at least one of an alkali metal hydroxide, an alkali carbonate, and an alkali oxalate.

24 . The apparatus of claim 23 , wherein a concentration of the alkali metal hydroxide in the basic solution ranges from 0.5 mol/L to 10 mol/L.

25 . A spherical precursor co-precipitate material for a cathode active material composition, having a composition represented by Mn x M y Co z (OH) 2 .

26 . The spherical precursor co-precipitate material of claim 25 , wherein M comprises one or more metal cations selected from one or more monovalent, divalent, trivalent or tetravalent cations and Ru.

27 . The spherical precursor co-precipitate material of claim 25 , wherein 0.01≦x≦0.30, 0≦y≦0.20, and 0.70≦z<1.00.

Assignees

• Apple Inc

Inventors

• Dai Hongli
• Johnson Christopher S
• Wu Huiming
• Carter John David

Classifications

• C01G53/50

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

• C01P2002/50

  Solid solutions · CPC title

• C01P2006/11

  Powder tap density · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• H01M4/505

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