Process for making a cathode active material and a precursor therefore, cathode active material and its use

Patent metadata

Field	Value
Publication number	US-10707486-B2
Application number	US-201615751308-A
Country	US
Kind code	B2
Filing date	Aug 10, 2016
Priority date	Aug 17, 2015
Publication date	Jul 7, 2020
Grant date	Jul 7, 2020

Abstract

The present invention is directed towards a process for making a particulate material according to the general formula (I): NiaCObMncMd(O)x(OH)y, wherein M is selected from Al and Ti, x is in the range of from 0.01 to 0.9, y is in the range of from 1.1 to 1.99, a is in the range of from 0.3 to 0.85, b is in the range of from 0.05 to 0.4, c is in the range of from 0.1 to 0.5, d is in the range of from 0.001 to 0.03, with a+b+c+d=1 said process comprising the following steps: (a) providing an aqueous slurry of particles of aluminum hydroxide or titanium dioxide, (b) adding an aqueous solution of water-soluble salts of nickel, cobalt and manganese and a solution of alkali metal hydroxide to the slurry according to step (a), thereby co-precipitating a layer of a mixed hydroxide of nickel and cobalt and manganese hydroxide on the particles according to step (a), (c) removing particles of (NiaCObMncAld)(OH)2+d or (NiaCObMncTid)(OH)2+2d so obtained and drying them in the presence of oxygen.

First claim

The invention claimed is:

1. A process for making a particulate material of formula (I):
Ni a Co b Mn c M d (O) x (OH) y   (I)

wherein
M is Al or Ti,
x is in the range of from 0.01 to 0.9,
y is in the range of from 1.1 to 1.99,
a is in the range of from 0.3 to 0.85,
b is in the range of from 0.05 to 0.4,
c is in the range of from 0.1 to 0.5,
d is in the range of from 0.001 to 0.03,
with a+b+c+d=1,

the process comprising:
(a) providing an aqueous slurry of particles of aluminium hydroxide or titanium dioxide,
(b) adding an aqueous solution of water-soluble salts of nickel, cobalt and manganese and a solution of alkali metal hydroxide to the slurry of (a), thereby co-precipitating a layer of a mixed hydroxide of nickel and cobalt and manganese hydroxide on the particles of (a), and
(c) removing particles of (Ni a Co b Mn c Al d )(OH) 2+d or (Ni a Co b Mn c Ti d )(OH) 2+2d so obtained and drying the particles in the presence of oxygen.

2. The process according to claim 1 , wherein, in the formula (I):
a is in the range of from 0.32 to 0.7,
b is in the range of from 0.25 to 0.35,
c is in the range of from 0.25 to 0.35, and
d is in the range of from 0.002 to 0.03.

3. The process according to claim 1 , wherein (a) is performed by precipitating aluminium hydroxide from a solution of alkali metal aluminate at a pH value in the range from 10 to 13.

4. A particulate material of formula (I):
Ni a CO b Mn c M d (O) x (OH) y   (I)

wherein:
M is Al or Ti,
x is in the range of from 0.01 to 0.9,
y is in the range of from 1.1 to 1.99,
a is in the range of from 0.3 to 0.85,
b is in the range of from 0.05 to 0.4,
c is in the range of from 0.1 to 0.5,
d is in the range of from 0.001 to 0.03,
with a+b+c+d=1; and
the particulate material has a surface according to BET multi-point measurement in the range of from 1.5 m 2 /g to 5.0 m 2 /g.

5. A process for manufacturing a cathode active material for a lithium ion battery, the process comprising:
(d) providing a particulate material according to claim 4 ,
(e) mixing said particulate material with at least one Li compound of Li 2 O, LiOH and Li 2 CO 3 to obtain a mixture, and
(f) calcining the mixture at a temperature of from 800 to 950° C.

6. The process according to claim 5 , wherein (f) last for 3 to 12 hours.

7. The process according to claim 5 , wherein (f) is performed in an oxygen-containing atmosphere.

8. The process according to claim 5 , wherein a molar ratio of lithium to a sum of Ni, Co, Mn and M is in the range of from 1.02 to 1 to 1.25 to 1.

9. A cathode active material, consisting essentially of particles of formula (II):
Li 1+w (Ni a Co b Mn c M d ) 1-w O 2   (II)

wherein:
M is Al or Ti,
w is in the range of from 0.01 to 0.15,
a is in the range of from 0.32 to 0.7,
b is in the range of from 0.2 to 0.35,
c is in the range of from 0.1 to 0.35,
d is in the range of from 0.001 to 0.03,
with a+b+c+d=1;
the cathode active material has a surface according to BET multi-point measurement in the range of from 1.5 m 2 /g to 5 m 2 /g;
M is homogeneously dispersed within the particles; and
the particles have an average particle diameter D50 in the range of from 3 to 8 μm.

10. The cathode active material according to claim 9 , which has a specific conductivity in the range of from 10 −5 to 10 −3 S/cm.

11. A cathode, comprising:
(A) at least one cathode active material according to claim 9 ,
(B) carbon in electrically conductive form,
(C) a binder material, and
(D) a current collector.

12. The cathode according to claim 11 , comprising, relative to a sum of (A), (B), and (C):
80 to 95% by weight of the cathode active material (A),
3 to 17% by weight of carbon (B), and
3 to 10% by weight of the binder material (C).

13. An electrochemical cell, comprising:
at least one cathode according to claim 11 .

14. The electrochemical cell according to claim 13 , further comprising:
an electrolyte comprising at least one flame retardant selected from the group consisting of trimethyl phosphate, CH 3 —P(O)(OCH 3 ) 2 , triphenylphosphate, and tris-(2,2,2-trifluoroethyl)phosphate.

Assignees

• Basf Se

Inventors

• Schroedle Simon
• Ryll Thomas Michael
• Volkov Aleksei
• Shin Ji-Yong
• Lampert Jordan K

Classifications

• C01G53/82 Primary

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

• Y02E60/10

  Energy storage using batteries · CPC title

• C01P2004/50

  Agglomerated particles · CPC title

• C01P2004/32

  Spheres · CPC title

• C01P2006/11

  Powder tap density · CPC title