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

Patent metadata

Field	Value
Publication number	US-2018358615-A1
Application number	US-201615751308-A
Country	US
Kind code	A1
Filing date	Aug 10, 2016
Priority date	Aug 17, 2015
Publication date	Dec 13, 2018
Grant date	—

Abstract

The present invention is directed towards a process for making a particulate material according to the general formula (I): Ni a CO b Mn c M d (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 (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 them in the presence of oxygen.

First claim

1 . A process for making a particulate material of general 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, said process comprising: (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 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 mime of from 0.002 to 0.03.

3 . The process according to claim 1 , wherein (a) is performed by precipitating aluminum 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 said 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 0.3 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 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 said particles; and said 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, containing
(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 , containing: relative to a sum of (A), (B), and (C),
80 to 95% b 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, containing
at least one cathode according to claim 11 .

14 . The electrochemical cell according to claim 13 , further containing
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

• H01M10/0567

  characterised by the additives · CPC title

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• C01P2004/32

  Spheres · CPC title

• C01P2006/11

  Powder tap density · CPC title

• C01P2002/52

  containing elements as dopants · CPC title