Precursors of cathode materials for a rechargeable lithium ion battery

Patent metadata

Field	Value
Publication number	US-2020017370-A1
Application number	US-201916568756-A
Country	US
Kind code	A1
Filing date	Sep 12, 2019
Priority date	Mar 8, 2017
Publication date	Jan 16, 2020
Grant date	—

Abstract

A method for manufacturing a cobalt based hydroxide carbonate compound having a malachite-rosasite mineral structure, comprising the steps of:
providing an first aqueous solution comprising a source of Co, providing a second aqueous solution comprising Na 2 CO 3 , mixing both solutions in a precipitation reactor at a temperature above 70° C., thereby precipitating a cobalt based hydroxide carbonate compound whilst evacuating from the reactor any CO 2 formed by the precipitation reaction, wherein the residence time of the compound in the reactor is between 1 and 4 hours, and recovering the cobalt based hydroxide carbonate compound. The cobalt based hydroxide carbonate compound is used as a precursor of a lithium cobalt based oxide usable as an active positive electrode material in lithium ion batteries.

First claim

1 . A method for manufacturing a cobalt based hydroxide carbonate compound, comprising the steps of:
providing a first aqueous solution comprising a source of Co, providing a second aqueous solution comprising Na 2 CO 3 , mixing both solutions in a precipitation reactor at a temperature above 70° C., thereby precipitating a cobalt based hydroxide carbonate compound whilst evacuating from the reactor any CO 2 formed by the precipitation reaction, wherein the residence time of the compound in the reactor is between 1 and 4 hours, and recovering the cobalt based hydroxide carbonate compound.

2 . The method according to claim 1 , wherein the second aqueous solution comprises:
a solution of at least 2N Na 2 CO 3 , or a solution comprising between 0.5 and 3 mol/L of Na 2 CO 3 and between 1 and 6 mol/L NaOH, wherein the Na content in the Na 2 CO 3 is as high or higher than twice the Na content in the NaOH.

3 . The method according to claim 1 , wherein the first aqueous solution further comprises a source of one or more of Ni, Mn, Al, Mg and Ti.

4 . The method according to claim 1 , wherein the first solution comprising a source of Co comprises CoSO 4 , and further comprises one or more of MgSO 4 , Al 2 (SO 4 ) 3 , NiSO 4 and MnSO 4 , wherein one or more of Mg, Al, Ni and Mn are present in a molar ratio versus the Co content of between 0.2 and 5 mol %.

5 . The method according to claim 1 , wherein during the step of mixing both solutions a nanometric powder comprising one or more of TiO 2 , MgO or Al 2 O 3 is added.

6 . The method according to claim 1 , wherein the step of recovering the cobalt based hydroxide carbonate compound comprises the substep of transferring the compound to a settlement reactor coupled to the precipitation reactor, and whereafter from the settlement reactor the settled compound is recirculated to the precipitation reactor.

7 . A method for manufacturing a lithiated cobalt based oxide, comprising the steps of claim 1 , and subsequently additionally comprising the steps of:
mixing the cobalt based hydroxide carbonate compound with a source of Li, and sintering the mixture at a temperature above 950° C. in an oxygen containing atmosphere.

8 . The method according to claim 7 , wherein the precipitated cobalt based hydroxide carbonate compound comprises Na as an impurity between 0.1 and 0.3 wt %, and wherein either:
during the step of mixing the cobalt based hydroxide carbonate compound with the source of Li, or during the step of sintering the mixture;
adding a sulfate compound, whereby the molar quantity of SO 4 is equal to or higher than the molar content of Na, and subsequently comprising the step of washing the lithiated cobalt based oxide with water, and drying the lithiated cobalt based oxide.

9 . The method according to claim 8 , wherein the sulfate compound is one of Li 2 SO 4 , NaHSO 4 , CoSO 4 and Na 2 S 2 O 8 .

10 . A cobalt based hydroxide carbonate compound, having the general formula [Co 1-a A a ] 2 (OH) 2 CO 3 , A being one or more of Ni, Mn, Al, Ti, Zr and Mg, with a≤0.05.

11 . The cobalt based hydroxide carbonate compound of claim 10 , further comprising Na as an impurity of up to 0.3 wt %.

12 . The cobalt based hydroxide carbonate compound of claim 10 , having a particle size distribution with D50 between 15 and 25 μm and a span <0.80.

13 . The cobalt based hydroxide carbonate compound of claim 10 , wherein the compound has a spherical morphology and a tap density >1.8 g/cm 3 .

14 . The cobalt based hydroxide carbonate compound of claim 10 , wherein A is one or both of Al and Mg, with 0.002≤a≤0.020, and wherein one or both of Al and Mg is homogeneously doped in the compound.

15 . A cathode active material powder prepared from the cobalt based hydroxide carbonate compound of claim 10 .

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Kim Dae-Hyun
• Paulsen Jens
• Oh Jindoo
• Blangero Maxime

Classifications

• C01P2002/72

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M4/525 Primary

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title