Precursors for cathode material with improved secondary battery performance and method to prepare the precursors

Patent metadata

Field	Value
Publication number	US-11476461-B2
Application number	US-201716492206-A
Country	US
Kind code	B2
Filing date	Mar 14, 2017
Priority date	Mar 14, 2017
Publication date	Oct 18, 2022
Grant date	Oct 18, 2022

Abstract

A crystalline precursor compound for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor having a general formula M(O)x(OH)2-x-y(CO3)y, with 0<x≤1, 0<y<0.03 and M=NiaMnbCocAd. A being a dopant, with 0.30≤a<0.90, 0.10≤b<0.40, 0.10≤c<0.40, d<0.05 and a+b+c+d=1, the precursor having a Na content less than 200 ppm, a S content less than 250 ppm, the precursor having a specific surface area with a BET value expressed in m2/g and a tap density TD expressed in g/cm3, with a ratio BET/TD>30.104 cm5/g2.

First claim

The invention claimed is:

1. A crystalline precursor compound for manufacturing a lithium transition metal based oxide powder usable as an active positive electrode material in lithium-ion batteries, the precursor having a general formula M(O) x (OH) 2-x-y (CO 3 ) y , with 0≤x≤1, 0<y≤0.03 and M=Ni a Mn b Co c A d , A being a dopant, with 0.30≤a≤0.90, 0.10≤b≤0.40, 0.10≤c≤0.40, d≤0.05 and a+b+c+d=1, the precursor having a Na content less than 200 ppm, a S content less than 250 ppm, the precursor having a specific surface area with a BET value expressed in m 2 /g and a tap density TD expressed in g/cm 3 , with a ratio BET/TD≥30.10 4 cm 5 /g 2 .

2. The crystalline precursor compound of claim 1 , having a tap density TD≥1.0 g/cm 3 .

3. The crystalline precursor compound of claim 1 , having a BET value≥35 m 2 /g.

4. The crystalline precursor compound of claim 1 , having a Na content less than 100 ppm, a S content less than 200 ppm, and the sum of the Na and the S content being less than 300 ppm.

5. The crystalline precursor compound of claim 1 , having a BET value≥45 m 2 /g.

6. The crystalline precursor compound of claim 1 , having a tap density TD≥1.2 g/cm 3 .

7. The crystalline precursor compound of claim 1 , having a median particle size (D50) between 5-25 μm.

8. The crystalline precursor compound of claim 1 , having a carbon content ≤0.15 wt %.

9. A method for preparing the crystalline precursor compound according to claim 1 , the method comprising the steps of:
providing a MSO 4 sulfate feed solution comprising Ni—, Mn—, Co— and A-ions,
providing an ionic solution comprising one or both of a carbonate and a bicarbonate solution, the ionic solution further comprising one or both of Na— and K-ions,
mixing the sulfate feed solution and the ionic solution in a reactor with a CO 3 /M molar ratio≥1.0, thereby precipitating a M-carbonate intermediate product, and
dispersing the M-carbonate intermediate product in a NaOH solution at a temperature between 70 and 95° C. with a OH/M molar ratio≥2.0, thereby precipitating a crystalline precursor.

10. The method according to claim 9 , wherein the OH/M molar ratio is between 2.0 and 2.1.

11. The method according to claim 9 , wherein the molar ratio CO 3 /M≥1.05.

12. The method according to claim 9 , further comprising the additional steps of:
filtering and washing the precursor until the conductivity of the filtrate reaches at most 50 μS/cm, and
drying the filtered and washed precursor at a temperature between 120 and 160° C. for 12-36 hrs. in an air atmosphere.

13. The method according to claim 9 , wherein the MSO 4 sulfate feed solution has a molar content M feed , and the method further comprises
in addition to the MSO 4 sulfate feed and the ionic solution, providing a slurry comprising seeds comprising M′-ions and having a molar metal content M′ seeds , wherein M′═Ni x′ Mn y′ Co z′ A′ n′ , A′ being a dopant, with 0≤x′≤1, 0≤y′≤1, 0≤z′≤1, 0≤n′≤1 and x′+y′+z′+n′=1,
mixing the sulfate feed solution, the ionic solution and the slurry in a reactor with a CO 3 /M molar ratio≥1.0 and a molar ratio M′ seeds /M feed between 0.001 and 0.1, thereby precipitating the M-carbonate intermediate product on the seeds, and
dispersing the M-carbonate intermediate product precipitated on the seeds in the NaOH solution.

14. The method according to claim 13 , wherein M=M′.

15. The method according to claim 13 , wherein the seeds have a median particle size D50 between 0.1 and 3 μm, and wherein the M′-ions are present in a water insoluble compound that is one of M′CO 3 , M′(OH) 2 , M′-oxide or M′OOH.

Assignees

• Umicore Nv
• Umicore Korea Ltd

Inventors

• Paulsen Jens
• Nelis Daniël
• Hu Jin
• Zhu Liang
• Robert Eric

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2006/40

  Electric properties · CPC title

• H01M4/505 Primary

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

• C01P2002/72

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