Non-homogenous positive electrode materials combining high safety and high power in a Li rechargeable battery

• US 8,673,170 B2
• Filed: 01/29/2010
• Issued: 03/18/2014
• Est. Priority Date: 02/20/2009
• Status: Active Grant

• Current Assignee: Umicore S.A.
• Original Assignee: Umicore S.A.
• Inventors: Levasseur, Stephane, Carlach, Philippe, De Palma, Randy, Van Thournout, Michle
• Primary Examiner(s): Nguyen, Khanh Tuan
• Application Number:
  US13/201,896
• Publication Number:
  US 20120104311A1
• Time in Patent Office: 1,509 Days
• Field of Search: 252/182.1, 429/217, 429/221, 429/231.3
• US Class Current: 252/182.1
• CPC Class Codes: C01G 51/42 containing alkali metals, e.g. LiCoO2
• CPC Class Codes: C01G 53/42 containing alkali metals, e.g. LiNiO2
• CPC Class Codes: C01P 2002/52 containing elements as dopants
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2002/88 by thermal analysis data, e.g. TGA, DTA, DSC
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/51 Particles with a specific particle size distribution
• CPC Class Codes: C01P 2004/61 Micrometer sized, i.e. from 1-100 micrometer
• CPC Class Codes: C01P 2006/37 Stability against thermal decomposition
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 4/1391 of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/13915 containing halogen atoms, e.g. LiCoOxFy
• CPC Class Codes: H01M 4/525 of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

The invention relates to a Li_aNi_xCo_yM_zO_2±eA_f composite oxide for use as a cathode material in a rechargeable battery, with a non-homogenous Ni/Al ratio in the particles, allowing excellent power and safety properties when used as positive electrode material in Li battery. More particularly, in the formula 0.9<a<1.1, 0.3≦x≦0.9, 0≦y≦0.4, 0<z≦0.35, e=0, 0≦f≦0.05 and 0.9<(x+y+z+f)<1.1; M consists of either one or more elements from the group Al, Mg and Ti; A consists of either one or more elements from the group S and C. The powder has a particle size distribution defining a D10, D50 and D90; and said x and z parameters varying with the particles size of said powder, and is characterized in that either one or both of: x1−x2≧0.010 and z2−z1≧0.010; x1 and z1 being the parameters corresponding to particles having a particle size D90; and x2 and z2 being the parameters corresponding to particles having a particle size D10.

Claims

1. A lithium metal oxide powder for use as a cathode material in a rechargeable battery, having the general formula Li_aNi_xCo_yM_zO_2±

eA_f, wherein

0.9<

a<

1.1, 0.3≦

x≦

0.9, 0<

y≦

0.4, 0<

z≦

0.35, e<

0.02, 0≦

f≦

0.05 and 0.9<

(x+y+z+f)<

1.1;

wherein M comprises one or more elements selected from the group consisting of Al, Mg, and Ti;

A comprises either one or both of S and C;

wherein said powder has a particle size distribution defining a D10, D50 and D90; and

said x and z parameters vary with the particle size of said powder;

wherein either one or both of;

x1−

x2≧

0.010 and

z2−

z1≧

0.010;

x1 and z1 being the parameters corresponding to particles having a particle size D90; and

x2 and z2 being the parameters corresponding to particles having a particle size D10.

2. The powder of claim 1, wherein both x1−

x2≧

0.030 and z2−

z1≧

0.030.

3. The powder of claim 2, wherein x1−

x2≧

0.050 and z2−

z1≧

0.050.

4. The powder of claim 1, wherein the Ni content of said powder increases with increasing particle size, and the M content of said powder decreases with increasing particle size.

5. The powder of claim 1, wherein A comprises S and C, with f≦

0.02, and M comprises Al.

6. The powder of claim 1, wherein A comprises C, with f≦

0.01, and M comprises Al.

7. The powder of claim 6, having a general formula Li_aNi_0.80Co_0.15Al_0.05C_0.01O₂.

8. A process for manufacturing the powder of claim 1, comprising:

providing at least two Li_aNi_xCo_yM_zO<sub>2±

e</sub>A_f precursor powders having different particle size distributions with different D10 and D90 values, wherein a powder having lower D10 and D90 values has a lower Ni content and a higher M content than a powder having higher D10 and D90 values,

mixing said at least two precursor powders together with a lithium precursor, and

heating said mixture at a temperature of at least 600°

C.

9. The process of claim 8, wherein the lithium precursor is lithium hydroxide.

10. The process of claim 8, wherein said precursor powders comprise hydroxide or oxyhydroxide compositions obtained by precipitating metal sulphates, nitrates, chlorides or carbonates in the presence of an alkali hydroxide and a chelating agent.

11. The process of claim 10, wherein the chelating agent is ammonia.

12. The process of claim 8, wherein the Co content of said precursor powders is identical.