Positive electrode material having a size dependent composition

Patent metadata

Field	Value
Publication number	US-9748570-B2
Application number	US-201214119924-A
Country	US
Kind code	B2
Filing date	May 14, 2012
Priority date	May 30, 2011
Publication date	Aug 29, 2017
Grant date	Aug 29, 2017

Abstract

The invention relates to cathode materials for Li-ion batteries having a size dependent compositions. The lithium metal oxide powder has a general formula Li a Ni x Co y Mn z M′ m O 2±e A f , with 0.9<a<1.1, 0.2≦x≦0.9, 0<y≦0.4, 0<z≦0.7, 0≦m≦0.35, e<0.02, 0≦f≦0.05 and 0.9<(x+y+z+m+f)<1.1; M′ consisting of either one or more elements from the group Al, Mg, Ti, Cr, V, Fe and Ga; A consisting of either one or more elements from the group F, C, Cl, S, Zr, Ba, Y, Ca, B, Sn, Sb, Na and Zn. The powder has a particle size distribution defining a D10 and a D90; wherein either x1−x2≧0.005; or z2−z1≧0.005; or both x1−x2≧0.005 and z2−z1≧0.005; x1 and z1 being the values of x and z of particles having a particle size D90; and x2 and z2 being the values of x and z of particles having a particle size D10.

First claim

The invention claimed is:

1. A lithium metal oxide powder for use as a cathode material in a rechargeable battery, having a general formula Li a Ni x Co y Mn z M′ m O 2±e A f , with 0.9<a<1.1, 0.2≦x≦0.9, 0<y≦0.4, 0<z≦0.7, m=0, e<0.02, f=0 and 0.9<(x+y+z+m+f)<1.1;
M′ comprising one or more elements selected from the group consisting of Al, Mg, Ti, Cr, V, Fe and Ga; A comprising one or more elements selected from the group consisting of F, C, Cl, S, Zr, Ba, Y, Ca, B, Sn, Sb, Na and Zn; the powder having a particle size distribution defining a D10 and a D90; and wherein either
x1−x2≧0.005; or
z2−z1≧0.005; or
both x1−x2≧0.005 and z2−z1>0.005;
x1 and z1 being the values of x and z of particles having a particle size D90; and x2 and z2 being the values of x and z of particles having a particle size D10, and wherein −0.005≦y1−y2≦0.005, y1 being the value of y of particles having a particle size D90; and y2 being the value of y of particles having a particle size D10, and
one of
a) 0.30≦x≦0.40, 0.30≦y≦0.35 and 0.25≦z≦0.35;
b) 0.45≦x≦0.55, 0.15≦y≦0.25 and 0.25≦z≦0.35;
c) 0.60≦x≦0.70, 0.10≦y≦0.20 and 0.20≦z≦0.30; and
d) 0.20≦x≦0.30, 0.05≦y≦0.15 and 0.60≦z≦0.70.

2. The oxide powder of claim 1 , wherein both x1−x2≧0.010 and z2−z1>0.010.

3. The oxide powder according to claim 1 , wherein the Ni content of the powder increases with increasing particle size, and the Mn content of the powder decreases with increasing particle size.

4. The oxide powder according to claim 1 , wherein A comprises S and C and M′ comprises Mg and/or Al.

5. The oxide powder according to claim 4 , wherein A comprises C and M′ comprises Al.

6. A process for the manufacture of a powder according to claim 1 , comprising:
providing a M-precursor powder, with M=Ni x Co y Mn z M′ m A f , and having a particle size distribution defining a D10 and a D90; wherein either x1−x2≧0.005; or z2−z1≧0.005; or both x1−x2≧0.005 and z2−z1≧0.005; x1 and z1 being the values of x and z of particles having a particle size D90; and x2 and z2 being the values of x and z of particles having a particle size D10,
mixing the M-precursor powder with a lithium precursor, and
heating the mixture at a temperature of at least 800° C.

7. The process according to claim 6 , wherein providing a M-precursor powder comprises:
providing at least two M-precursor powders having different particle size distributions characterized by different D10 and D90 values, wherein a M-precursor powder having a lower D10 and D90 value has one or both of a lower Ni content and a higher Mn content, than a M-precursor powder having a higher D10 and D90 value; and
mixing the at least two M-precursor powders.

8. The process according to claim 7 , wherein the at least two M-precursor powders are mixed with a lithium precursor, before heating the mixture at a temperature of at least 800° C.

9. The process according to claim 7 , wherein both the Ni content of the powder having a lower D10 and D90 value is lower than the Ni content of the powder having a higher D10 and D90 value, and the Mn content of the powder having a lower D10 and D90 value is higher than the Mn content of the powder having a higher D10 and D90 value.

10. The process according to claim 9 , wherein the difference between the Co content of the M-precursor powder having a lower D10 and D90 value, and the Co content of the M-precursor powder having a higher D10 and D90 value, is less than each one of the differences between the Ni and Mn contents of the M-precursor powders.

11. The process according to claim 6 , wherein the M-precursor powder comprises hydroxide or oxyhydroxide compositions obtained by precipitating metal sulphates, nitrates, chlorides or carbonates in the presence of an alkali hydroxide and a chelating agent.

Assignees

• De Palma Randy
• Paulsen Jens
• Kim Jihye
• Umicore Nv

Inventors

• De Palma Randy
• Paulsen Jens
• Kim Jihye

Classifications

• H01M10/0525

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

• H01M10/052

  Li-accumulators · 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

• H01M4/505 Primary

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

• C01G53/50

  of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2 · CPC title