Nano-sized structured layered positive electrode materials to enable high energy density and high rate capability lithium batteries

• US 20090297947A1
• Filed: 05/22/2009
• Published: 12/03/2009
• Est. Priority Date: 05/30/2008
• Status: Active Grant

• Current Assignee: UChicago Argonne LLC (University of Chicago)
• Original Assignee: UChicago Argonne LLC (University of Chicago)
• Inventors: Deng, Haixia, Belharouak, Ilias, Amine, Khalil
• Granted Patent: US 8,277,683 B2
• Time in Patent Office: Days
• US Class Current: 429/218.1
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/0497 Chemical precipitation
• CPC Class Codes: H01M 4/485 of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy H01M4/505, H01M4/525 take precedence
• CPC Class Codes: H01M 4/505 of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
• 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

Nano-sized structured dense and spherical layered positive active materials provide high energy density and high rate capability electrodes in lithium-ion batteries. Such materials are spherical second particles made from agglomerated primary particles that are Li_1+α(Ni_xCo_yMn_z)_1−tM_tO_2−dR_d, where M is selected from can be Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, or a mixture of any two or more thereof, R is selected from F, Cl, Br, I, H, S, N, or a mixture of any two or more thereof, and 0≦α≦0.50; 0<x≦1; 0≦y≦1; 0<z≦1; 0≦t≦1; and 0≦d≦0.5. Methods of preparing such materials and their use in electrochemical devices are also described.

Claims

1. A material comprising

a plurality of metal oxide secondary particles comprising primary particles,

wherein;

an average primary particle size is about 1 nm to 500 nm;

an average secondary particle size is about 1 μ

m to 100 μ

m;

the material is a positive active material;

and further wherein the primary particles comprise

Li_1+α

(Ni_xCo_yMn_z)<sub>1−

t</sub>M_tO<sub>2−

d</sub>R_d;

wherein

M is selected from Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, or a mixture of any two or more thereof;

R is selected from F, Cl, Br, I, H, S, N, or a mixture of any two or more thereof; and

0≦

α

≦

0.50;

0<

x≦

1;

0≦

y≦

1;

0<

z≦

1;

0≦

t≦

1; and

0≦

d≦

0.5.

2. The material of claim 1, wherein the average primary particle size is about 5 nm to 200 nm, and the average secondary particle size is about 1 μ

m to 30 μ

m.

3. The material of claim 1, wherein the secondary particles are spherical.

4. The material of claim 1, wherein the primary particles comprise

Li_1+α

′

Ni_x′

Mn_z′

O<sub>2−

d′</sub>

F_d;

wherein α

′

is from 0 to 0.2, x′

is from 0.1 to 0.6, z′

is from 0.2 to 0.6, and d′

is from 0 to 0.1.

5. The material of claim 1, where the primary particles comprise

Li_1+α

′

Ni_x′

Co_y′

Mn_z″

O<sub>2−

d′</sub>

F_d′

, wherein α

′

is from 0 to 0.2, x′

is from 0.1 to 0.6, y′

is from 0.01 to 0.4, z″

is from 0.1 and 0.6, and d′

is from 0 to 0.1.

6. The material of claim 1, wherein:

the primary particles comprise a composite formula of β

LiMe′

O_2′

(1−

β

)Li₂Me″

O₃;

0<

β

<

1;

Me′

is one or more ions having an average oxidation state of three with at least one ion being Ni; and

Me″

is one or more ions having an average oxidation state of four with at least one ion being Mn.

7. The material of claim 6, wherein the LiMe′

O₂ and Li₂Me″

O₃ are layered and the ratio of Li to Me′ and

Me″

is greater than one but less than two.

8. The material of claim 1, wherein the primary particles comprise Li_1.1Ni_0.2Mn_0.6O₂.

9. The material of claim 1, wherein the primary particles comprise Li_1.3Ni_0.2Mn_0.6O₂.

18. The material of claim 1, wherein the material further comprises a carbon-coating.

19. An electrochemical device comprising:

a positive electrode comprising the material of claim 1;

a negative electrode;

and a non-aqueous electrolyte.

10. A process for preparing a material comprising:

preparing an acidic solution;

preparing a basic solution;

combining the acidic solution with the basic solution; and

precipitating a nano-sized structured precursor from the combined acidic and basic solutions to provide the material;

wherein;

the material comprises a plurality of metal oxide secondary particles comprising primary particles;

the average primary particle size is about 1 nm to 200 nm; and

the average secondary particle size is about 1 μ

m to 30 μ

m.

11. The process of claim 10, wherein the nano-sized structured precursor comprises

(Ni_xCo_yMn_z)₁₋

tM_tCO<sub>3−

d</sub>R_d;

M is selected from Al, Mg, Fe, Cu, Zn, Cr, Ag, Ca, Na, K, In, Ga, Ge, V, Mo, Nb, Si, Ti, Zr, or a mixture of any two or more thereof;

R is selected from F, Cl, Br, I, H, S, N, or a mixture of any two or more thereof; and

0<

x≦

1, 0≦

y≦

1, 0<

z≦

1, 0≦

t≦

1, and 0≦

d≦

1.

12. The process of claim 10, wherein the step of preparing the acid solution comprises:

dissolving a metal precursor salt, M′

_δ

X′

_γ

, in distilled water or an organic solvent;

wherein;

M′

is selected from Ni, Co, Mn, Al, Mg, Fe, Cu, Zn, V, Mo, Nb, Cr, Si, Ti, Zr, or a mixture of any two or more thereof; and

X′

is selected from NO₃⁻

, SO₄²⁻

, CO₃²⁻

, PO₄³⁻

, F⁻

, Cl⁻

, Br⁻

, I⁻

, or a mixture of any two more thereof;

1≦

δ

≦

3; and

1≦

γ

≦

3.

13. The process of claim 12, wherein M′

is nickel, cobalt, manganese, or a mixture of any two or more thereof.

14. The process of claim 10, wherein the step of preparing the basic solution comprises dissolving a precipitating agent or chelating agent in distilled water or an organic solvent, wherein the precipitating agent or chelating agent is selected from sodium carbonate, sodium hydrogen carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, sodium oxalate, sodium hydrogen oxalate, or a mixture of any two or more thereof.

15. The process of claim 10, further comprising calcining the nano-sized structured precursor at about 100°

C. to 1000°

C.

16. The process of claim 10, further comprising introducing a lithium source to the nano-sized structured precursor.

17. The method of claim of 16, wherein the lithium source is selected from lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium oxalate, lithium benzoate, lithium fluoride, lithium chloride, lithium bromide, lithium iodide, lithium oxide, lithium peroxide, lithium sulfate, lithium alloys, lithium silicate, lithium aluminate, lithium phosphate, or a mixture of any two or more thereof.