NON-AQUEOUS, HIGH CAPACITY CATHODE MATERIAL FOR LITHIUM SECONDARY BATTERY, AND METHOD FOR PREPARING SAME

• US 20160372739A1
• Filed: 10/29/2014
• Published: 12/22/2016
• Est. Priority Date: 12/17/2013
• Status: Active Grant

• Current Assignee: Korea Electronics Technology Institute (Government of South Korea)
• Original Assignee: Korea Electronics Technology Institute (Government of South Korea)
• Inventors: KIM, Youngjun, KIM, Jeomsoo, CHO, Woosuk, WOO, Sanggil, YIM, Taeeun, LEE, Kyungjun, PARK, Yeonggwang, SONG, Junho
• Granted Patent: US 10,431,812 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C01G 53/006 Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen nickelates C01G53/40
• CPC Class Codes: C01G 53/50 of the type [MnO2]n- , e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2004/62 Submicrometer sized, i.e. from 0.1-1 micrometer
• CPC Class Codes: C01P 2004/80 Particles consisting of a mixture of two or more inorganic phases
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: C01P 2006/90 Other properties not specified above
• CPC Class Codes: H01M 10/0525 Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• CPC Class Codes: H01M 2004/028 Positive electrodes
• CPC Class Codes: H01M 4/0402 Methods of deposition of the material
• CPC Class Codes: H01M 4/043 involving compressing or compaction
• CPC Class Codes: H01M 4/0471 involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• CPC Class Codes: H01M 4/131 Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• CPC Class Codes: H01M 4/136 Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• 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 4/1397 of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
• CPC Class Codes: H01M 4/366 as layered products
• CPC Class Codes: H01M 4/483 for non-aqueous cells H01M4/485 takes 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: H01M 4/5825 : Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

The present invention relates to a non-aqueous cathode material for lithium secondary batteries using a spherical transition metal complex carbonate, and a method for preparing same. According to the present invention, since the surface of a spherical transition metal complex carbonate, which is prepared by using a cobalt material, nickel material, manganese material, carboxyl group material, and ammonia material, is coated with titanium dioxide. In addition, by mixing the prepared, surface-coated transition metal complex carbonate with a lithium material and heat-treating the resultant material, it is possible to prepare a spherical Li-rich cathode material having a primary particle size of 200 nm or more, and a 0.1C capacity of 250 mAh/g or more, and capable of implementing 96% or more of the initial capacity in a full cell after charging and discharging 60 times.

Claims

1. A method of preparing a non-aqueous cathode material for a lithium secondary battery, the method comprising:

a process of preparing a spherical transition metal complex carbonate by co-precipitating an aqueous solution in which a nickel material, a cobalt material, a manganese material, a carboxyl group material, and an ammonia material are mixed;

a process of coating a surface of the spherical transition metal complex carbonate with nano-sized titanium dioxide; and

a process of preparing a lithium-rich cathode material by mixing a lithium material with the transition metal complex carbonate coated with nano-sized titanium dioxide and performing a heat treatment thereon to prepare a spherical lithium-rich cathode material substituted with other metals.

2. The method of claim 1, where in the process of coating, the spherical transition metal complex carbonate coated with nano-sized titanium dioxide has a composition ratio of Ni_xCo_yMn₁₋

x−

yTi_zCO₃ (0.0<

x≦

0.3, 0.0<

y≦

0.2, 0.01≦

z≦

0.1, 0.5≦

1−

x−

y) and an average particle size of 5 to 25 μ

m.

3. The method of claim 1, where in the process of preparing a spherical transition metal complex carbonate, a concentration of each of the cobalt material, nickel material, manganese material, carboxyl group material, and ammonia material is in a range of 0.5 to 2 M,

wherein the cobalt material, nickel material, manganese material, carboxyl group material, and ammonia material are co-precipitated in a ratio of (cobalt material+nickel material+manganese material):

carboxyl group material;

ammonia material=1;

1.8 to 2.5;

0.5 to 1.5 or less, and a pH of a mixed aqueous solution is maintained in a range of 7 to 9.

4. The method of claim 1, wherein the process of coating comprises:

a process of mixing the transition metal complex carbonate with a suspension containing nano-sized titanium dioxide; and

a process of coating a surface of the transition metal complex carbonate with the nano-sized titanium dioxide by drying the suspension that was mixed with the transition metal complex carbonate.

5. The method of claim 1, wherein the process of preparing a lithium-rich cathode material comprises:

mixing lithium carbonate with the transition metal complex carbonate coated with titanium dioxide; and

performing a heat treatment on a mixture thereof.

6. The method of claim 5, where in the process of preparing a lithium-rich cathode material, the heat treatment is performed at a temperature in a range of 900 to 1100°

C.

7. The method of claim 1, further comprising, after the process of preparing a lithium-rich cathode material:

a process of pulverizing the lithium-rich cathode material into a powder.

8. The method of claim 1, where in the process of preparing a lithium-rich cathode material, the lithium-rich cathode material has a composition ratio of Li_wNi_xCo_yMn₁₋

x−

yTi_zO₂ (0.0<

x≦

0.3, 0.0<

y<

0.2, 0.5≦

1−

x−

y−

z, 0.01≦

z≦

0.1, 1.2≦

w≦

1.7), is spherical, and has an average particle size of 5 to 25 μ

m.

9. A non-aqueous cathode material for a lithium secondary battery, the non-aqueous cathode material having a composition ratio of Li_wNi_xCo_yMn₁₋

x−

yTi_zO₂ (0.0<

x≦

0.3, 0.0<

y<

0.2, 0.5≦

1−

x−

y−

z, 0.01≦

z≦

0.1, 1.2≦

w≦

1.7), a spherical shape, and an average particle size of 5 to 25 μ

m.