High-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof

• US 10,446,830 B2
• Filed: 09/01/2017
• Issued: 10/15/2019
• Est. Priority Date: 12/28/2016
• Status: Active Grant

• Current Assignee: Sichuan Fuhua New Energy Hi-Tech Co., Ltd.
• Original Assignee: Sichuan Fuhua New Energy Hi-Tech Co., Ltd.
• Inventors: Liu, Xingquan, Liu, Yiding, He, Zhenhua
• Primary Examiner(s): Cullen, Sean P
• Application Number:
  US15/694,665
• Publication Number:
  US 20180183045A1
• Time in Patent Office: 774 Days
• Field of Search: 4292313
• 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 53/66 containing alkaline earth metals, e.g. SrNiO3, SrNiO2
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2004/03 obtained by SEM
• CPC Class Codes: C01P 2006/40 Electric properties
• CPC Class Codes: H01M 4/1315 containing halogen atoms, e.g. LiCoOxFy
• 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 4/505 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

The present invention discloses a high-voltage ternary positive electrode material for lithium-ion battery and preparation method thereof. The chemical formula of the material is LiNi_0.6-xMg_xCo_0.2-yAl_yMn_0.2-zTi_zO_2-dF_d, wherein 0<x,y,z,d≤0.05. The precursor of the positive electrode material is synthesized by gradient co-precipitation method and the positive electrode material is prepared by solid phase method. The content of nickel in the synthesized precursor particles has a gradient distribution from the inside to the outside. The obtained precursor is mixed and grinded evenly with the lithium source and the fluorine source at a certain ratio and put into the tube furnace. The obtained precursor is then pre-sintered in the oxygen-enriched air atmosphere and then heated up to be sintered, to obtain the target product. The positive electrode material for lithium-ion battery prepared by the method is free from impurity phase and has a good crystallinity, which is a high energy density positive electrode material.

Claims

1. A method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery, wherein a molecular formula of the positive electrode material of the lithium-ion battery is LiNi_0.6-xMg_xCo_0.2-yAl_yMn_0.2-zTi_zO_2-dF_d, wherein 0<

x≤

0.05, 0<

y≤

0.05, 0<

z≤

0.05, and 0<

d≤

0.05;

wherein the method comprises the following steps;

step 1;

weighing a sample including a nickel source material, a magnesium source material, a cobalt source material, an aluminum source material, a manganese source material and, a titanium source material at a molar ratio of Ni;

Mg;

Co;

Al;

Mn;

Ti=(0.6−

x);

x;

(0.2−

y);

y;

(0.2−

z);

z;

dividing the sample into two parts at molar ratios of (Ni+Mg);

(Co+Al);

(Mn+Ti)=5;

2;

3 and 7;

2;

1 respectively, and dissolving the two parts respectively in deionized water to obtain a solution a and a solution b;

step 2, mixing a sodium hydroxide solution with ammonia to form a solution c, wherein the solution c is composed of the sodium hydroxide at a concentration of 2.0 mol/L and the ammonia at a concentration of 0.5 mol/L;

step 3, uniformly dropping the solution a and the solution c into a beaker containing deionized water, and then uniformly dropping the solution b and the solution c into the beaker and placing the beaker in a water bath at a temperature of 50 to 80°

C. and stirring continuously;

step 4, adding the ammonia into a mixed solution obtained from the step 3, adjusting pH to be 11, and stirring continuously for 5 hours, then raising the temperature to 70°

C. and aging for 12 hours;

step 5, filtering and washing a product obtained from the step 4 until no sulfate ion is detected using BaCl₂ solution, and then drying the product in a blast oven and grinding the product evenly;

step 6, mixing a precursor obtained from the step 5 with a lithium source and a fluorine source, grinding a mixture evenly and drying the mixture using absolute ethanol as a dispersant; and

step 7, grinding the mixture obtained from the step 6 evenly, and putting the mixture in a tube furnace, raising a temperature to 450-550°

C. at 5°

C./min in an oxygen air atmosphere, and pre-sintering the mixture for 5-10 hours;

then raising the temperature to 700-850°

C. at 2°

C./min, and sintering the mixture for 10-24 hours;

grinding the product after natural cooling in the oxygen atmosphere, and obtaining the positive electrode material LiNi_0.6-xMg_xCo_0.2-yAl_yMn_0.2-zTi_zO_2-dF_d the lithium-ion battery, wherein the positive electrode material has a layered structure, and nickel has gradient distribution in particles.

2. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 1, the nickel source material is at least one material selected from the group consisting of nickel sulfate, nickel nitrate, nickel acetate, nickel chloride and nickel hydroxide.

3. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 1, the magnesium source material is at least one material selected from the group consisting of magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium chloride, magnesium oxide, and magnesium hydroxide.

4. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 1, the cobalt source material is at least one material selected from the group consisting of cobalt sulfate, cobalt nitrate, cobalt acetate, cobalt chloride and a hydroxide of cobalt and an oxide of cobalt.

5. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 1, the aluminum source material is at least one material selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum hydroxide and an oxide of aluminum.

6. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 1, the manganese source material is at least one material selected from the group consisting of manganese sulfate, manganese nitrate, manganese acetate, manganese chloride and a hydroxide of manganese and an oxide of manganese, wherein the hydroxide of manganese and the oxide of manganese is any one of chemical manganese dioxide and electrolytic manganese dioxide.

7. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 1, the titanium source material is at least one material selected from the group consisting of butyl titanate, titanyl sulfate and titanium dioxide.

8. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 6, a molar ratio of a lithium source material, the nickel source material, the magnesium source material, the cobalt source material, the aluminum source, the manganese source material, the titanium source material and a fluorine source material is (1-1.1):

(0.6−

x);

x;

(0.2−

y);

y;

(0.2−

z);

z;

d.

9. The method for preparing a high-voltage ternary positive electrode material of a lithium-ion battery according to claim 1, wherein in the step 6, a lithium source material is at least one material selected from the group consisting of lithium carbonate, lithium nitrate, lithium acetate, lithium chloride and lithium hydroxide, and a fluorine source material is at least one material selected from the group consisting of lithium fluoride and ammonium fluoride.