Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof

Patent metadata

Field	Value
Publication number	US-11855285-B2
Application number	US-202016847048-A
Country	US
Kind code	B2
Filing date	Apr 13, 2020
Priority date	Apr 19, 2019
Publication date	Dec 26, 2023
Grant date	Dec 26, 2023

Abstract

The present invention discloses a full-gradient nickel cobalt manganese positive electrode material, a ruthenium oxide coated material and a preparation method thereof. The material has a chemical formula of LiNixCoyMn(1-x-y)O2, wherein, 0.5≤x≤0.9, 0.05≤y≤0.40, 1-x-y>0. A content of the nickel element is gradually decreased from a core portion to an outer surface of the full-gradient nickel cobalt manganese positive electrode material. A content of the manganese element is gradually increased from the core portion to the outer surface of the full-gradient nickel cobalt manganese positive electrode material. And, a content of the cobalt element is uniformly distributed in the full-gradient nickel cobalt manganese positive electrode material. The present invention also discloses a preparation method of the full-gradient nickel cobalt manganese positive electrode material. The present invention also discloses a preparation method of the ruthenium oxide coated material.

First claim

What is claimed is:

1. A method of preparing a ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material comprising:
coating a full gradient nickel cobalt manganese positive electrode material with a ruthenium oxide to obtain the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material, wherein the full gradient nickel cobalt manganese positive electrode material comprising material represented by a chemical formula of LiNi x Co y Mn (1-x-y) O 2 , wherein, 0.5≤x≤0.9, 0.05≤y≤0.40, 1-x-y>0, the method further comprises the following steps:
(1) mixing the full-gradient nickel cobalt manganese positive electrode material with a ruthenium source in an alcohol solution to obtain a mixture, heating and stirring the mixture in a closed atmosphere of an ammonia gas, and then evaporating to obtain a mixed powder; and,
(2) heat-treating the mixed powder obtained in the step (1) in an oxygen-containing atmosphere to obtain the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material;
a content of the nickel element is gradually decreased from a core portion to an outer surface of the full-gradient nickel cobalt manganese positive electrode material;
a content of the manganese element is gradually increased from the core portion to the outer surface of the full-gradient nickel cobalt manganese positive electron material, and
a content of the cobalt element is uniformly distributed in the full-gradient nickel cobalt manganese positive electrode material.

2. The method of preparing a ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material according to claim 1 , wherein in the step (1), a molar ratio of ruthenium element in the ruthenium source to total moles of nickel, cobalt and manganese in the full-gradient nickel cobalt manganese positive electrode material is 0.005-0.050:1; the ruthenium source is one or more selected from the group consisting of ruthenium chloride, ruthenium nitrate, ruthenium sulfide or ammonium hexachlororuthenate, and hydrates thereof; a volume-to-mass ratio of the alcohol solution to the total mass of the full-gradient nickel cobalt manganese positive electrode material and the ruthenium source is 20-80:1; the alcohol solution is one or more selected from the group consisting of anhydrous ethanol, ethylene glycol or methanol; the ammonia gas atmosphere is produced by placing a container having a full-gradient nickel cobalt manganese positive electrode material, a ruthenium source, and an alcohol solution in a closed vessel containing ammonia water, and the ammonia water being volatilized into ammonia gas in a heating and stirring reaction, forming an ammonia gas atmosphere; a volume ratio of the ammonia water to the alcohol solution is 0.4-0.8:1; a mass fraction of the ammonia water is 20-30%; the temperature of the heating and stirring reaction is 40-60° C., the stirring speed is 100-200r/min, and the reaction time is 4-8h.

3. The method of preparing a ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material according to claim 1 , wherein in the step (2), the heat-treating temperature is 300-500° C., and the heat-treating time is 4-8h; the oxygen-containing atmosphere is one or more selected from the group consisting of an air atmosphere, an oxygen atmosphere or an ozone atmosphere.

4. A method of preparing a ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material, comprising:
coating a full gradient nickel cobalt manganese positive electrode material with a ruthenium oxide to obtain the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material, wherein the full gradient nickel cobalt manganese positive electrode material comprising material represented by a chemical formula of LiNi x Co y Mn (1-x-y) O 2 , wherein, 0.5≤x≤0.9, 0.05≤y≤0.40, 1-x-y>0, the method further comprises the following steps
(1) mixing the full-gradient nickel cobalt manganese positive electrode material with a ruthenium source in an alcohol solution to obtain a mixture, heating and stirring the mixture in a closed atmosphere of an ammonia gas, and then evaporating to obtain a mixed powder; and,
(2) heat-treating the mixed powder obtained in the step (1) in an oxygen-containing atmosphere to obtain the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material;
a content of the nickel element is gradually decreased from a core portion to an outer surface of the full-gradient nickel cobalt manganese positive electrode material,
a content of the manganese element is gradually increased from the core portion to the outer surface of the full-gradient nickel cobalt manganese positive electrode material, and
a content of the cobalt element is uniformly distributed in the full-gradient nickel cobalt manganese positive electrode material, and
the full-gradient nickel cobalt manganese positive electrode material is in the form of spherical particles having an average particle diameter of 3-10 μm.

5. A method of preparing a ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material, comprising:
coating a full gradient nickel cobalt manganese positive electrode material with a ruthenium oxide to obtain the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material, wherein the full-gradient nickel cobalt manganese positive electrode material comprises material represented by a chemical formula of LiNi x Co y Mn (1-x-y) O 2 , wherein, 0.5≤x≤0.9, 0.05≤y≤0.40, 1-x-y>0, a coating layer of the ruthenium oxide has a thickness of 2-10 nm and the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material is represented by a chemical formula of LiNi x Co y Mn (1-x-y) O 2 @RuO 2 , wherein 0.5≤x≤0.9, 0.05≤x≤0.9, 0.05≤y≤0.40, 1-x-y>0 having a mass percentage of the ruthenium oxide is 0.5-5.0%, the ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material being in the form of spherical particles having an average particle diameter of 3-10 μm; and the method further comprises the following steps
(1) mixing the full-gradient nickel cobalt manganese positive electrode material with a ruthenium source in an alcohol solution, heating and stirring the reaction in a closed atmosphere of an ammonia gas, and then evaporating to obtain a mixed powder, the full-gradient nickel cobalt manganese positive electrode material comprises material represented by a chemical formula of LiNi x Co y Mn (1-x-y) O 2 , wherein, 0.5≤x≤0.9, 0.05≤y≤0.40, 1-x-y>0; and,
(2) heat-treating the mixed powder obtained in the step (1) in an oxygen-containing atmosphere to obtain a ruthenium oxide coated full-gradient nickel cobalt manganese positive electrode material;
a content of the nickel element is gradually decreased from a core portion to an outer surface of the full-gradient nickel cobalt manganese positive electrode material,
a content of the manganese element is gradually increased from the core portion to the outer surface of the full-gradient nickel cobalt manganese positive electrode material, and
a content f the cobalt element is uniformly distributed in the full-gradient nickel cobalt manganese positive electrode material.

Assignees

• Univ Central South

Inventors

• Tong Hui
• Zhou Qijie
• Zhang Bao
• Wang Xu
• Yao Yingying
• Yu Wanjing
• Zheng Junchao

Classifications

• 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

• H01M4/04

  Processes of manufacture in general · CPC title

• H01M10/0525

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

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/366 Primary

  as layered products · CPC title