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Positive electrode active material particle including core containing lithium cobalt oxide and coating layer containing boron and fluorine, and preparation method thereof

專利號
US10868309B2
公開日期
2020-12-15
申請人
LG Chem, Ltd.
發(fā)明人
Bo Ram Lee; Sung Bin Park; Young Uk Park; Chi Ho Jo; Hyuck Hur; Wang Mo Jung
IPC分類
H01M4/36; H01M4/525; H01M4/62; H01M10/0525; H01M10/0568; C01G51/00; H01M2/10; H01M4/02
技術(shù)領(lǐng)域
lithium,electrode,positive,active,cobalt,material,coating,fluorine,oxide,may
地域： Seoul

摘要

Provided is a positive electrode active material particle including a core containing lithium cobalt oxide represented by the following Chemical Formula 1; and a coating layer containing boron (B) and fluorine (F), which is coated on the surface of the core: Li1+xCo1?xO2??(1)

說明書

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
TECHNICAL FIELD

The present application is based on, and claims priority from, Korean Patent Application No. 10-2016-0038865, filed on Mar. 31, 2016, the disclosure of which is hereby incorporated by reference herein in its entirety.

The present invention relates to a positive electrode active material particle including a core containing lithium cobalt oxide and a coating layer containing boron and fluorine, and a preparation method thereof.

BACKGROUND ART

As technology development and demands for mobile devices increase, demands for secondary batteries as energy sources are rapidly increasing. Among the secondary batteries, lithium secondary batteries having high energy density and working potential, a long cycle life, and a low self-discharge rate have been commercialized and widely used.

Further, with growing concerns about environmental issues, many researches have been conducted on electric vehicles and hybrid electric vehicles which may be employed in place of fossil fuel-based vehicles such as gasoline vehicles, diesel vehicles, etc., which are one of major causes of air pollution. Although nickel-metal hydride secondary batteries have been mainly used as power sources for such electric vehicles and hybrid electric vehicles, use of lithium secondary batteries having high energy density and discharge voltage has been actively studied, and some of them are in a commercialization stage.

權(quán)利要求

1
The invention claimed is:1. A positive electrode active material particle, comprisinga core including lithium cobalt oxide represented by the following Chemical Formula 1; anda coating layer including boron (B) and fluorine (F), which is coated on the surface of the core:
Li1+xCo1?xO2??(1)wherein ?0.03≤x≤0.1, andwherein lithium in the core is in an excessive amount.2. The positive electrode active material particle of claim 1, wherein in the coating layer, the boron and fluorine form a chemical bond with lithium.3. The positive electrode active material particle of claim 1, wherein the boron and fluorine form a chemical bond with lithium of the core.4. The positive electrode active material particle of claim 1, wherein the boron and fluorine exist in a compound of forming a chemical bond with lithium, independently of the core.5. The positive electrode active material particle of claim 2, wherein the boron and fluorine, together with lithium, exist as LiBF4.6. The positive electrode active material particle of claim 1, wherein a weight of the coating layer is 0.5% by weight to 5% by weight with respect to a weight of the core.7. The positive electrode active material particle of claim 1, wherein the positive electrode active material particle exhibits a capacity retention rate of 90% or more, as measured in a coin-type half cell at an upper voltage limit of 4.5 V at 45° C. during 50 cycles.8. A method of preparing a positive electrode active material particle for a secondary battery, the method comprising:(a) preparing a first lithium cobalt oxide represented by the following Chemical Formula 2;
Li1+yCo1?yO2??(2)?(wherein ?0.03≤y≤0.1)(b) dry-mixing the first lithium cobalt oxide and a first compound including all of boron and fluorine, or dry-mixing the first lithium cobalt oxide, a second compound including boron, and a third compound including fluorine; and(c) heat-treating the mixture after the dry-mixing of (b).9. The method of claim 8, wherein the first compound is one or more selected from the group consisting of NH4BF4, NaBF4, (CH3)3O(BF4), (C2H5)4N(BF4), (C6H5)3C(BF4), (CH3)4N(BF4), (CH3CH2CH2)4N(BF4), and C3H10BF4P.10. The method of claim 8, wherein the second compound is one or more selected from the group consisting of B2O3, H3BO3, (C6H5O)3B, B2H4O4, C6H5B(OH)2, CH3OC6H4B(OH)2, and C6H12BNO3.11. The method of claim 8, wherein the third compound is one or more selected from the group consisting of NH4HF2, NH4F, (CH3)4NF, (CH3CH2)4NF, PVdF (polyvinylidene fluoride), PVdF-HFP (poly(vinylidene fluoride-co-hexafluoropropylene)), PVF (polyvinyl fluoride), PTFE (polytetrafluoroethylene) and ETFE (ethylene tetrafluoroethylene).12. The method of claim 8, wherein the dry-mixing of (b) is performed by high energy milling.13. The method of claim 8, wherein the heat-treatment of (c) is performed at 300° C. to 600° C.14. The method of claim 8, wherein the heat-treatment of (c) is performed at 450° C. to 500° C.15. The method of claim 8, wherein the heat-treatment of (c) is performed for 3 hours to 7 hours.16. A secondary battery comprising a positive electrode including the positive electrode active material particle of claim 1, a negative electrode, and an electrolyte.17. The secondary battery of claim 16, wherein the electrolyte includes LiPF6 as a lithium salt, and PF5 which is a decomposition product of LiPF6 reacts with a coating layer of the positive electrode active material particle to be converted into PF6? which is a less reactive anion than PF5.18. The secondary battery of claim 16, wherein at least part of the coating layer of the positive electrode active material particle is dissolved into the electrolyte.19. A battery pack comprising the secondary battery of claim 16.20. A device comprising the battery pack of claim 19.21. A positive electrode active material particle, comprisinga core including lithium cobalt oxide represented by the following Chemical Formula 1; anda coating layer including boron (B) and fluorine (F), which is coated on the surface of the core:
Li1+xCo1?xO2??(1)wherein ?0.03≤x≤0.1, andwherein a weight of the coating layer is 0.5% by weight to 5% by weight with respect to a weight of the core.
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