Lithium secondary battery

Patent metadata

Field	Value
Publication number	US-12476242-B2
Application number	US-202318479926-A
Country	US
Kind code	B2
Filing date	Oct 3, 2023
Priority date	Aug 28, 2019
Publication date	Nov 18, 2025
Grant date	Nov 18, 2025

Abstract

Provided is a lithium secondary battery, and the lithium secondary battery of the present invention includes: a positive electrode including a first lithium-metal oxide including secondary particles formed by aggregating primary particles having a particle diameter of 2 μm or less and a second lithium-metal oxide including nickel and at least one or more metals selected from the group consisting of manganese (Mn) and cobalt (Co) and including particles having a primary particle diameter of 2 μm or more; a negative electrode; a separator interposed between the positive electrode and the negative electrode; and an electrolyte, wherein the electrolyte includes a lithium salt, a nonaqueous organic solvent, and a difluorophosphite compound containing at least one or more difluorophosphite groups.

First claim

What is claimed is:

1 . A lithium secondary battery comprising:
a positive electrode comprising a first lithium-metal oxide comprising secondary particles formed by aggregating primary particles having a particle diameter of less than 2 μm, and a second lithium-metal oxide comprising nickel and at least one or more metals and comprising primary particles having a particle diameter of 2 μm or more, wherein the at least one or more metals comprises manganese, cobalt, or both; a negative electrode; a separator interposed between the positive electrode and the negative electrode; and an electrolyte comprising a lithium salt, a nonaqueous organic solvent, and a compound containing at least one difluorophosphite group and at least one or more olefin groups, wherein the compound containing at least one difluorophosphite group and at least one or more olefin groups is represented by the following Chemical Formula 4 or Chemical Formula 5:

wherein
R 1 to R 3 are independently of one another hydrogen, *—(CH 2 ) r —OPF 2 , C1-C10 alkyl, or C2-C10 alkenyl;
L is C1-C10 alkylene, and the alkylene of L may be further substituted by one or more selected from the group consisting of C1-C10 alkyl, *—(CH 2 ) a —OPF 2 , and

R′ is hydrogen or —OPF 2 ;
a and b are independently of each other an integer of 0 to 5;
q is an integer of 0 to 5; and
r is an integer of 0 to 5,

wherein
ring D is mono-, bi-, or tri-C6-C20 cycloalkenyl,
wherein the compound containing at least one difluorophosphite group and at least one or more olefin groups is comprised at 0.1 to 5 wt %, based on a total weight of the electrolyte.

2 . The lithium secondary battery of claim 1 , wherein the first lithium-metal oxide comprises secondary particles formed by aggregating primary particles having a particle diameter of 0.62 um or more and less than 2 μm, the second lithium-metal oxide comprises primary particles having a particle diameter of 2 μm or more and 8 μm or less.

3 . The lithium secondary battery of claim 1 , wherein the first lithium-metal oxide has a core-shell structure comprising a core part and a shell part having a concentration gradient region in which one or more metals other than lithium has a concentration gradient, and is represented by the following Chemical Formula 11, and in the following Chemical Formula 11, at least one of M1, M2, and M3 has a concentration gradient in the concentration gradient region:
Li x (M1) a (M2) b (M3) c O y   [Chemical Formula 11]
wherein M1, M2, and M3 are independently of one another selected from the group consisting of Ni, Co, Mn, Na, Mg, Ca, Ti, V, Cr, Cu, Zn, Ge, Sr, Ag, Ba, Zr, Nb, Mo, Al, Ga, and B; and 0<x≤1.1, 2y≤2.02, 0≤a≤1, 0≤b≤1, 0<c<1, and 0<a+b+c≤1 are satisfied.

4 . The lithium secondary battery of claim 3 , wherein the shell part has a thickness range of 0.1 to 2 μm from a first lithium-metal oxide surface to the core part which is in a center side.

5 . The lithium secondary battery of claim 3 , wherein M1 is Ni, and 0.6≤a≤0.95 and 0.05≤b+c≤0.4 are satisfied.

6 . The lithium secondary battery of claim 1 , wherein
the second lithium-metal oxide is represented by the following Chemical Formula 12:
Li x Ni a CO b Mn c (M4) d (M5) e O y   [Chemical Formula 12]

wherein M4 comprises one or more elements selected from the group consisting of Ti, Zr, Al, Mg, and Cr; M5 comprises any one or two or more elements selected from the group consisting of Sr, Y, W, and Mo; and 0<x<1.5, 2≤y≤2.02, 0<a<1, 0<b<1, 0<c<1, 0≤d≤0.03, 0≤e≤0.030, and 0<a+b+c≤1 are satisfied.

7 . The lithium secondary battery of claim 6 , wherein in Chemical Formula 12, d and e are 0, and 0.5≤a<1, 0.01≤b≤0.3, and 0.01≤c<1 are satisfied.

8 . The lithium secondary battery of claim 1 , wherein a content of the first lithium-metal oxide is higher than a content of the second lithium-metal oxide in the positive electrode.

9 . The lithium secondary battery of claim 1 , wherein the compound containing at least one difluorophosphite group and at least one or more olefin groups is any one or more selected from a compound represented by the following Chemical Formula 21, a compound represented by the following Chemical Formula 22, a compound represented by the following Chemical Formula 23, a compound represented by the following Chemical Formula 24, a compound represented by the following Chemical Formula 25, a compound represented by the following Chemical Formula 26, a compound represented by the following Chemical Formula 27, a compound represented by the following Chemical Formula 28, a compound represented by the following Chemical Formula 29, a compound represented by the following Chemical Formula 30, a compound represented by the following Chemical Formula 31, a compound represented by the following Chemical Formula 32, and a compound represented by the following Chemical Formula 33.

10 . The lithium secondary battery of claim 1 , wherein the electrolyte further comprises one or two or more additional additives selected from the group consisting of oxalatoborate-based compounds, oxalatophosphate-based additives, fluorine-substituted carbonate-based compounds, vinylidene carbonate-based compounds and sulfinyl group-containing compounds,
wherein the additional additive is comprised at 0.1 to 10.0 wt %, based on the total weight of the electrolyte.

11 . The lithium secondary battery of claim 10 , wherein the one or two or more additional additives include fluoroethylene carbonate, difluoroethylene carbonate, fluorodimethyl carbonate, fluoroethylmethyl carbonate, vinylene carbonate, vinylethylene carbonate, lithium bis (oxalato) borate (LiBOB), lithium difluorobis (oxalato) phosphate (LiDFBOP), ethanesultone, 1,3-propanesultone, 1,4-butanesultone, ethenesultone, 1,3-propenesultone, 3-fluoro-1,3-propanesultone, 1,4-butenesultone, ethylene sulfate, propylene sulfate, 2,3-butylene sulfate, 1,3-propylene sulfate, or 1,3-butylene sulfate.

Assignees

• Sk On Co Ltd

Inventors

• Do Young Hoon
• Lee Yoon Ji
• Cho Yong Hyun
• Cho In Haeng

Classifications

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M4/366

  as layered products · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M2300/0034

  Fluorinated solvents · CPC title

• H01M2004/028

  Positive electrodes · CPC title