Non-aqueous electrolyte and lithium secondary battery including the same
A non-aqueous electrolyte includes a lithium salt, an organic solvent, and an additive, wherein the additive includes a compound represented by Formula 1 below, and such non-aqueous electrolyte may be excellent in electrode film protection and an O 2 scavenging effect, so that cycle properties and resistance properties of a lithium secondary battery including the non-aqueous electrolyte may be simultaneously improved, and the amount of gas generation may be significantly reduced: all the variables are described herein.
1 . A non-aqueous electrolyte comprising:
a lithium salt;
an organic solvent; and
an additive,
wherein the additive comprises at least one of a compound represented by Formula 1-A or a compound represented by Formula 1-B:
wherein in Formula 1-A and Formula 1-B, R 1 each independently comprises a halogen, a nitrile group, a propargyl group, an ether group, a ketone group, a carboxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted alkoxy group, a boron group, a borate group, an isocyanate group, an isothiocyanate group, a silyl group, a siloxane group, a sulfone group, a sulfonate group, a sulfate group, or a combination of two or more thereof, and
R 2 is a substituent represented by Formula 2,
wherein in Formula 2, R 3 is each independently selected from an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, * is a bonding site,
n is an integer of 0 to 4.
2 . The non-aqueous electrolyte of claim 1 , wherein the additive comprises at least one of compounds represented by Formula 1-a, Formula 1-b, Formula 1-c, or Formula 1-d:
wherein in Formula 1-a, Formula 1-b, Formula 1-c, and Formula 1-d, R 1 and R 2 are defined as in Formula 1-A and Formula 1-B.
3 . The non-aqueous electrolyte of claim 1 , wherein the at least one of a compound represented by Formula 1-A or the compound represented by Formula 1-B is included in an amount of 0.01 wt % to 10 wt %, based on a total weight of the non-aqueous electrolyte.
4 . The non-aqueous electrolyte of claim 1 , wherein the lithium salt comprises at least one of LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiAlO 4 , LiAlCl 4 , LiPF 6 , LiSbF 6 , LiAsF 6 , LiB 10 Cl 10 , LiB(C 2 O 4 ) 2 (LiBOB), LiCF 3 SO 3 , LiN(SO 2 F) 2 (LiFSI), LiCH 3 SO 3 , LiCF 3 CO 2 , LiCH 3 CO 2 , or LiN(SO 2 CF 2 CF 3 ) 2 (LiBETI).
5 . The non-aqueous electrolyte of claim 1 , wherein the non-aqueous electrolyte comprises the lithium salt at a molar concentration of 0.5 M to 5.0 M.
6 . The non-aqueous electrolyte of claim 1 , wherein the organic solvent comprises at least one of a cyclic carbonate-based organic solvent, a linear carbonate-based organic solvent, a linear ester-based organic solvent, or a cyclic ester-based organic solvent.
7 . The non-aqueous electrolyte of claim 1 , wherein the additive further comprises at least one additional additive selected from vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, propane sultone, propene sultone, succinonitrile, adiponitrile, ethylene sulfate, LiPO 2 F 2 , lithium difluorooxalatoborate (LiODFB), lithium bis-(oxalato) borate (LiBOB), 3-trimethoxysilanyl-propyl-N-aniline (TMSPa), or tris(trimethylsilyl)phosphite (TMSPi).
8 . The non-aqueous electrolyte of claim 1 , wherein the additive comprises at least one compound represented by Formula 1-a-1, Formula 1-a-2, Formula 1-a-3, Formula 1-a-4, Formula 1-a-5, Formula 1-a-6, Formula 1-b-1, Formula 1-b-2, Formula 1-b-3, Formula 1-b-4, Formula 1-b-5, Formula 1-b-6, Formula 1-c-1, Formula 1-c-2, Formula 1-d-1, or Formula 1-d-2:
9 . The lithium secondary battery of claim 1 , wherein R 3 is an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms.
10 . A lithium secondary battery comprising:
a positive electrode comprising a positive electrode active material;
a negative electrode comprising a negative electrode active material;
a separator interposed between the positive electrode and the negative electrode; and
a non-aqueous electrolyte according to claim 1 .
11 . The lithium secondary battery of claim 10 , wherein the positive electrode active material comprises a hyper-lithium manganese-rich oxide containing 50 mol % or greater of Mn among all metals excluding lithium, and having a molar ratio of lithium to transition metals greater than 1.
12 . The lithium secondary battery of claim 11 , wherein the hyper-lithium manganese-rich oxide is a compound represented by Formula 6:
wherein in Formula 6 above, M 1 is one or more selected from W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, or Mo, and 0.05≤s≤1, 0≤t≤0.5, 0≤u≤0.3, 0.5≤v<1.0, 0≤w≤0.2, and 0≤z≤1.
13 . The lithium secondary battery of claim 10 , wherein at least a portion of the compound represented by Formula 1-A or the compound represented by Formula 1-B is bonded to a reactive oxygen compound generated from the positive electrode.