Electrolyte for lithium secondary battery and lithium secondary battery comprising same

Abstract

The present invention relates to an electrolyte for a lithium secondary battery and a lithium secondary battery comprising same, wherein the electrolyte comprises a non-aqueous organic solvent, a lithium salt, and an additive, and the additive includes an additive of chemical formula 1.

Description

Electrolyte for lithium secondary batteries and lithium secondary batteries including the same

[0001] The present invention relates to an electrolyte for a lithium secondary battery and a lithium secondary battery containing the same.

[0002]

[0003] Recently, accompanied by the rapid proliferation of battery-powered electronic devices such as mobile phones, laptop computers, and electric vehicles, the demand for high-energy-density, high-capacity rechargeable batteries is rapidly increasing. Accordingly, research and development to improve the performance of lithium-ion batteries is actively underway.

[0004] A lithium secondary battery is a battery comprising a positive electrode and a negative electrode containing an active material capable of lithium ion intercalation and deintercalation, and an electrolyte, which produces electrical energy through oxidation and reduction reactions when lithium ions are intercalated or deintercalated from the positive and negative electrodes.

[0005] The electrolyte for these lithium secondary batteries consists of a lithium salt dissolved in a non-aqueous organic solvent. The characteristics of a lithium secondary battery are determined by complex reactions between the anode and the electrolyte, and between the cathode and the electrolyte. Therefore, the use of an appropriate electrolyte is one of the important variables for improving the performance of a lithium secondary battery.

[0006]

[0007] One embodiment provides an electrolyte for a lithium secondary battery that provides a low resistance increase rate and a low gas generation rate after high-temperature storage.

[0008] Another embodiment provides an electrolyte for a lithium secondary battery that provides a rapid charging effect.

[0009] Another embodiment provides a lithium secondary battery comprising the above electrolyte.

[0010]

[0011] 1. One embodiment provides an electrolyte for a lithium secondary battery comprising a non-aqueous organic solvent; a lithium salt; and an additive, wherein the additive comprises an additive of the following chemical formula 1:

[0012] [Chemical Formula 1]

[0013]

[0014] (In the above chemical formula 1

[0015] R 11 , R 12 , R 13 , R 14 and n are each as defined in the description of the invention below).

[0016] In 2.1, in the above chemical formula 1-1, R 16 is a substituted or unsubstituted C2 to C20 alkenyl group, and R 15 The electrolyte for a lithium secondary battery is a substituted or unsubstituted C1 to C20 alkylene group.

[0017] In 3.1 or 2, in the above formula 1-1, R 16 Electrolyte for lithium secondary batteries, which is an allyl group, metaallyl group, or vinyl group.

[0018] 4.1 to 3, an electrolyte for a lithium secondary battery comprising one or more of the additives of Formula 1 and Formula 2 below:

[0019] [Chemical Formula 1-2]

[0020]

[0021] (In the above chemical formula 1-2,

[0022] R 21 and R 22Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and

[0023] R 23 ...is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or the following chemical formula 1-3,

[0024] R 24 is the following chemical formula 1-3.

[0025] [Chemical Formula 1-3]

[0026]

[0027] (In the above chemical formula 1-3,

[0028] R 25 R in the above chemical formula 1-1 15 Identical to what is defined in,

[0029] R 26 is a single bond or a substituted or unsubstituted C2 to C18 alkylene group).

[0030] 5.1 to 4, an electrolyte for a lithium secondary battery comprising one or more of the additives of Formula 1 below, Formulas 1-4 to 1-9:

[0031] [Chemical Formula 1-4]

[0032]

[0033] [Chemical Formula 1-5]

[0034]

[0035] [Chemical Formula 1-6]

[0036]

[0037] [Chemical Formula 1-7]

[0038]

[0039] [Chemical Formula 1-8]

[0040]

[0041] [Chemical Formula 1-9]

[0042] .

[0043] 6.1 to 5, an electrolyte for a lithium secondary battery, wherein the additive of Formula 1 is included in an amount of 0.05 to 5 weight% with respect to the total amount of the electrolyte.

[0044] 7.1 to 6, an electrolyte for a lithium secondary battery, wherein the additive of Formula 1 is included in at least 95% by weight of the total additive of the electrolyte.

[0045] Electrolyte for a lithium secondary battery, wherein, in 8.1 to 7, the non-aqueous organic solvent is a mixture containing ethylene carbonate (EC): ethylmethyl carbonate (EMC): dimethyl carbonate (DMC) in a volume ratio of 10 to 40: 10 to 40: 40 to 80.

[0046] 9. Electrolyte for a lithium secondary battery, wherein, in 1 to 8, the lithium salt is one or more selected from the group consisting of LiPF6, LiClO4, LiBF4, lithium bis(fluorosulfonyl)imide (LiFSI), LiTFSI, LiSO3CF3, LiBOB, LiFOB, LiDFBP, LiTFOP, LiPO2F2, LiSbF6, LiAsF6, LiAlO2, LiAlCl4, LiCl, LiI, LiN(SO3C2F5)2, Li(FSO2)2N, and LiC4F9SO3.

[0047] 10. Electrolyte for a lithium secondary battery in which, in 1 to 9, the concentration of the lithium salt is 0.1M to 2.0M.

[0048] 11. Another embodiment provides a lithium secondary battery comprising a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; and an electrolyte, wherein the electrolyte comprises the electrolyte.

[0049] 12. A lithium secondary battery, wherein the positive electrode active material comprises a lithium transition metal composite oxide having a nickel content of 80 mol% or more relative to 100 mol% of a metal excluding lithium.

[0050] 13. A lithium secondary battery in which, in 11 or 12, the lithium transition metal composite oxide comprises a lithium composite oxide represented by the following chemical formula 2:

[0051] [Chemical Formula 2]

[0052] Li a1 Ni x1 M 1 y1 M 2 z1 O 2-b1 X b1

[0053] In the above chemical formula 2, 0.9≤a1≤1.8, 0.3≤x1≤1, 0≤y1≤0.7, 0≤z1≤0.7, 0.9≤x1+y1+z1≤1.1, and 0≤b1≤0.1, and

[0054] M 1 and M 2 Each is independently one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is one or more elements selected from the group consisting of F, P, and S.

[0055] 14.13 A lithium secondary battery in which, in the above chemical formula 2, 0.8≤x1≤1, 0≤y1≤0.2, and 0≤z1≤0.2.

[0056] 15. A lithium secondary battery in which, in 11 to 14, the negative electrode active material comprises at least one of graphite and a Si composite.

[0057] 16. A lithium secondary battery in which, in 11 to 15, the lithium secondary battery is a cylindrical, prismatic, pouch-type, or coin-type battery.

[0058]

[0059] An electrolyte according to one embodiment can provide the effect of improving the performance and lifespan of a lithium secondary battery by providing a low resistance increase rate and a low gas generation rate after high-temperature storage during secondary battery activation, and by providing a rapid charging effect.

[0060]

[0061] FIG. 1 is a conceptual diagram briefly illustrating a lithium secondary battery according to one embodiment of the present invention.

[0062] FIGS. 2 to 5 are cross-sectional views schematically illustrating a lithium secondary battery according to one embodiment.

[0063] Figure 6 shows the 1H NMR spectrum results of the compound of formula 1-4 according to the synthesis example.

[0064]

[0065] In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention are described with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and various modifications can be made. The description of these embodiments is provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention.

[0066] In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the components are exaggerated for the effective description of the technical content. Throughout the specification, parts indicated by the same reference numeral represent the same components.

[0067] Unless otherwise specified in this specification, the singular form may also include the plural. Additionally, unless otherwise specified, "A or B" may mean "comprising A, comprising B, or comprising A and B." As used herein, "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components to the mentioned components.

[0068] In this specification, "combination of these" may mean a mixture of components, a laminate, a composite, a copolymer, an alloy, a blend, and a reaction product, etc.

[0069] In this specification, "substitution" means that, unless otherwise defined, at least one hydrogen of a substituent or compound is substituted with a deuterium, a halogen group, a hydroxyl group, an amino group, a C1 to C30 amine group, a nitro group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 fluoroalkyl group, a cyano group, or a combination thereof.

[0070] Specifically, "substitution" may mean that at least one hydrogen in the substituent or compound is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C6 to C30 arylsilyl group, a C3 to C30 cycloalkyl group, a C3 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C10 fluoroalkyl group, or a cyano group. For example, "substitution" may mean that at least one hydrogen in the substituent or compound is substituted with deuterium, a halogen group, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C1 to C10 fluoroalkyl group, or a cyano group. Alternatively, "substitution" may mean that at least one hydrogen in the substituent or compound is substituted with a deuterium, a halogen group, a C1 to C5 alkyl group, a C6 to C18 aryl group, a C1 to C5 fluoroalkyl group, or a cyano group. For example, "substitution" may mean that at least one hydrogen in the substituent or compound is substituted with a deuterium, a cyano group, a halogen group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a biphenyl group, a terphenyl group, a trifluoromethyl group, or a naphthyl group.

[0071] Unless otherwise defined in this specification, "*" means a part connected to the same or different atoms or chemical formulas.

[0072] Unless otherwise specifically mentioned in the chemical formulas described in this specification, hydrogen may be considered to be bonded in the structure of the chemical formula.

[0073] FIG. 1 is a conceptual diagram briefly illustrating a lithium secondary battery according to embodiments of the present invention. Referring to FIG. 1, the lithium secondary battery may include a positive electrode (10), a negative electrode (20), a separator (30), and an electrolyte (ELL).

[0074] The positive electrode (10) and the negative electrode (20) may be spaced apart from each other with a separator (30) in between. The separator (30) may be placed between the positive electrode (10) and the negative electrode (20). The positive electrode (10), the negative electrode (20), and the separator (30) may come into contact with an electrolyte (ELL). The positive electrode (10), the negative electrode (20), and the separator (30) may be impregnated within the electrolyte (ELL).

[0075] The electrolyte (ELL) may be a medium for transferring lithium ions between the positive electrode (10) and the negative electrode (20). Within the electrolyte (ELL), the lithium ions may pass through a separator (30) and move toward the positive electrode (10) or the negative electrode (20).

[0076] positive electrode (10)

[0077] A positive electrode (10) for a lithium secondary battery may include a current collector (COL1) and a positive electrode active material layer (AML1) formed on the current collector (COL1). The positive electrode active material layer (AML1) may include a positive electrode active material and may further include a binder and / or a conductive material.

[0078] For example, the anode (10) may further include an additive that can serve as a sacrificial anode.

[0079] The content of the positive active material in the positive active material layer (AML1) may be 90% to 99.5% by weight with respect to 100% by weight of the positive active material layer (AML1). The content of the binder and the conductive material may each be 0.5% to 5% by weight with respect to 100% by weight of the positive active material layer (AML1).

[0080] The above binder serves to adhere the positive active material particles well to each other and also to adhere the positive active material well to the current collector (COL1). Representative examples of binders include, but are not limited to, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, (meth)acrylated styrene-butadiene rubber, epoxy resin, (meth)acrylic resin, polyester resin, nylon, etc.

[0081] The above conductive material is used to impart conductivity to the electrode, and any electronically conductive material that does not cause chemical changes can be used in the battery being constructed. Examples of conductive materials include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanofiber, carbon nanotube; metal-based materials in the form of metal powder or metal fibers containing copper, nickel, aluminum, silver, etc.; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0082] Al can be used as the current collector (COL1), but is not limited thereto.

[0083] positive electrode active material

[0084] As the positive active material in the positive active material layer (AML1), a compound capable of reversible intercalation and deintercalation of lithium (a lithated intercalation compound) may be used. Specifically, one or more composite oxides of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof may be used.

[0085] The above composite oxide may be a lithium transition metal composite oxide, and specific examples include a lithium nickel-based oxide, a lithium cobalt-based oxide, a lithium manganese-based oxide, a lithium iron phosphate-based compound, a cobalt-free nickel-manganese-based oxide, or a combination thereof.

[0086] As an example, a compound represented by any one of the following chemical formulas may be used. Li a A 1-b X b O 2-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Mn 2-b X b O 4-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b X c O 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Mn b X c O 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni b Co c L 1 d G e O2(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0≤e≤0.1); Li a NiG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a CoG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-b G b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Lia Mn2G b O4(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-g G g PO4(0.90≤a≤1.8, 0≤g≤0.5); Li (3-f) Fe2(PO4)3(0≤f≤2); Li a FePO4(0.90≤a≤1.8).

[0087] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; X is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; L 1 is Mn, Al, or a combination thereof.

[0088] For example, the above-mentioned positive electrode active material may be a high-nickel positive electrode active material in which the nickel content relative to 100 mol% of the metal excluding lithium in the lithium transition metal composite oxide is 80 mol% or more, 85 mol% or more, 90 mol% or more, 91 mol% or more, or 94 mol% or more and 99 mol% or less. The high-nickel positive electrode active material can achieve high capacity and can be applied to high-capacity, high-density lithium secondary batteries.

[0089] Negative electrode (20)

[0090] A negative electrode (20) for a lithium secondary battery comprises a current collector (COL2) and a negative electrode active material layer (AML2) located on the current collector (COL2). The negative electrode active material layer (AML2) comprises a negative electrode active material and may further comprise a binder and / or a conductive material.

[0091] For example, the negative electrode active material layer (AML2) may contain 90% to 99% by weight of negative electrode active material, 0.5% to 5% by weight of binder, and 0% to 5% by weight of conductive material.

[0092] The above binder serves to effectively bond the negative electrode active material particles to each other and also to effectively bond the negative electrode active material to the current collector (COL2). As the binder, a non-aqueous binder, an aqueous binder, a dry binder, or a combination thereof may be used.

[0093] Examples of the above-mentioned non-aqueous binders include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene propylene copolymer, polystyrene, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamide imide, polyimide, or combinations thereof.

[0094] The above-mentioned water-based binder may be selected from styrene-butadiene rubber, (meth)acrylated styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, (meth)acrylic rubber, butyl rubber, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, poly(meth)acrylonitrile, ethylenepropylenediene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, (meth)acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

[0095] When a water-based binder is used as the above-mentioned cathode binder, a cellulose-based compound capable of imparting viscosity may be further included. As this cellulose-based compound, one or more types such as carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, or alkali metal salts thereof may be mixed and used. Na, K, or Li may be used as the alkali metal.

[0096] The above dry binder is a polymer material capable of fiberization, and may be, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyethylene oxide, or a combination thereof.

[0097] The above conductive material is used to impart conductivity to the electrode, and any electronically conductive material that does not cause chemical changes can be used in the battery being constructed. Specific examples include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjenblack, carbon fiber, carbon nanofiber, carbon nanotube; metal-based materials in the form of metal powder or metal fibers including copper, nickel, aluminum, silver, etc.; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0098] As the current collector (COL2), copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, and combinations thereof may be used.

[0099] cathode active material

[0100] The negative electrode active material in the negative electrode active material layer (AML2) comprises a material capable of reversibly intercalating / deintercalating lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.

[0101] A material capable of reversibly intercalating / deintercalating the above lithium ions may be a carbon-based negative electrode active material, such as crystalline carbon, amorphous carbon, or a combination thereof. Examples of the crystalline carbon include graphite such as amorphous, plate-like, flake-like, spherical, or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, etc.

[0102] As the above lithium metal alloy, an alloy of lithium and a metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn may be used.

[0103] As a material capable of doping and undoping the above lithium, a Si-based negative electrode active material or a Sn-based negative electrode active material may be used. The Si-based negative electrode active material may be silicon, a silicon-carbon composite, SiOx (0 < x < 2), a Si-Q alloy (wherein Q is selected from alkali metals, alkaline earth metals, group 13 elements, group 14 elements (excluding Si), group 15 elements, group 16 elements, transition metals, rare earth elements, and combinations thereof), or a combination thereof. The Sn-based negative electrode active material may be Sn, SnO2, a Sn-based alloy, or a combination thereof.

[0104] The silicon-carbon composite may be a composite of silicon and amorphous carbon. According to one embodiment, the silicon-carbon composite may be in the form of silicon particles and amorphous carbon coated on the surface of the silicon particles. For example, it may include a secondary particle (core) assembled from silicon primary particles and an amorphous carbon coating layer (shell) located on the surface of the secondary particle. The amorphous carbon may also be located between the silicon primary particles, so that, for example, the silicon primary particles may be coated with amorphous carbon. The secondary particles may be dispersed in an amorphous carbon matrix.

[0105] The silicon-carbon composite may further include crystalline carbon. For example, the silicon-carbon composite may include a core comprising crystalline carbon and silicon particles and an amorphous carbon coating layer located on the surface of the core.

[0106] The above Si-based or Sn-based negative electrode active material can be used in combination with a carbon-based negative electrode active material.

[0107] Separator (30)

[0108] Depending on the type of lithium secondary battery, a separator (30) may be present between the positive electrode (10) and the negative electrode (20). As such a separator (30), polyethylene, polypropylene, polyvinylidene fluoride, or a multilayer film of two or more layers thereof may be used, and of course, a mixed multilayer film such as a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, or a polypropylene / polyethylene / polypropylene three-layer separator may be used.

[0109] The separator (30) may include a porous substrate and a coating layer comprising an organic material, an inorganic material, or a combination thereof located on one or both sides of the porous substrate.

[0110] The porous substrate may be a polymer membrane formed from any one of the following: polyolefins such as polyethylene and polypropylene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyacetal; polyamide; polyimide; polycarbonate; polyetherketone; polyaryletherketone; polyetherimide; polyamideimide; polybenzimidazole; polyethersulfone; polyphenylene oxide; cyclic olefin copolymer; polyphenylene sulfide; polyethylene naphthalate; glass fiber; Teflon; and polytetrafluoroethylene, or a copolymer or mixture of two or more of these.

[0111] The above organic material may include a polyvinylidene fluoride-based polymer or a (meth)acrylic-based polymer.

[0112] The above inorganic materials are Al2O3, SiO2, TiO2, SnO2, CeO2, MgO, NiO, CaO, GaO, ZnO, ZrO2, Y2O3, It may include, but is not limited to, inorganic particles selected from SrTiO3, BaTiO3, Mg(OH)2, boehmite, and combinations thereof.

[0113] The above organic and inorganic materials may exist mixed in a single coating layer, or may exist in a stacked form with a coating layer containing organic materials and a coating layer containing inorganic materials.

[0114] Electrolyte (ELL)

[0115] The electrolyte (ELL) for lithium secondary batteries contains a non-aqueous organic solvent and a lithium salt.

[0116] The above-mentioned non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.

[0117] The above-mentioned non-aqueous organic solvent may be a carbonate-based, ester-based, ether-based, ketone-based, or alcohol-based solvent, an aprotic solvent, or a combination thereof.

[0118] The above carbonate-based solvents may include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), ethylmethyl carbonate (EMC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), etc.

[0119] Ester-based solvents such as methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methylpropionate, ethylpropionate, decanolide, mevalonolactone, valerolactone, and caprolactone may be used.

[0120] As ether-based solvents, dibutyl ether, tetraglame, diglame, dimethoxyethane, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofuran, etc. may be used. Additionally, as ketone-based solvents, cyclohexanone, etc. may be used. As alcohol-based solvents, ethyl alcohol, isopropyl alcohol, etc. may be used, and as aprotic solvents, nitriles such as R-CN (where R is a straight-chain, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms and may include a double bond, an aromatic ring, or an ether group); amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane, 1,4-dioxolane; sulfolanes, etc. may be used.

[0121] The above-mentioned non-aqueous organic solvent can be used alone or in a mixture of two or more types.

[0122] In addition, when using a carbonate-based solvent, a mixture of cyclic carbonates and chain carbonates can be used, and the cyclic carbonates and chain carbonates can be mixed in a volume ratio of 1:1 to 1:9.

[0123] The above lithium salt is a substance that dissolves in an organic solvent and acts as a source of lithium ions within the battery, enabling the basic operation of a lithium secondary battery and facilitating the movement of lithium ions between the anode and cathode. Representative examples of lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiAlO2, LiAlCl4, LiPO2F2, LiCl, LiI, LiN(SO3C2F5)2, Li(FSO2)2N (lithium bis(fluorosulfonyl)imide (LiFSI), LiC4F9SO3, LiN(C x F 2x+1 SO2)(C y F 2y+1It may include one or more selected from SO2)(x and y are integers from 1 to 20), lithium trifluoromethane sulfonate, lithium tetrafluoroethane sulfonate, lithium difluorobis(oxalate)borate (LiDFOB), lithium difluorobis(oxalate)phosphate (LiDFOP), and lithium bis(oxalate)borate (LiBOB).

[0124] lithium secondary battery

[0125] Lithium secondary batteries can be classified into cylindrical, prismatic, pouch, coin, etc., depending on their shape. FIGS. 2 to 5 are schematic diagrams illustrating lithium secondary batteries according to one embodiment, where FIG. 2 is a cylindrical battery, FIG. 3 is a prismatic battery, and FIGS. 4 and 5 are pouch-type batteries. Referring to FIGS. 2 to 5, the lithium secondary battery (100) may include an electrode assembly (40) with a separator (30) interposed between a positive electrode (10) and a negative electrode (20), and a case (50) in which the electrode assembly (40) is housed. The positive electrode (10), the negative electrode (20), and the separator (30) may be impregnated with an electrolyte (not shown). The lithium secondary battery (100) may include a sealing member (60) that seals the case (50) as in FIG. 2. In addition, in FIG. 3, the lithium secondary battery (100) may include a positive lead tab (11) and a positive terminal (12), a negative lead tab (21) and a negative terminal (22). As shown in FIG. 4 and FIG. 5, the lithium secondary battery (100) may include electrode tabs (70), namely a positive tab (71) and a negative tab (72), which serve as electrical passages for inducing current formed in the electrode assembly (40) to the outside.

[0126] Hereinafter, the electrolyte of a lithium secondary battery according to one embodiment of the present invention will be described in more detail.

[0127] An electrolyte for a lithium secondary battery according to one embodiment comprises the above-described non-aqueous organic solvent; a lithium salt; and an additive, wherein the additive comprises the additive of Formula 1 described below.

[0128] The above electrolyte can be prepared by dissolving a lithium salt in a non-aqueous organic solvent, adding an additive of Formula 1, and then mixing it. The process of mixing the electrolyte is widely known in the field of electrolyte manufacturing, and a person skilled in the art can appropriately select and use it.

[0129] A non-aqueous organic solvent according to one embodiment of the present invention may include one or more of the non-aqueous organic solvents described above.

[0130] In one embodiment, the non-aqueous organic solvent may be a mixture containing ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) in a volume ratio of 10 to 40: 10 to 40: 40 to 80. Here, the volume ratio is a value based on 100 volume% of the total of ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC). Within the above range, it is easy to implement the effects of the additive described below, and it may be easy to provide a low resistance increase rate, a low gas generation rate, and a rapid charging effect after high-temperature storage in a lithium secondary battery containing the nickel-containing cathode active material described below.

[0131] A lithium salt according to one embodiment of the present invention may include one or more selected from the group consisting of LiPF6, LiClO4, LiBF4, lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), LiSO3CF3, LiBOB (Lithium bis(oxalate)borate), LiDFOB (Lithium difluoro(oxalato)borate), LiDFBP (Lithium difluoro(bisoxalato)phosphate), LiTFOP (Lithium Tetrafluoro Oxalato Phosphate), LiPO2F2, LiSbF6, LiAsF6, LiAlO2, LiAlCl4, LiCl, LiI, LiN(SO3C2F5)2, Li(FSO2)2N, and LiC4F9SO3. According to one embodiment, LiPF6 may be used as the lithium salt.

[0132] The concentration of the lithium salt may be 0.1M to 3.0M. Specifically, the concentration of the lithium salt may be 0.5M or higher and 1.0M or higher. The concentration of the lithium salt may be 3.0M or lower, 2.5M or lower, and 2.0M or lower. In the present invention, when the concentration of the lithium salt is 0.1M to 2.0M, the conductivity and viscosity of the electrolyte can be appropriately maintained.

[0133] additives

[0134] An additive according to one embodiment of the present invention includes an additive of Formula 1 to be described later.

[0135] The additive of Chemical Formula 1 is a compound having a ring with an SO4 structure as described in Chemical Formula 1 below, which lowers the resistance increase rate after high-temperature storage and, at the same time, includes oxygen and a double bond in the substituents attached to the ring, thereby forming a uniform film on the cathode as the double bond is decomposed by reduction, and can provide a gas generation reduction effect and a rapid charging effect.

[0136] The additive of Chemical Formula 1 above is represented by Chemical Formula 1 below. The electrolyte may contain one or more additives of Chemical Formula 1 below:

[0137] [Chemical Formula 1]

[0138]

[0139] In the above chemical formula 1,

[0140] n is 0 or 1, and

[0141] R 11 to R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or the following chemical formula 1-1.

[0142] R 11 to R 14 At least one of them is the following chemical formula 1-1,

[0143] [Chemical Formula 1-1]

[0144]

[0145] (In the above chemical formula 1-1

[0146] R 15 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 alkoxylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group, and

[0147] R 16is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and

[0148] However, R 15 is a substituted or unsubstituted C2 to C20 alkenylene group or R 16 is a substituted or unsubstituted C2 to C20 alkenyl group)).

[0149] In the above chemical formula 1-1, R 16 is a substituted or unsubstituted C2 to C20 alkenyl group, and R 15 It may be a substituted or unsubstituted C1 to C20 alkylene group. In this case, the effect of providing a uniform film formation effect and a low gas generation rate on the surface of the cathode may be higher.

[0150] For example, R 16 ... may be a substituted or unsubstituted C2 to C10 alkenyl group, or a substituted or unsubstituted C2 to C5 alkenyl group, or a substituted or unsubstituted C2 to C5 alkenyl group. For example, R 16 It can be an allyl group, a metaallyl group, or a vinyl group.

[0151] For example, R 15 It may be a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C1 to C5 alkylene group, or a substituted or unsubstituted C1 to C3 alkylene group.

[0152] R in Chemical Formula 1 above 13 and R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, or the above formula 1-1, and R 13 and R 14At least one of them may be the above chemical formula 1-1. For example, R 13 and R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C5 alkyl group, or the above formula 1-1, and R 13 and R 14 At least one of them may be the above chemical formula 1-1.

[0153] R 11 and R 12 Each may independently be hydrogen, a substituted or unsubstituted C1 to C20 alkyl group. For example, R 11 and R 12 Each may independently be hydrogen or a substituted or unsubstituted C1 to C5 alkyl group. In this case, the preparation of the compound of Formula 1 may be easy.

[0154] The additive of Chemical Formula 1 above may be one or more of the additives of Chemical Formula 1-2 below:

[0155] [Chemical Formula 1-2]

[0156]

[0157] (In the above chemical formula 1-2,

[0158] R 21 and R 22 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and

[0159] R 23...is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or the following chemical formula 1-3,

[0160] R 24 is the following chemical formula 1-3.

[0161] [Chemical Formula 1-3]

[0162]

[0163] (In the above chemical formula 1-3,

[0164] R 25 R in the above chemical formula 1-1 15 Identical to what is defined in,

[0165] R 26 is a single bond or a substituted or unsubstituted C2 to C18 alkylene group).

[0166] The additive of the above chemical formula 1 may be one or more of the following chemical formulas 1-4 to 1-9:

[0167] [Chemical Formula 1-4]

[0168]

[0169] [Chemical Formula 1-5]

[0170]

[0171] [Chemical Formula 1-6]

[0172]

[0173] [Chemical Formula 1-7]

[0174]

[0175] [Chemical Formula 1-8]

[0176]

[0177] [Chemical Formula 1-9]

[0178]

[0179] The additive of Formula 1 and the additive of Formula 1-2 can each be synthesized through conventional synthesis methods known to those skilled in the art. For example, the additive can be prepared by oxidation using SOCl2 with a diol intermediate having a double bond and two alcohol groups.

[0180] The additive of Formula 1 above may be included in an amount of 0.05 to 5 weight percent relative to the total amount of the electrolyte. Within this range, after high-temperature storage in the electrolyte containing the non-aqueous organic solvent and the lithium salt, there may be effects of providing a low resistance increase rate, a low gas generation rate, and rapid charging.

[0181] Specifically, the additive of Formula 1 may be included in an amount of 0.1 to 5 weight%, 0.25 to 5 weight%, or 0.5 to 5 weight% relative to the total amount of the electrolyte. When the content of the additive is within the above range, the above-described effect is significantly enhanced, and there may be an additional effect of not increasing the resistance of the battery.

[0182] In one embodiment, the additive of Formula 1 may be included in an amount of 95% by weight or more of the total additive in the electrolyte, for example, 95 to 100% by weight, 99 to 100% by weight, or 100% by weight. Within this range, the processability of the battery can be improved by ensuring that the effect of the battery is not achieved without the additional additive described above.

[0183] Thus, by including the additive of Formula 1 in the combination of the above-described non-aqueous organic solvent and lithium salt, the electrolyte according to the present invention can realize a lithium secondary battery with improved lifespan characteristics and stability by providing a low resistance increase rate, a low gas generation rate, and rapid charging after high-temperature storage in a lithium secondary battery that includes a positive electrode active material, particularly a lithium nickel-based oxide.

[0184] In another embodiment of the present invention, a lithium secondary battery may be provided comprising: a positive electrode comprising a positive active material; a negative electrode comprising a negative active material; and an electrolyte, wherein the electrolyte comprises a non-aqueous organic solvent; a lithium salt; and an additive, and the additive comprises an additive of Formula 1.

[0185] The above-mentioned lithium secondary battery may be applied to automobiles, mobile phones, and / or various types of electric devices, etc., but the present invention is not limited thereto.

[0186] The above-mentioned positive electrode active material may be a lithium transition metal composite oxide, and specific examples include a lithium nickel-based oxide, a lithium cobalt-based oxide, a lithium manganese-based oxide, a lithium iron phosphate-based compound, a cobalt-free nickel-manganese-based oxide, or a combination thereof.

[0187] As an example, a compound represented by any one of the following chemical formulas may be used. Li a A 1-b X b O 2-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Mn 2-b X b O 4-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b X c O 2-α D α(0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Mn b X c O 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni b Co c L 1 d G e O2(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0≤e≤0.1); Li a NiG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a CoG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-b G b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn2G b O4(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-g G g PO4(0.90≤a≤1.8, 0≤g≤0.5); Li (3-f) Fe2(PO4)3(0≤f≤2); Li a FePO4(0.90≤a≤1.8).

[0188] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; X is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; L 1 is Mn, Al, or a combination thereof.

[0189] The above positive active material may include, for example, a lithium nickel-based oxide represented by the following chemical formula 2, a lithium cobalt-based oxide represented by the following chemical formula 3, a lithium iron phosphate-based compound represented by the following chemical formula 4, a cobalt-free lithium nickel-manganese-based oxide represented by the chemical formula 5, or a combination thereof.

[0190] In one embodiment, the positive electrode active material may be a lithium nickel-based oxide represented by the following chemical formula 2. A battery comprising a positive electrode containing a lithium nickel-based oxide as a positive electrode active material and the electrolyte together comprises

[0191] [Chemical Formula 2]

[0192] Li a1 Ni x1 M 1 y1 M 2 z1 O 2-b1 X b1

[0193] In the above chemical formula 2, 0.9≤a1≤1.8, 0.3≤x1≤1, 0≤y1≤0.7, 0≤z1≤0.7, 0.9≤x1+y1+z1≤1.1, and 0≤b1≤0.1, and M 1 and M 2 Each is independently one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is one or more elements selected from the group consisting of F, P, and S.

[0194] In the above chemical formula 2, 0.6≤x1≤1, 0≤y1≤0.4, and 0≤z1≤0.4, or 0.8≤x1≤1, 0≤y1≤0.2, and 0≤z1≤0.2.

[0195] [Chemical Formula 3]

[0196] Li a2 Co x2 M 3 y2 O 2-b2 Xb2

[0197] In the above chemical formula 3, 0.9≤a2≤1.8, 0.7≤x2≤1, 0≤y2≤0.3, 0.9≤x2+y2≤1.1, and 0≤b2≤0.1, and M 3 is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Se, Si, Sn, Sr, Ti, V, W, Y, Zn and Zr, and X is one or more elements selected from the group consisting of F, P, and S.

[0198] [Chemical Formula 4]

[0199] Li a3 Fe x3 M 4 y3 PO 4-b3 X b3

[0200] In the above chemical formula 4, 0.9≤a3≤1.8, 0.6≤x3≤1, 0≤y3≤0.4, and 0≤b3≤0.1, and M 4 is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Mg, Mn, Mo, Ni, Se, Si, Sn, Sr, Ti, V, W, Y, Zn and Zr, and X is one or more elements selected from the group consisting of F, P, and S.

[0201] [Chemical Formula 5]

[0202] Li a4 Ni x4 Mn y4 M 5 z4 O 2-b4 X b4

[0203] In the above chemical formula 5, 0.9≤a2≤1.8, 0.8≤x4<1, 0 <y4≤0.2, 0≤z4≤0.2, 0.9≤x4+y4+z4≤1.1, 및 0≤b4≤0.1이고 M 5is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Fe, Mg, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is one or more elements selected from the group consisting of F, P, and S.

[0204] For example, the above-mentioned positive electrode active material may be a high-nickel positive electrode active material in which the nickel content relative to 100 mol% of the metal excluding lithium in the lithium transition metal composite oxide is 80 mol% or more, 85 mol% or more, 90 mol% or more, 91 mol% or more, or 94 mol% or more and 99 mol% or less. The high-nickel positive electrode active material can achieve high capacity and can be applied to high-capacity, high-density lithium secondary batteries.

[0205] In a specific embodiment, the negative electrode active material may include at least one of graphite and a Si composite.

[0206] When the above-mentioned cathode active material includes a Si composite and graphite together, the Si composite and graphite may be included in the form of a mixture, in which case the Si composite:graphite may be included in a weight ratio of 1:99 to 50:50 based on a total of 100 parts by weight. More specifically, the Si composite:graphite may be included in a weight ratio of 3:97 to 20:80, 4:96 to 20:80, or 5:95 to 20:80.

[0207] The above Si composite comprises a core containing Si-based particles and an amorphous carbon coating layer, for example, the Si-based particles are a Si-C composite, SiO xIt may include one or more of (0 < x ≤ 2) and Si alloys. For example, the Si-C composite may include a core containing Si particles and crystalline carbon and an amorphous carbon coating layer located on the surface of the core. The crystalline carbon may include, for example, graphite, and more specifically, natural graphite, artificial graphite, or a mixture thereof.

[0208] When the positive electrode contains a high-nickel-based positive electrode active material and the negative electrode contains graphite, the effect of improving the high-temperature stability of the lithium secondary battery can be maximized.

[0209]

[0210] Examples and comparative examples of the present invention are described below. However, the following examples are merely one example of the present invention, and the present invention is not limited to the following examples.

[0211] Synthetic example

[0212] 100 mmol of 3-Allyloxy-1,2-propanediol and 300 mmol of thionyl chloride are placed in a 500 ml round-bottom flask with 200 ml of methylene chloride and stirred in an ice bath. After stirring for 2 hours, the reaction mixture is concentrated. To the concentrated intermediate, 200 mmol of sodium periodate, 200 ml of methylene chloride, 0.2 mol of ruthenium chloride, and 100 ml of distilled water are added and stirred at room temperature (25°C). Once the reaction is complete, the mixture is extracted three times with distilled water and methylene chloride, then the distilled water of the organic layer is removed using magnesium sulfate and dried with a vacuum pump to finally obtain the compound of Formula 1-4.

[0213] The NMR results of the prepared compound are shown in Fig. 6. Referring to Fig. 6, it can be seen that the compound of Chemical Formula 1-4 was prepared.

[0214] [Chemical Formula 1-4]

[0215]

[0216] Examples and Comparative Examples

[0217] Example 1

[0218] (1) Preparation of electrolyte

[0219] An electrolyte was prepared by dissolving 1.25 M LiPF6 in a carbonate-based solvent mixed with ethylene carbonate, ethylmethyl carbonate, and dimethyl carbonate in a volume ratio of 20:30:50 (based on a total volume of 100), adding 0.25 wt% of the additive of Chemical Formula 1-4, and mixing.

[0220] (2) Manufacturing of lithium secondary batteries

[0221] LiNi 0.91 Co 0.08 Al 0.01 A cathode active material slurry was prepared by mixing O297 wt%, artificial graphite powder 0.5 wt%, carbon black (Ketjenblack) 1 wt%, and polyvinylidene fluoride (PVdF) 1.5 wt%, adding the mixture to N-methyl-2-pyrrolidone (NMP), and stirring for 30 minutes using a mechanical stirrer. The slurry was applied to a thickness of about 60 μm on a 20 μm thick aluminum current collector using a doctor blade, dried in a hot air dryer at 100 ℃ for 0.5 hours, dried again under vacuum at 120 ℃ for 4 hours, and then rolled to produce a cathode.

[0222] A cathode active material slurry was prepared by mixing 98 wt% of a cathode active material, in which a graphite and Si composite was mixed in a weight ratio of 95.8:4.2, 1 wt% of styrene-butadiene rubber (SBR), and 1 wt% of carboxymethylcellulose (CMC), adding the mixture to distilled water, and stirring for 60 minutes using a mechanical stirrer. The slurry was applied to a thickness of about 60 μm on a 10 μm thick copper current collector using a doctor blade, dried in a hot air dryer at 100 ℃ for 0.5 hours, dried once more under vacuum conditions at 120 ℃ for 4 hours, and then rolled to produce a cathode.

[0223] An electrode assembly was manufactured by assembling the above positive electrode and the above negative electrode with a separator made of polyethylene material with a thickness of 16 μm, and a circular lithium secondary battery was manufactured by injecting the above electrolyte.

[0224]

[0225] Examples 2 to 4

[0226] An electrolyte and a battery were prepared in the same manner as in Example 1, except that the content of the additive of Formula 1-4 in Example 1 was changed as shown in Table 1 below.

[0227]

[0228] Comparative Example 1

[0229] The electrolyte and battery were prepared in the same manner as in Example 1, except that the additive of Formula 1-4 was not included in Example 1.

[0230]

[0231] Comparative Example 2

[0232] An electrolyte and a battery were prepared in the same manner as in Example 1, except that 0.25% by weight of the additive of Formula 6 below was included instead of the additive of Formula 1-4 above in Example 1.

[0233] [Chemical Formula 6]

[0234]

[0235]

[0236] Comparative Example 3

[0237] An electrolyte and a battery were prepared in the same manner as in Example 1, except that 0.25% by weight of the additive of Formula 7 below was included instead of the additive of Formula 1-4 above in Example 1.

[0238] [Chemical Formula 7]

[0239]

[0240]

[0241] Comparative Example 4

[0242] An electrolyte and a battery were prepared in the same manner as in Example 1, except that 0.25% by weight of the additive of Formula 8 below was included instead of the additive of Formula 1-4 above in Example 1.

[0243] [Chemical Formula 8]

[0244]

[0245]

[0246] Evaluation example

[0247] The lithium secondary battery was evaluated in the following manner.

[0248] Evaluation Example 1: High-temperature storage characteristic evaluation, DCIR (direct current internal resistance) increase rate

[0249] For the lithium secondary batteries according to the examples and comparative examples, the initial DC resistance (DCIR, unit: mΩ) was measured using the △V / △I (change in voltage / change in current) value, the maximum energy state inside the battery was made to a fully charged state (SOC (state of charge) 100%), and after storing it at 60°C for 60 days in this state, the DC resistance (DCIR, unit: mΩ) was measured, and the DCIR increase rate (%) was calculated according to the following formula.

[0250] [ceremony]

[0251] DCIR Growth Rate (%) = (DCIR after 60 days of storage / Initial DCIR) × 100

[0252] Evaluation Example 2: Evaluation of Rapid Charging Characteristics

[0253] For the lithium secondary batteries according to the examples and comparative examples, charging and discharging were performed at C-rates of 0.1C, 0.2C, 0.5C, 1C, 2C, and 5C for each of the 5 cycles at 25°C and 2.5V - 4.2V, and discharging at a C-rate of 0.5C for each of the 5 cycles, and the capacity retention rate was calculated by referring to Evaluation 3. Table 2 below shows the capacity retention rate after 30 cycles.

[0254] Evaluation Example 3: Evaluation of High-Temperature Gas Generation Characteristics

[0255] High-temperature gas generation characteristics were evaluated for lithium secondary batteries according to the examples and comparative examples. To this end, the maximum energy state inside the battery was made to a fully charged state (SOC 100%), and after storing it at a high temperature (60°C) for 1 day and 7 days in this state, the amount of gas generated (thickness mL) was evaluated, respectively. The gas generation increase rate was calculated as [(amount of gas generated after storing at 60°C for 7 days) / (amount of gas generated after supplementing at 60°C for 1 day)] × 100.

[0256] The results of the above evaluation example are shown in Tables 1 and 2 below.

[0257] Additive DCIR Type Content 0 days (mΩ) 60 days (mΩ) Growth Rate (%) Example 1 Chemical Formula 1-40.259.4911.44121 Example 2 Chemical Formula 1-40.59.0910.03110 Example 3 Chemical Formula 1-419.7310.98113 Example 4 Chemical Formula 1-459.8011.02112 Comparative Example 1--9.4311.71124 Comparative Example 2 Chemical Formula 60.259.9211.65117 Comparative Example 3 Chemical Formula 70.259.6512.80133 Comparative Example 4 Chemical Formula 80.259.9112.06122

[0258] Additive Rapid Charging (%) Gas Generation Amount (mL) Type Content 1 Day 7 Days Increase Rate (%) Example 1 Chemical Formula 1-4 0.25 97.1 10.29 13.55 13 1.7 Example 2 Chemical Formula 1-4 0.59 7.6 10.22 13.10 12 8.2 Example 3 Chemical Formula 1-4 19 7.4 10.3 11 3.87 13 4.5 Example 4 Chemical Formula 1-4 5 97.2 10.32 13.97 13 5.4 Comparative Example 1-- 96.7 10.4 11 4.50 13 9.3 Comparative Example 2 Chemical Formula 60.25 96.5 10.35 14.08 13 6.0 Comparative Example 3 Chemical Formula 70.25 96.4 10.44 14.45 13 8.4 Comparative Example 4 Chemical Formula 80.2596.510.5814.84140.3

[0259]

[0260] synthesis

[0261] Referring to Tables 1 and 2 above, it can be sufficiently anticipated that the electrolyte of the example can improve high voltage life and high temperature performance in a lithium secondary battery containing a high-nickel cathode active material based on the results of Evaluations 1 to 3.

[0262] However, referring to Tables 1 and 2 above, Comparative Example 1, which does not contain the additive of Formula 1 of the present invention, and Comparative Examples 2 to 4, which contain an additive with a structure different from Formula 1 of the present invention, had inferior rapid charging characteristics compared to the example and had a problem of generating a large amount of gas.

[0263]

[0264] Although preferred embodiments of the present invention have been described above, the present invention is not limited thereto and can be implemented with various modifications within the scope of the claims, the detailed description of the invention, and the attached drawings, and it is obvious that such modifications also fall within the scope of the present invention.

Claims

It comprises a non-aqueous organic solvent; a lithium salt; and an additive, The above additive is an electrolyte for a lithium secondary battery comprising the additive of Chemical Formula 1 below: [Chemical Formula 1] In the above chemical formula 1, n is 0 or 1, and R 11 to R 14 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or the following chemical formula 1-1. R 11 to R 14 At least one of them is the following chemical formula 1-1, [Chemical Formula 1-1] (In the above chemical formula 1-1 R 15 is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C1 to C20 alkoxylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C2 to C20 heteroarylene group, and R 16 is a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and However, R 15 is a substituted or unsubstituted C2 to C20 alkenylene group or R 16 is a substituted or unsubstituted C2 to C20 alkenyl group). In paragraph 1, In the above chemical formula 1-1, R 16 is a substituted or unsubstituted C2 to C20 alkenyl group, and R 15 The electrolyte for a lithium secondary battery is a substituted or unsubstituted C1 to C20 alkylene group. In paragraph 1 or 2, In the above chemical formula 1-1, R 16 Electrolyte for lithium secondary batteries, which is an allyl group, metaallyl group, or vinyl group. In any one of paragraphs 1 through 3, An electrolyte for a lithium secondary battery comprising one or more of the additives of the following chemical formula 1-2, wherein the additive of the above chemical formula 1: [Chemical Formula 1-2] (In the above chemical formula 1-2, R 21 and R 22 Each is independently hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and R 23 ...is hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, a substituted or unsubstituted C2 to C20 heteroaryl group, or the following chemical formula 1-3, R 24 is the following chemical formula 1-3. [Chemical Formula 1-3] (In the above chemical formula 1-3, R 25 R in the above chemical formula 1-1 15 Identical to what is defined in, R 26 is a single bond or a substituted or unsubstituted C2 to C18 alkylene group). In any one of paragraphs 1 through 4, An electrolyte for a lithium secondary battery comprising one or more of the additives of Chemical Formula 1 below, ranging from Chemical Formulas 1-4 to 1-9: [Chemical Formula 1-4] [Chemical Formula 1-5] [Chemical Formula 1-6] [Chemical Formula 1-7] [Chemical Formula 1-8] [Chemical Formula 1-9] . In any one of paragraphs 1 through 5, An electrolyte for a lithium secondary battery, wherein the additive of the above chemical formula 1 is included in an amount of 0.05 to 5 weight% relative to the total amount of the electrolyte. In any one of paragraphs 1 through 6, An electrolyte for a lithium secondary battery, wherein the additive of the above chemical formula 1 is included in at least 95% by weight of the total additive of the electrolyte. In any one of paragraphs 1 through 7, The above non-aqueous organic solvent is An electrolyte for a lithium secondary battery, comprising a mixture of ethylene carbonate (EC), ethylmethyl carbonate (EMC), and dimethyl carbonate (DMC) in a volume ratio of 10 to 40: 10 to 40: 40 to 80. In any one of paragraphs 1 through 8, The above lithium salt is one or more selected from the group consisting of LiPF6, LiClO4, LiBF4, lithium bis(fluorosulfonyl)imide (LiFSI), LiTFSI, LiSO3CF3, LiBOB, LiFOB, LiDFBP, LiTFOP, LiPO2F2, LiSbF6, LiAsF6, LiAlO2, LiAlCl4, LiCl, LiI, LiN(SO3C2F5)2, Li(FSO2)2N, and LiC4F9SO3, for an electrolyte for a lithium secondary battery. In any one of paragraphs 1 through 9, An electrolyte for a lithium secondary battery having a lithium salt concentration of 0.1M to 2.0M. Anode containing a positive electrode active material; A cathode comprising a cathode active material; and A lithium secondary battery comprising an electrolyte according to any one of claims 1 to 10. A lithium secondary battery according to claim 11, wherein the positive electrode active material comprises a lithium transition metal composite oxide having a nickel content of 80 mol% or more relative to 100 mol% of a metal excluding lithium. In Article 11 or Article 12, A lithium secondary battery comprising a lithium transition metal composite oxide represented by the following chemical formula 2: [Chemical Formula 2] Li a1 Ni x1 M 1 y1 M 2 z1 O 2-b1 X b1 In the above chemical formula 2, 0.9≤a1≤1.8, 0.3≤x1≤1, 0≤y1≤0.7, 0≤z1≤0.7, 0.9≤x1+y1+z1≤1.1, and 0≤b1≤0.1, and M 1 and M 2 Each is independently one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, Fe, Mg, Mn, Mo, Nb, Si, Sn, Sr, Ti, V, W, and Zr, and X is one or more elements selected from the group consisting of F, P, and S. In Paragraph 13, A lithium secondary battery in the above chemical formula 2, wherein 0.8≤x1≤1, 0≤y1≤0.2, and 0≤z1≤0.

2. In any one of paragraphs 11 through 14, A lithium secondary battery in which the above-mentioned negative electrode active material comprises at least one of graphite and Si composites. In any one of paragraphs 11 through 15, The above lithium secondary battery is a lithium secondary battery that is a cylindrical, prismatic, pouch-type, or coin-type battery.

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