CA3263260A1 - Lithium secondary battery - Google Patents

Abstract

The present invention provides a lithium secondary battery including a negative electrode, a positive electrode positioned opposite to the negative electrode, a separator disposed between the negative electrode and the positive electrode, and a non-aqueous electrolyte, wherein the negative electrode includes a silicon-based active material, the silicon-based active material comprises a compound represented by SiOx, wherein 0≤x<2, the non-aqueous electrolyte includes a lithium salt, an organic solvent, and an additive, the additive includes a first additive and a second additive, the first additive includes a coumarin-based compound represented by a specific formula, and the second additive includes at least one of lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium difluoro(oxalato)borate (LiDFOB), lithium difluorophosphate (LiDFP), or lithium difluorobis-(oxalate)phosphate (LiDFOP).

Description

1 DESCRIPTION LITHIUM SECONDARY BATTERY 5 [TECHNICAL FIELD] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority from Korean Patent Application No. 10-2022-0103657 filed on August 18, 2022, the disclosure of which is incorporated by reference herein. 10 TECHNICAL FIELD

[0002] The present disclosure relates to a lithium secondary battery. [BACKGROUNDART]

[0003] Lately, there has been a rapid expansion in the 15 application of lithium secondary batteries to power storage supply of large-area devices such as automobiles and power storage devices, as well as power supply of electronic devices such as electrical, electronic, communication, and computer devices, resulting in a rising demand for high- 20 capacity, high-output, and high-stability secondary batteries.

[0004] The lithium secondary batteries are mainly provided with a positive electrode composed of lithium-containing transition metal oxide, a negative electrode responsible for 25 storing lithium, and an electrolyte serving as a medium that2 delivers lithium ions, and a separator. In this case, the negative electrode may include a negative electrode active material such as a carbon-based active material or a siliconbased active material. 5 [0005] As for the lithium secondary batteries, a film (SEI film) is formed on the positive electrode and/or the negative electrode in an initial activation process, and this may protect the positive electrode and the negative electrode over the running of batteries, and prevent electrolyte 10 consumption caused by side reactions of the electrolyte. When failing to form a solid electrode film on the positive electrode and/or the negative electrode in the initial activation process, there may be degradation in capacity and lifespan. 15 [0006] In particular, among negative electrode active materials, the silicon-based active material is taking center stage as a material exhibiting higher capacity than the carbon-based active material, but the material brings about great changes in volume due to intercalation and 20 deintercalation of lithium. The volume expansion of the silicon-based active material causes a number of issues, such as deterioration in the durability of the pre-formed SEI film, continuous consumption of the electrolyte due to the generation of new negative electrode active materials, 25 and an increase in the thickness of the SEI film, leading to3 degradation in capacity and lifespan. [DISCLOSURE OF THE INVENTION] [TECHNICAL PROBLEM] 5 [0007] An aspect of the present invention provides a lithium secondary battery that may form a flexible and highly durable film on a negative electrode containing a silicon-based active material to reduce electrolyte side reactions and improve high-temperature cycle lifespan performance and 10 high-temperature storage performance. [TECHNICAL SOLUTION]

[0008] According to an aspect of the present invention, there is provided a lithium secondary battery including a negative electrode, a positive electrode positioned opposite 15 to the negative electrode, a separator disposed between the negative electrode and the positive electrode, and a nonaqueous electrolyte, wherein the negative electrode includes a negative electrode active material, the negative electrode active material includes a silicon-based active material, 20 the non-aqueous electrolyte includes a lithium salt, an organic solvent, and an additive, the additive includes a first additive and a second additive, the first additive includes a compound represented by Formula 1 below, and the second additive includes at least one of lithium 25 fluoromalonato(difluoro)borate (LiFMDFB), lithium4 difluoro(oxalato)borate (LiDFOB), lithium difluorophosphate (LiDFP), or lithium difluorobis-(oxalate)phosphate (LiDFOP). [0009] [Formula 1] 5 [0010] In Formula 1 above, R each independently includes halogen, a nitrile group, a propargyl group, an ester 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 10 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 n is an integer 15 selected from 0 to 6. [ADVANTAGEOUS EFFECTS]

[0011] A lithium secondary battery according to the present disclosure includes a negative electrode containing a silicon-based active material, and a non-aqueous electrolyte 20 including a first additive which is a coumarin-based compound having a specific structural formula and a second additive containing lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium difluoro(oxalato)borate (LiDFOB), or the like. When5 both the first additive and the second additive are included in the non-aqueous electrolyte, a flexible, highly restorable, and highly durable film may be formed on the negative electrode. Accordingly, the lithium secondary 5 battery according to the present disclosure forms the SEI film described above in a silicon-based negative electrode that provides concerns over electrolyte side reactions caused by extensive volume expansion to prevent SEI film breakage, the electrolyte side reactions, and an increase in 10 resistance due to an increase in the thickness of the electrode film, and may thus improve performance of the lithium secondary battery, particularly high-temperature cycle lifespan performance and high-temperature storage performance. 15 [MODE FOR CARRYING OUT THE INVENTION]

[0012] It will be understood that words or terms used in the specification and claims of the present disclosureshall not be construed as being limited to having the meaning defined in commonly used dictionaries. It will be further 20 understood that the words or terms should be interpreted as having meanings that are consistent with their meanings in the context of the relevant art and the technical idea of the disclosure, based on the principle that an inventor may properly define the meaning of the words or terms to best 25 explain the disclosure.6

[0013] It will be further understood that the terms “include,” “comprise,” or "have" when used in this specification, specify the presence of stated features, numbers, steps, elements, or combinations thereof, but do 5 not preclude the presence or addition of one or more other features, numbers, steps, elements, or combinations thereof.

[0014] Meanwhile, prior to describing the present disclosure, unless otherwise specified in the present disclosure, "*" indicates a portion connected between ends of the same or 10 different atoms or formulas.

[0015] In addition, as used herein, "a" and "b" in the description of "a to b carbon atoms" indicate the number of carbon atoms included in a specific functional group. That is, the functional group may include "a" to "b" carbon atoms. 15 For example, the term "alkyl group having 1 to 5 carbon atoms" indicates an alkyl group including 1 to 5 carbon atoms, that is, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, (CH3)2CHCH2-, CH3CH2CH2CH2CH2-, (CH3)2CHCH2CH2-, or the like.

[0016] In addition, as used herein, both an alkyl group and 20 an aryl group may be substituted or unsubstituted. Unless otherwise defined, the term "substituted" indicates that at least one hydrogen bonded to carbon is substituted with an element other than hydrogen, and for example, it means being substituted with an alkyl group having 1 to 20 carbon atoms, 25 an alkenyl group having 2 to 20 carbon atoms, an alkynyl7 group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, a heterocycloalkyl group having 3 to 12 carbon atoms, a 5 heterocycloalkenyl group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, a halogen atom, a fluoroalkyl group having 1 to 20 carbon atoms, a nitro group, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a haloaryl 10 group having 6 to 20 carbon atoms, or the like.

[0017] Hereinafter, various aspects of the present invention will be described in more detail.

[0018] Lithium secondary battery

[0019] The present disclosure relates to a lithium secondary 15 battery.

[0020] Specifically, a lithium secondary battery according to an embodiment of the present invention includes a negative electrode, a positive electrode positioned opposite to the negative electrode, a separator disposed between the 20 negative electrode and the positive electrode, and a nonaqueous electrolyte, wherein the negative electrode includes a negative electrode active material, the negative electrode active material includes a silicon-based active material, the non-aqueous electrolyte includes a lithium salt, an 25 organic solvent, and an additive, the additive includes a8 first additive and a second additive, the first additive includes a compound represented by Formula 1 below, and the second additive includes at least one of lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium 5 difluoro(oxalato)borate (LiDFOB), lithium difluorophosphate (LiDFP), or lithium difluorobis-(oxalate)phosphate (LiDFOP). [0021] [Formula 1]

[0022] In Formula 1 above, R each independently includes 10 halogen, a nitrile group, a propargyl group, an ester 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, 15 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 n is an integer selected from 0 to 6. 20 [0023] The lithium secondary battery according to the present disclosure includes a negative electrode containing a silicon-based active material, and a non-aqueous electrolyte including a first additive and a second additive9 containing lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium difluoro(oxalato)borate (LiDFOB), or the like. When both the first additive and the second additive are included in the non-aqueous electrolyte, a flexible, highly 5 restorable, and highly durable film may be formed on the negative electrode. Accordingly, the lithium secondary battery according to the present disclosure forms the SEI film described above in a silicon-based negative electrode that provides concerns over electrolyte side reactions 10 caused by extensive volume expansion to prevent SEI film breakage, the electrolyte side reactions, and an increase in resistance due to an increase in the thickness of the electrode film, and may thus improve performance of the lithium secondary battery, particularly high-temperature 15 cycle lifespan performance and high-temperature storage performance.

[0024] In this case, the lithium secondary battery of the present disclosure may be manufactured according to a typical method known in the art. For example, a negative electrode, 20 a positive electrode, and a separator between the negative electrode and positive electrode are sequentially stacked to form an electrode assembly, and then the electrode assembly is inserted into a battery case, and a non-aqueous electrolyte according to the present disclosure is injected 25 to manufacture the lithium secondary battery of the present10 disclosure. [0025] (1) Negative electrode

[0026] The negative electrode includes a negative electrode active material. 5 [0027] The negative electrode active material includes a silicon-based active material.

[0028] The silicon-based active material is beneficial as having higher capacity and higher energy density than a carbon-based active material such as graphite, but is 10 unfavorable as exhibiting changes in the volume of the active material upon charging and discharging. The expansion and contraction in the volume of the silicon-based active material causes conductive disconnection in the negative electrode, resulting in increased resistance and decreased 15 lifespan performance. In addition, the SEI film of the negative electrode formed in an activation process of a lithium secondary battery may be broken due to the volume change of the silicon-based active material, and this promotes side reactions of an electrolyte to cause an 20 increase in resistance due to an increase in the thickness of the SEI film and depletion of the electrolyte, resulting in degradation in lifespan performance and storage characteristics.

[0029] In order to resolve the limitations, the present 25 disclosure uses a non-aqueous electrolyte in which a first11 additive and a second additive which will be described later are used as the additive together along with a negative electrode including a silicon-based active material. The using of the combined first and second additives allows the 5 SEI film formed on the negative electrode to have improved flexibility (restorability) and durability, leading to excellent restorability in the volume change of the siliconbased active material, and prevention of SEI film breakage to significantly prevent the electrolyte side reactions and 10 the electrolyte depletion, and accordingly, a lithium secondary battery having excellent lifespan performance and storage performance is obtainable.

[0030] The silicon-based active material may include a compound represented by SiOx (0≤x<2). As SiO2 does not react 15 with lithium ions and thus is not able to store lithium, x is preferably within the above range. Specifically, the silicon-based active material may include at least one of Si or SiOx (0.7≤x≤1.2, specifically x=1).

[0031] The silicon-based active material may have an average 20 diameter (D50) of 1 μm to 30 μm, preferably 2 μm to 15 μm, in terms of ensuring structural stability upon charging and discharging and reducing side reactions with an electrolyte.

[0032] The negative electrode active material may further include a carbon-based active material in addition to the 25 silicon-based active material.12

[0033] The carbon-based active material may include at least one of artificial graphite, natural graphite, hard carbon, soft carbon, carbon black, graphene, or fibrous carbon, and may preferably include at least one of artificial graphite 5 or natural graphite.

[0034] The carbon-based active material may have an average diameter (D50) of 10 μm to 30 μm, preferably 15 μm to 25 μm, in terms of ensuring structural stability upon charging and discharging and reducing side reactions with an electrolyte. 10 [0035] When the negative electrode active material includes a silicon-based active material and a carbon-based active material, the silicon-based active material and the carbonbased active material may be in a weight ratio of 1:99 to 50:50, specifically 3:97 to 20:80, and more specifically 15 3:97 to 10:90.

[0036] In an embodiment, the negative electrode active material may not contain a carbon-based active material.

[0037] The negative electrode may include a negative electrode current collector and a negative electrode active 20 material layer disposed on at least one surface of the negative electrode current collector. In this case, the negative electrode active material may be included in the negative electrode active material layer.

[0038] The negative electrode current collector is not 25 particularly limited as long as it has conductivity without13 causing chemical changes in batteries. Specifically, copper, stainless steel, aluminum, nickel, titanium, fired carbon, or copper or stainless steel that is surface-treated with carbon, nickel, titanium, silver, or the like may be used as 5 the negative electrode current collector.

[0039] The negative electrode current collector may generally have a thickness of 3 μm to 500 μm.

[0040] The negative electrode current collector may have fine irregularities formed on a surface thereof to improve 10 bonding strength of a negative electrode active material. For example, the negative electrode current collector may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam body, and a non-woven fabric body.

[0041] The negative electrode active material layer is 15 disposed on at least one surface of the negative electrode current collector. Specifically, the negative electrode active material layer may be disposed on one surface or both surfaces of the negative electrode current collector.

[0042] The negative electrode active material layer may 20 include the negative electrode active material in an amount of 60 wt% to 99 wt%, preferably 75 wt% to 95 wt%.

[0043] The negative electrode active material layer may further include a binder and a conductive material, along with the negative electrode active material. 25 [0044] The binder is used to improve the performance of14 batteries through improved adhesion between the negative electrode active material layer and the negative electrode current collector, and may include, for example, at least any one of a polyvinylidene fluoride-hexafluoropropylene 5 copolymer (PVDF-co-HFP), polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, 10 polypropylene, polyacrylic acid, an ethylene-propylene-diene monomer (EPDM), a sulfonated EPDM, styrene butadiene rubber (SBR), fluorine rubber, or a material in which hydrogen thereof is substituted with Li, Na, or Ca, or may also include various copolymers thereof. 15 [0045] The negative electrode active material layer may include the binder in an amount of 0.5 wt% to 30 wt%, preferably 1 wt% to 15 wt%, and more preferably 5 wt% to 10 wt%.

[0046] The conductive material is not particularly limited 20 as long as it has conductivity without causing chemical changes in batteries, and, for example, a conductive material, such as: graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal black; 25 conductive fibers such as carbon fibers or metal fibers;15 conductive tubes such as carbon nanotubes; fluorocarbon; metal powder such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide whiskers or potassium titanate whiskers; conductive metal oxide such as titanium 5 oxide; or polyphenylene derivatives, may be used.

[0047] The negative electrode active material layer may include the conductive material in an amount of 0.5 wt% to 30 wt%, preferably, 1 wt% to 25 wt%.

[0048] The negative electrode active material may have a 10 thickness of 10 μm to 100 μm, preferably 50 μm to 80 μm.

[0049] A negative electrode slurry including a negative electrode active material and/or a binder, a conductive material, and a solvent for forming a negative electrode slurry may be applied onto at least one surface of the 15 negative electrode current collector, and then dried and roll pressed to prepare the negative electrode.

[0050] The solvent for forming the negative electrode slurry may include at least one of distilled water, N-methyl-2- pyrrolidone (NMP), ethanol, methanol, or isopropyl alcohol, 20 preferably distilled water, in terms of facilitating the dispersion of, for example, the negative electrode active material, the binder and/or the conductive material. [0051] (2) Positive electrode

[0052] The positive electrode is positioned opposite to the 25 negative electrode.16

[0053] The positive electrode may include a positive electrode current collector, and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector. 5 [0054] The positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in batteries. To be specific, the positive electrode current collector may include at least one of copper, stainless steel, aluminum, nickel, titanium, 10 fired carbon, or an aluminum-cadmium alloy, and may preferably include aluminum.

[0055] The positive electrode current collector may generally have a thickness of 3 μm to 500 μm.

[0056] The positive electrode current collector may have 15 fine irregularities formed on a surface thereof to improve bonding strength of a positive electrode active material. For example, the positive electrode current collector may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam body, and a non-woven fabric body. 20 [0057] The positive electrode active material layer is disposed on at least one surface of the positive electrode current collector. Specifically, the positive electrode active material layer may be disposed on one surface or both surfaces of the positive electrode current collector. 25 [0058] The positive electrode active material layer may17 include a positive electrode active material.

[0059] The positive electrode active material is a compound capable of reversibly intercalating and deintercalating lithium, and may specifically include a lithium transition 5 metal composite oxide including lithium and at least one transition metal selected from nickel, cobalt, manganese, or aluminum, preferably, a lithium transition metal composite oxide including lithium and transition metal containing nickel, cobalt, or manganese. 10 [0060] For example, the lithium transition metal composite oxide may include lithium-manganese-based oxide (e.g., LiMnO2, LiMn2O4, etc.), lithium-cobalt-based oxide (e.g., LiCoO2, etc.), lithium-nickel-based oxide (e.g., LiNiO2, etc.), lithium-nickel-manganese-based oxide (e.g., LiNi1- 15 YMnYO2 (where 0<Y<1), LiMn2-zNizO4 (where 0<z<2), etc.), lithium-nickel-cobalt-based oxide (e.g., LiNi1-Y1CoY1O2 (where 0<Y1<1), etc.), lithium-manganese-cobalt-based oxide (e.g., LiCo1-Y2MnY2O2 (where 0<Y2<1), LiMn2-z1Coz1O4 (where 0<z1<2), etc.), lithium-nickel-manganese-cobalt-based oxide (e.g., 20 Li(NipCoqMnr1)O2 (where 0<p<1, 0<q<1, 0<r1<1, and p+q+r1=1) or Li(Nip1Coq1Mnr2)O4 (where 0<p1<2, 0<q1<2, 0<r2<2, and p1+q1+r2=2), etc.), or lithium-nickel-cobalt-transition metal (M) oxide (e.g., Li(Nip2Coq2Mnr3MS2)O2 (where M is selected from the group consisting of aluminum (Al), iron 25 (Fe), vanadium (V), chromium (Cr), titanium (Ti), tantalum18 (Ta), magnesium (Mg), and molybdenum (Mo), and p2, q2, r3, and S2 are each an atomic fraction of independent elements, wherein 0<p2<1, 0<q2<1, 0<r3<1, 0<S2<1, and p2+q2+r3+S2=1), etc.), and any one thereof or a compound of two or more 5 thereof may be included. Among these, in terms of being able to increase the capacity and stability of a battery, the lithium transition metal composite oxide may be LiCoO2, LiMnO2, LiNiO2, a lithium nickel-manganese-cobalt oxide (e.g., Li(Ni0.6Mn0.2Co0.2)O2, Li(Ni0.5Mn0.3Co0.2)O2, Li(Ni0.7Mn0.15Co0.15)O2, 10 or Li(Ni0.8Mn0.1Co0.1)O2, etc.), or a lithium-nickel-cobaltaluminum oxide (e.g., Li(Ni0.8Co0.15Al0.05)O2, etc.), or the like, and when considering an remarkable improvement effect according to the control of type and content ratio of constituent elements forming a lithium transition metal 15 composite oxide, the lithium transition metal composite oxide may be Li(Ni0.6Mn0.2Co0.2)O2, Li(Ni0.5Mn0.3Co0.2)O2, Li(Ni0.7Mn0.15Co0.15)O2, or Li(Ni0.8Mn0.1Co0.1)O2, or the like, and any one thereof or a mixture of two or more thereof may be used. 20 [0061] More specifically, the positive electrode active material may be a lithium transition metal composite oxide, and may contain nickel in an amount of 60 mol% or greater, with respect to the total number of moles of transition metals included in the lithium transition metal composite 25 oxide. Specifically, the positive electrode active material19 is a lithium transition metal composite oxide, and the transition metal includes nickel, and at least one selected from manganese, cobalt, or aluminum, and may include nickel in an amount of 60 mol% or greater, specifically 60 mol% to 5 90 mol%, with respect to the total number of moles of the transition metal. When the lithium transition metal composite oxide using such a high nickel content is used together with the above-described non-aqueous electrolyte, it is preferable for the purpose of reducing by-products in 10 the gas phase generated by structural collapse.

[0062] In addition, the positive electrode active material may include a lithium composite transition metal oxide represented by Formula A below. [0063] [Formula A] 15 Li1+x(NiaCobMncMd)O2

[0064] In Formula A above, M is at least one of 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 1+x, a, b, c, and d are each an atomic fraction of independent elements(0≤x≤0.2, 0.50≤a<1, 20 0<b≤0.25, 0<c≤0.25, 0≤d≤0.1, a+b+c+d=1).

[0065] Preferably, a, b, c, and d may be 0.70≤a≤0.95, 0.025≤b≤0.20, 0.025≤c≤0.20, and 0≤d≤0.05, respectively.

[0066] In addition, a, b, c, and d may be 0.80≤a≤0.95, 0.025≤b≤0.15, 0.025≤c≤0.15, and 0≤d≤0.05, respectively. 25 [0067] In addition, a, b, c, and d may be 0.85≤a≤0.90,20 0.05≤b≤0.10, 0.05≤c≤0.10, and 0≤d≤0.03, respectively.

[0068] The positive electrode active material layer may include the positive electrode active material in an amount of 80 wt% to 99 wt%, preferably 92 wt% to 98.5 wt%, in 5 consideration of exhibiting sufficient capacity of the positive electrode active material.

[0069] The positive electrode active material layer may further include a binder and/or a conductive material together with the above-described positive electrode active 10 material.

[0070] The binder is a component that supports the binding of an active material and a conductive material and the binding to a collector, and may specifically include at least one of polyvinylidene fluoride, polyvinyl alcohol, 15 carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, an ethylene-propylene-diene terpolymer (EPDM), a sulfonated EPDM, styrene-butadiene rubber, or fluorine rubber, and may 20 preferably include polyvinylidene fluoride.

[0071] The binder may be included in an amount of 1 wt% to 20 wt%, preferably 1.2 wt% to 10 wt% in the positive electrode active material layer for the purpose of sufficiently securing the binding strength between 25 components such as the positive electrode active material.21

[0072] The conductive material may be used to support and improve the conductivity of a secondary battery, and is not particularly limited as long as it has conductivity without causing chemical changes in batteries. Specifically, the 5 positive electrode conductive material may include at least one of graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal black; conductive fibers such as carbon fibers or metal fibers; 10 conductive tubes such as carbon nanotubes; fluorocarbon; metal powder such as aluminum or nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; or polyphenylene derivatives, and may preferably include carbon black for the 15 purpose of improving conductivity.

[0073] The conductive material may be included in an amount of 1 wt% to 20 wt%, preferably 1.2 wt% to 10 wt%, in the positive electrode active material layer for the purpose of sufficiently securing electrical conductivity. 20 [0074] The positive electrode active material may have a thickness of 30 μm to 400 μm, preferably 40 μm to 110 μm.

[0075] A positive electrode slurry including a positive electrode active material and optionally a binder, a conductive material, and a solvent for forming a positive 25 electrode slurry may be applied onto the positive electrode22 current collector, and then dried and roll pressed to prepare the positive electrode.

[0076] The solvent for forming a positive electrode slurry may include an organic solvent such as N-methyl-2- 5 pyrrolidone (NMP). The positive electrode slurry may have a solid content of 40 wt% to 90 wt%, specifically 50 wt% to 80 wt%. [0077] (3) Separator

[0078] A typically used porous polymer film, for example, a 10 porous polymer film prepared from a polyolefin-based polymer, such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, or an ethylene/methacrylate copolymer, may be used alone or in a lamination therewith as the separator. Also, a typical 15 porous nonwoven fabric, for example, a nonwoven fabric formed of high melting point glass fibers or polyethylene terephthalate fibers may be used, but the present disclosureis not limited thereto. Furthermore, a coated separator including a ceramic component or a polymer 20 component may be used to secure heat resistance or mechanical strength, and the separator having a single layer or multilayer structure may be used. [0079] (4) Non-aqueous electrolyte

[0080] A non-aqueous electrolyte according to the present 25 disclosure includes a lithium salt, an organic solvent, and23 an additive, the additive includes a first additive and a second additive, the first additive includes a compound represented by Formula 1 below, and the second additive includes at least one of lithium 5 fluoromalonato(difluoro)borate (LiFMDFB), lithium difluoro(oxalato)borate (LiDFOB), lithium difluorophosphate (LiDFP), or lithium difluorobis-(oxalate)phosphate (LiDFOP). [0081] [Formula 1] 10 [0082] In Formula 1 above, R each independently includes halogen, a nitrile group, a propargyl group, an ester 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 15 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 n is an integer 20 selected from 0 to 6.

[0083] The non-aqueous electrolyte according to the present disclosure includes, as an additive, a first additive containing a coumarin-based compound having a specific24 structural formula, and a second additive containing lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium difluoro(oxalato)borate (LiDFOB), or the like. When both the first additive and the second additive are included in 5 the non-aqueous electrolyte, a flexible, highly restorable, and highly durable film may be formed on the negative electrode. Accordingly, the lithium secondary battery according to the present disclosure forms the SEI film described above in a silicon-based negative electrode that 10 provides concerns over electrolyte side reactions caused by extensive volume expansion to prevent SEI film breakage, the electrolyte side reactions, and an increase in resistance due to an increase in the thickness of the electrode film, and may thus improve performance of the lithium secondary 15 battery, particularly high-temperature cycle lifespan performance and high-temperature storage performance.

[0084] Meanwhile, in the case of not using a silicon-based active material as a negative electrode active material, for example, when the above-described non-aqueous electrolyte is 20 applied to a negative electrode containing a carbon-based active material alone, the use of the combined first and second additives may rather cause an increase in resistance, and may thus have insignificantly improved or rather reduced effects, compared to the case in which the first additive or 25 the second additive is used alone.25 [0085] 1) Lithium salt

[0086] As a lithium salt used in the present disclosure, various lithium salts commonly used in non-aqueous electrolytes for lithium secondary batteries may be used 5 without limitation. For example, the lithium salt may include Li+ as a cation, and may include at least any one of F-, Cl-, Br-, I-, NO3-, N(CN)2-, BF4-, ClO4-, AlO4-, AlCl4-, PF6-, SbF6-, AsF6-, B10Cl10-, BF2C2O4-, BC4O8-, PF4C2O4-, PF2C4O8-, (CF3)2PF4-, (CF3)3PF3-, (CF3)4PF2-, (CF3)5PF-, (CF3)6P-, CF3SO3-, 10 C4F9SO3-, CF3CF2SO3-, (FSO2)2N-, CF3CF2(CF3)2CO-, (CF3SO2)2CH-, CH3SO3-, CF3(CF2)7SO3-, CF3CO2-, CH3CO2-, SCN-, or (CF3CF2SO2)2Nas an anion.

[0087] Specifically, the lithium salt may include at least one of LiCl, LiBr, LiI, LiBF4, LiClO4, LiAlO4, LiAlCl4, LiPF6, 15 LiSbF6, LiAsF6, LiB10Cl10, LiBOB (LiB(C2O4)2), LiCF3SO3, LiFSI (LiN(SO2F)2), LiCH3SO3, LiCF3CO2, LiCH3CO2, or LiBETI (LiN(SO2CF2CF3)2). Specifically, the lithium salt may include at least one of LiBF4, LiClO4, LiPF6, LiBOB (LiB(C2O4)2), LiCF3SO3, LiTFSI (LiN(SO2CF3)2), LiFSI 20 ((LiN(SO2F)2), or LiBETI (LiN(SO2CF2CF3)2).

[0088] The non-aqueous electrolyte may include the lithium salt at a concentration of 0.5 M to 5 M, specifically 0.8 M to 4 M, and more specifically 0.8 M to 2.0 M. When the concentration of the lithium salt satisfies the above range, 25 lithium ion yield (Li+ transference number) and the26 dissociation degree of lithium ions are improved, and accordingly, batteries may have improved output characteristics. [0089] 2) Organic solvent 5 [0090] An organic solvent is a non-aqueous solvent commonly used in lithium secondary batteries and is not particularly limited as long as its decomposition due to an oxidation reaction or the like may be minimized in the charging/discharging process of secondary batteries. 10 [0091] Specifically, the organic solvent may include 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.

[0092] Specifically, the organic solvent may include a 15 cyclic carbonate-based organic solvent, a linear carbonatebased organic solvent, or a mixture thereof.

[0093] The cyclic carbonate-based organic solvent is an organic solvent that may well dissociate lithium salt in an electrolyte due to high permittivity as a highly viscous 20 organic solvent, and specifically may include at least one of ethylene carbonate (EC), fluoroethylene carbonate (FEC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3- butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, or vinylene carbonate, and may more specifically 25 include at least one of ethylene carbonate (EC) or27 fluoroethylene carbonate (FEC), and may more specifically include fluoroethylene carbonate (FEC). The fluoroethylene carbonate (FEC) may form an SEI film having a high content of inorganic components such as LiF on the negative electrode, 5 thereby increasing the durability of the SEI film, and this may lead to improvements in lifespan performance and storage characteristics, particularly when the fluoroethylene carbonate (FEC) is applied to a negative electrode including a silicon-based active material. 10 [0094] The linear carbonate-based organic solvent is an organic solvent having low viscosity and low permittivity, and may specifically include at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, or 15 ethylpropyl carbonate, and may more specifically include at least one of ethylmethyl carbonate (EMC) or diethyl carbonate (DEC), and may more specifically include diethyl carbonate (DEC). The diethyl carbonate is a symmetrical linear carbonate and is free from transesterification, and may thus 20 preferably prevent degradation in reduction stability caused by generation of by-products from the transesterification reaction. The diethyl carbonate is particularly preferable when applied to a negative electrode containing a siliconbased active material. 25 [0095] The organic solvent may be a mixture of a cyclic28 carbonate-based organic solvent and a linear carbonate-based organic solvent. In this case, the cyclic carbonate-based organic solvent and the linear carbonate-based organic solvent may be mixed in a volume ratio of 5:95 to 40:60, 5 specifically a volume ratio of 7:93 to 30:70, or a volume ratio of 8:92 to 30:70, and more specifically a volume ratio of 8:92 to 20:80. When the mixing ratio of the cyclic carbonate-based organic solvent and the linear carbonatebased organic solvent satisfies the above range, both high 10 permittivity and low viscosity are satisfied, and excellent ionic conductivity may be achieved.

[0096] In addition, in order to prepare an electrolyte having high ionic conductivity, the organic solvent may further include at least one ester-based organic solvent 15 selected from a linear ester-based organic solvent or a cyclic ester-based organic solvent, along with at least one carbonate-based organic solvent selected from the cyclic carbonate-based organic solvent or the linear carbonatebased organic solvent. 20 [0097] The linear ester-based organic solvent may specifically include at least one of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, or butyl propionate.

[0098] In addition, the cyclic ester-based organic solvent 25 may specifically include at least one of γ-butyrolactone, γ-29 valerolactone, γ-caprolactone, σ-valerolactone, orε- caprolactone.

[0099] Meanwhile, the organic solvent may be used by adding an organic solvent commonly used in a non-aqueous electrolyte 5 without limitation, when needed. For example, at least one organic solvent selected from an ether-based organic solvent, a glyme-based solvent, or a nitrile-based organic solvent may be further included.

[00100] As the ether-based solvent, any one of dimethyl 10 ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, ethylpropyl ether, 1,3-dioxolane (DOL), or 2,2-bis(trifluoromethyl)-1,3-dioxolane (TFDOL), or a mixture of two or more thereof may be used, but is the embodiment is not limited thereto. 15 [00101] The glyme-based solvent, as a solvent having higher permittivity and lower surface tension than a linear carbonate-based organic solvent, and being less reactive with metal, may include at least one of dimethoxyethane (glyme, DME), diethoxyethane, digylme, tri-glyme, or tetra- 20 glyme (TEGDME), but is not limited thereto.

[00102] The nitrile-based solvent may include at least one of acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2- 25 fluorobenzonitrile, 4-fluorobenzonitrile,30 difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, 4- fluorophenylacetonitrile, or the like, but is not limited thereto. 5 [00103] 3) additive

[00104] The additive includes a first additive and a second additive.

[00105] The first additive includes a compound represented by Formula 1 below. 10 [00106] [Formula 1]

[00107] In Formula 1 above, R each independently includes halogen, a nitrile group, a propargyl group, an ester group, an ether group, a ketone group, a carboxy group, a 15 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 20 sulfone group, a sulfonate group, a sulfate group, or a combination of two or more thereof, and n is an integer selected from 0 to 6.

[00108] The first additive includes a coumarin-based31 compound having the above-described structural formula, and the coumarin-based compound is highly reducible in a negative electrode, and upon initial activation of a lithium secondary battery, a ring structure is ring-opened, and thus a 5 polyethylene oxide-based polymer-type SEI film is obtainable. The polymer-type SEI film is beneficial as having excellent flexibility and restorability. However, the SEI film derived from the first additive has poor durability, and accordingly, a second additive which will be described later 10 needs to be used in combination with the first additive to achieve the effect of improving high-temperature cycle lifespan performance and high-temperature storage performance, which are the objectives of the present disclosure. 15 [00109] In an embodiment, in Formula 1 above, R may each independently comprise a propargyl group, an ester group, an ether group, a ketone group, a carboxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a boron group, a borate group, 20 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.

[00110] In an embodiment, in Formula 1 above, R may specifically each independently comprise halogen (halogen 25 may be selected from F, Cl, Br, and I, and may specifically32 be F), a nitrile group, a propargyl group, an ester group, an ether group, or a combination of two or more thereof. These substituents exhibit excellent reducibility, are favorable in forming a polymer-type SEI film, and exhibit 5 the excellent performance of delivering lithium ions, and thus are preferable.

[00111] In Formula 1 above, n may be an integer selected from 0 to 6, specifically, an integer selected from 1 to 6, and more specifically, n may be 1. In Formula 1 above, when 10 n is 2 or greater, R may each be the same as or different from each other.

[00112] Specifically, the compound represented by Formula 1 above may comprise at least one a compound represented by Formula 2 below or a compound represented by Formula 3 below. 15 [00113] [Formula 2] [00114] [Formula 3]

[00115] In Formulas 2 and 3 above, R is the same as 20 defined in Formula 1 above.

[00116] The compounds represented by Formulas 2 and 333 each have a structure in which substituents are present at positions 3 and 7 (in accordance with IUPAC nomenclature) of a ring structure, and in this case, it is preferable in that the compounds are favorable in synthesizing at the position 5 as described above compared to other substitution positions. In particular, in the case of the compound represented by Formula 2 in which a substituent is present at position 3, it is more preferable in that the uniformity of reactions is improved upon reducing to a negative electrode. 10 [00117] Specifically, the compound represented by Formula 1 above may include at least one selected from the group consisting of compounds represented by Formulas 4 to 12 below. The compound represented by Formula 1 may specifically include at least one selected from the group consisting of 15 compounds represented by Formulas 4 to 7 below, in view of being more smoothly reduced to the negative electrode and more favorable in forming a polymer-type SEI film, and may more specifically include at least one selected from the group consisting of Formula 4, Formula 5, and Formula 7 below, 20 and the compound represented by Formula 1 may even more specifically include the compound represented by Formula 4 below, in terms of being highly reducible, and having an excellent effect of inhibiting transition metal elution along with the above-described effects. 25 [00118] [Formula 4]34 [00119] [Formula 5] [00120] [Formula 6] 5 [00121] [Formula 7] [00122] [Formula 8] 10 [00123] [Formula 9] o o35 [00124] [Formula 10] [00125] [Formula 11] 5 [00126] [Formula 12]

[00127] The non-aqueous electrolyte may include the first additive in an amount of 0.01 wt% to 10 wt%, specifically 10 0.05 wt% to 7 wt%, more specifically 0.1 wt% to 5 wt%, and more specifically 0.3 wt% to 2 wt%. When the amount of the compound represented by Formula 1 satisfies the above range, it is preferable in terms of sufficiently providing flexibility and restorability to the SEI film, and preventing 15 an increase in resistance of a lithium secondary battery due36 to excessive addition, which causes degradation in lifespan performance.

[00128] The second additive may include at least one of lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium 5 difluoro(oxalato)borate (LiDFOB), lithium difluorophosphate (LiDFP), or lithium difluorobis-(oxalate)phosphate (LiDFOP).

[00129] The second additive may include a lithium salt additive containing fluorine, and the above-described lithium salt additive may form an inorganic-type SEI film 10 such as LiF upon initial activation of a lithium secondary battery. The inorganic-type SEI film such as LiF has excellent adhesion to a negative electrode surface, but hardly covers the negative electrode surface entirely, making it difficult to sufficiently prevent electrolyte side 15 reactions.

[00130] In this aspect, the non-aqueous electrolyte is characterized in that a first additive and a second additive which are capable of forming a polymer-type/inorganic-type composite SEI film are used in combination. According to 20 the non-aqueous electrolyte according to the present disclosure, the polymer-type SEI film derived from the first additive covers the entire surface of the negative electrode to form an SEI film having excellent flexibility and restorability, and the inorganic-type SEI film derived from 25 the second additive is distributed in the polymer-type SEI37 film, and accordingly, the SEI film may have improved durability. In addition, the first additive (coumarin-based compound) forms radicals upon a reduction reaction, and the radicals promote the release of fluorine contained in the 5 second additive, and accordingly, the inorganic-type SEI film may be formed more smoothly. Therefore, the non-aqueous electrolyte according to the present disclosure may form an SEI film having flexibility, excellent restorability, and improved durability and strength on the negative electrode 10 surface to prevent electrolyte consumption due to electrolyte side reactions over the running of batteries and an increase in resistance due to an increase in the thickness of an electrode film, resulting in improved performance of a lithium secondary battery, particularly high-temperature 15 cycle lifespan performance and high-temperature storage performance. In particular, when the non-aqueous electrolyte according to the present disclosure is used with a negative electrode containing a silicon-based active material, an SEI film having flexibility and improved 20 durability may be formed on a silicon-based active material having extensive volume expansion over charging and discharging, and accordingly, it is preferable in that damage to the SEI film due to the volume expansion of the siliconbased active material is prevented, and an increase in the 25 thickness of the SEI film, which is caused by the surface38 exposure of a new silicon-based active material due to the volume expansion, and electrolyte consumption are prevented.

[00131] The second additive may specifically include at least one of lithium fluoromalonato(difluoro)borate (LiFMDFB) 5 or lithium difluoro(oxalato)borate (LiDFOB), and in this case, it is preferable in terms of supporting the improvement in performance delivering lithium ions by contributing to the formation of a polymeric ether and LiF components, which are favorable in physical strength upon reduction at a 10 negative electrode, and including an ester structure in the SEI film. In an embodiment, the second additive may specifically include lithium fluoromalonato(difluoro)borate (LiFMDFB). In an embodiment, the second additive may specifically include lithium difluoro(oxalato)borate 15 (LiDFOB).

[00132] The non-aqueous electrolyte may include the second additive in an amount of 0.01 wt% to 10 wt%, specifically 0.05 wt% to 7 wt%, more specifically 0.1 wt% to 5 wt%, and more specifically 0.3 wt% to 2 wt%. When the 20 amount of the compound represented by Formula 1 satisfies the above range, it is preferable in terms of sufficiently providing durability and strength to the SEI film, and preventing an increase in resistance of a lithium secondary battery due to excessive addition, which causes degradation 25 in lifespan performance.39

[00133] The first additive and the second additive are in a weight ratio of 5:95 to 95:5, specifically 10:90 to 92:8, more specifically 16:84 to 91:9, even more specifically 30:70 to 70: 30, and even more specifically 40:60 to 60:40, and 5 when the weight ratio described above is satisfied, it is preferable in that both the flexibility and durability of the SEI film may be improved to a desired level.

[00134] The additive may further include an additional additive(or an third additive) along with the first additive 10 and the second additive. The additional additive may be included in the non-aqueous electrolyte to prevent negative electrode collapse caused by decomposition of the nonaqueous electrolyte in a high-power setting, low-temperature high-rate discharge characteristics, high-temperature 15 stability, and prevent overcharging, and suppressing battery swelling at high temperature.

[00135] Specifically, the additional additive may include at least one of vinylene carbonate, vinyl ethylene carbonate, propane sultone, propene sultone, succinonitrile, 20 adiponitrile, ethylene sulfate, lithium bis-(oxalato)borate (LiBOB), tris(trimethylsilyl) phosphate (TMSPa), or tris(trimethylsilyl) phosphite (TMSPi), and may specifically be vinylene carbonate.

[00136] The non-aqueous electrolyte may include the 25 additional additive in an amount of 0.1 wt% to 15 wt%.40

[00137] In an embodiment, the electrolyte may not contain a silyl-containing additive.

[00138] The outer shape of the lithium secondary battery of the present disclosure is not particularly limited, and 5 thus a cylindrical shape using a can, a prismatic shape, a pouch shape, or a coin shape, may be used.

[00139] Hereinafter, various embodiments of the present invention will be described in more detail through specific embodiments. However, Examples shown below are illustrated 10 only for the understanding of the present invention, and the scope of the inventive concept is not limited thereto. It will be apparent to those skilled in the art that various modifications and alterations are possible within the scope and technical range of the present invention, and such 15 modifications and alterations fall within the scope of claims included herein.

[00140] Examples and Comparative Examples

[00141] Example 1 [00142] (Preparation of non-aqueous electrolyte) 20 [00143] As an organic solvent, a mixture of fluoro ethylene carbonate (FEC) and diethyl carbonate (DEC) at a volume ratio of 10:90 was used.

[00144] LiPF6 as a lithium salt, a compound represented by Formula 4 as a first additive, LiFMDFB as a second 25 additive, and vinylene carbonate (VC) as an additional41 additive were added to the organic solvent to prepare a nonaqueous electrolyte.

[00145] The LiPF6 was included at a concentration of 1.5 M in the non-aqueous electrolyte. 5 [00146] The compound represented by Formula 4 was included in an amount of 0.5 wt% in the non-aqueous electrolyte, the LiFMDFB was included in an amount of 0.5 wt% in the non-aqueous electrolyte, and the vinylene carbonate used as the additional additive was included in an 10 amount of 0.5 wt% in the non-aqueous electrolyte. [00147] [Formula 4] [00148] (Preparation of lithium secondary battery)

[00149] A positive electrode active material 15 (LiNi0.85Co0.05Mn0.07Al0.03O2), a conductive material (carbon nanotube), and a binder (polyvinylidene fluoride) were added in a weight ratio of 97.74:0.70:1.56 to N-methyl-2- pyrrolidone (NMP) as a solvent to prepare a positive electrode mixture slurry (solid content: 75.5 wt%). The 20 positive electrode mixture slurry was applied to one surface of a positive electrode current collector (Al thin film) having a thickness of 15 μm, and then dried and roll-pressed to prepare a positive electrode.42

[00150] A negative electrode active material (Si), a conductive material (carbon black), and a binder (styrenebutadiene rubber) were added in a weight ratio of 70.0:20.3:9.7 to distilled water as a solvent to prepare a 5 negative electrode mixture slurry (solid content: 26 wt%). The negative electrode mixture slurry was applied to one surface of a negative electrode current collector (Cu thin film) having a thickness of 15 μm, and then dried and rollpressed to prepare a negative electrode. 10 [00151] A polyethylene porous film separator was interposed between the prepared positive and negative electrodes in a dry room, and then the prepared non-aqueous electrolyte was injected to prepare a secondary battery.

[00152] Example 2 15 [00153] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that the first additive was added in an amount of 0.1 wt% to the non-aqueous electrolyte.

[00154] Example 3 20 [00155] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that the first additive was added in an amount of 5.0 wt% to the non-aqueous electrolyte.

[00156] Example 4 25 [00157] A non-aqueous electrolyte and a lithium secondary43 battery were prepared in the same manner as in Example 1, except that instead of the compound represented by Formula 4, the compound represented by Formula 5 below was included in an amount of 0.5 wt% as the first additive in the non- 5 aqueous electrolyte. [00158] [Formula 5]

[00159] Example 5

[00160] A non-aqueous electrolyte and a lithium secondary 10 battery were prepared in the same manner as in Example 1, except that instead of the compound represented by Formula 4, the compound represented by Formula 6 below was included in an amount of 0.5 wt% as the first additive in the nonaqueous electrolyte. 15 [00161] [Formula 6]

[00162] Example 6

[00163] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, 20 except that instead of the compound represented by Formula44 4, the compound represented by Formula 7 below was included in an amount of 0.5 wt% as the first additive in the nonaqueous electrolyte. [00164] [Formula 7] 5

[00165] Example 7

[00166] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that instead of LiFMDFB, LiDFP was included in an 10 amount of 0.5 wt% as the second additive in the non-aqueous electrolyte.

[00167] Example 8

[00168] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, 15 except that instead of LiFMDFB, LiDFOB was included in an amount of 0.5 wt% as the second additive in the non-aqueous electrolyte.

[00169] Example 9

[00170] A non-aqueous electrolyte and a lithium secondary 20 battery were prepared in the same manner as in Example 1, except that the second additive was added in an amount of45 0.1 wt% to the non-aqueous electrolyte.

[00171] Example 10

[00172] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, 5 except that the second additive was added in an amount of 5wt% to the non-aqueous electrolyte.

[00173] Example 11

[00174] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 8, 10 except that the second additive was added in an amount of 0.1 wt% to the non-aqueous electrolyte.

[00175] Example 12

[00176] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 8, 15 except that the second additive was added in an amount of 5wt% to the non-aqueous electrolyte.

[00177] Comparative Example 1

[00178] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, 20 except that the first additive and the second additive were not added.

[00179] Comparative Example 2

[00180] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, 25 except that the second additive was not added.46

[00181] Comparative Example 3

[00182] A non-aqueous electrolyte and a lithium secondary battery were prepared in the same manner as in Example 1, except that the first additive was not added. 5 [00183] [Table 1] Non-aqueous electrolyte Lit hiu m sal t (Li PF6 ) Organic solvent Additive Mol ar con cen tra tio n (M, wit h res pec t to non - aqu eou 1st additive 2nd additive Additiona l Additive Type Amou nt (wt% , with resp ect to nonaque ous elec trol yte) Type Amou nt (wt% , with resp ect to nonaque ous elec trol yte) Type Amou nt (wt% , with resp ect to nonaque ous elec trol yte)47 s ele ctr oly te) Example 1 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 LiFMDF B 0.5 VC 0.5 Example 2 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.1 LiFMDF B 0.5 VC 0.5 Example 3 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 5.0 LiFMDF B 0.5 VC 0.5 Example 4 1.5 FEC:DEC(volu me ratio 10:90) Form ula 5 0.5 LiFMDF B 0.5 VC 0.5 Example 5 1.5 FEC:DEC (volume ratio 10:90) Form ula 6 0.5 LiFMDF B 0.5 VC 0.5 Example 6 1.5 FEC:DEC (volume ratio 10:90) Form ula 7 0.5 LiFMDF B 0.5 VC 0.5 Example 7 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 LiDFP 0.5 VC 0.5 Example 8 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 LiDFOB 0.5 VC 0.5 Example 9 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 LiFMDF B 0.1 VC 0.5 Example 1.5 FEC:DEC Form 0.5 LiFMDF 5 VC 0.548 10 (volume ratio 10:90) ula 4 B Example 11 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 LiDFOB 0.1 VC 0.5 Example 12 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 LiDFOB 5 VC 0.5 Comparati ve Example 1 1.5 FEC:DEC (volume ratio 10:90) - - - - VC 0.5 Comparati ve Example 2 1.5 FEC:DEC (volume ratio 10:90) Form ula 4 0.5 - - VC 0.5 Comparati ve Example 3 1.5 FEC:DEC (volume ratio 10:90) - - LiFMDF B 0.5 VC 0.5

[00184] Experimental Example

[00185] Experimental Example 1: Evaluation of hightemperature cycle capacity retention

[00186] The lithium secondary batteries of Examples 1 to 5 12 and Comparative Examples 1 to 3 prepared above were charged up to 4.2 V in the conditions of CC/CV and 0.33 C at 45 °C using an electrochemical charger and discharger, and 300 cycles of charging and discharging were performed with discharging up to 3 V in the conditions of CC and 0.33 C as 10 one cycle, and capacity retention was measured.

[00187] The capacity retention was calculated through the following Equation, and the results are shown in Table 2.49

[00188] Capacity retention (%) = {(discharge capacity after 300th cycle)/(discharge capacity after 1st cycle)} × 100

[00189] Experimental Example 2: Evaluation of capacity 5 retention after high-temperature storage

[00190] The lithium secondary batteries of Examples 1 to 12 and Comparative Examples 1 to 3 prepared above were charged up to 4.2 V/55 mA in the conditions of 0.33 C/4.2 V constant current/constant voltage (CC/CV) at room 10 temperature and discharged up to 2.5 V in the condition of 0.33 C to perform initial charging and discharging, and then charged up to 4.2 V/55 mA in the conditions of 0.33 C/4.2 V constant current/constant voltage (CC/CV) at room temperature, and then stored at 60 °C. After storage, the 15 secondary batteries were charged up to 4.2 V/55 mA in the conditions of 0.33 C/4.2 V constant current/constant voltage (CC/CV) at room temperature, and discharged up to 2.5 V in the condition of 0.33 C to measure the capacity upon discharging. 20 [00191] The capacity retention was evaluated according to the following formula, and the results are shown in Table 2 below.

[00192] Capacity retention (%)=(discharge capacity after storage for N weeks/initial discharge capacity)×100 25 [00193] (where N is an integer of 1 or greater).50 [00194] [Table 2] Experimental Example 1 Experimental Example 2 High-temperature cycle capacity retention (%, 300 cycles) Capacity retention when stored for 8 weeks (%) Example 1 90.8 95.4 Example 2 85.4 91.2 Example 3 83.6 88.9 Example 4 82.5 87.1 Example 5 81.8 85.9 Example 6 84.5 90.3 Example 7 83.1 88.5 Example 8 89.7 94.8 Example 9 88.5 93.1 Example 10 85.6 90.8 Example 11 87.2 92.6 Example 12 84.9 88.4 Comparative Example 1 74.4 80.4 Comparative Example 2 76.8 81.2 Comparative Example 3 79.6 83.7

[00195] Referring to Table 2, it is determined that the lithium secondary batteries of Examples 1 to 12 using the non-aqueous electrolyte including the first additive and the 5 second additive according to the present disclosure had significantly improved high-temperature cycle lifespan performance and high-temperature storage performance, compared to the lithium secondary batteries of Comparative Examples 1 to 3.51

[00196] Reference Example

[00197] Reference Example 1 [00198] 1. Preparation of non-aqueous electrolyte

[00199] The same non-aqueous electrolyte used in Example 5 1 was used. [00200] 2. Preparation of lithium secondary battery

[00201] A positive electrode active material (Li[Ni0.85Co0.03Mn0.07Al0.03]O2), a conductive material (carbon nanotube), and a binder (polyvinylidene fluoride) were added 10 in a weight ratio of 97.74:0.70:1.56 to N-methyl-2- pyrrolidone (NMP) as a solvent to prepare a positive electrode mixture slurry (solid content: 75.5 wt%). The positive electrode mixture slurry was applied to one surface of a positive electrode current collector (Al thin film) 15 having a thickness of 15 μm, and then dried and roll-pressed to prepare a positive electrode.

[00202] A negative electrode active material (natural graphite), a conductive material (carbon black), and a binder (styrene-butadiene rubber (SBR)-carboxymethyl cellulose 20 (CMC)) were added in a weight ratio of 95.0:1.5:3.5 to distilled water as a solvent to prepare a negative electrode mixture slurry (solid content: 60 wt%). The negative electrode mixture slurry was applied to one surface of a negative electrode current collector (Cu thin film) having 25 a thickness of 15 μm, and then dried and roll-pressed to52 prepare a negative electrode.

[00203] A polyethylene porous film separator was interposed between the prepared positive and negative electrodes in a dry room, and then the prepared non-aqueous 5 electrolyte was injected to prepare a secondary battery.

[00204] Reference Example 2

[00205] A secondary battery was prepared in the same manner as in Reference Example 1, except that the non-aqueous electrolyte used in Comparative Example 2 was used as a non- 10 aqueous electrolyte.

[00206] Reference Example 3

[00207] A secondary battery was prepared in the same manner as in Reference Example 1, except that the non-aqueous electrolyte used in Comparative Example 3 was used as a non- 15 aqueous electrolyte.

[00208] Reference Experimental Example 1

[00209] The lithium secondary batteries of Reference Examples 1 to 3 prepared above were charged up to 4.2 V in the conditions of CC/CV and 0.33 C at 45 °C using an 20 electrochemical charger and discharger, and 300 cycles of charging and discharging were performed with discharging up to 3 V in the conditions of CC and 0.33 C as one cycle, and capacity retention was measured.

[00210] The capacity retention was calculated through the 25 following Equation, and the results are shown in Table 3.53

[00211] Capacity retention (%) = {(discharge capacity after 300th cycle)/(discharge capacity after 1st cycle)} × 100

[00212] Reference Experimental Example 2 5 [00213] The lithium secondary batteries of Reference Examples 1 to 3 prepared above were charged up to 4.2 V/55 mA in the conditions of 0.33 C/4.2 V constant current/constant voltage (CC/CV) at room temperature and discharged up to 2.5 V in the condition of 0.33 C to perform 10 initial charging and discharging, and then charged up to 4.2 V/55 mA in the conditions of 0.33 C/4.2 V constant current/constant voltage (CC/CV) at room temperature, and then stored at 60 °C. After storage, the secondary batteries were charged up to 4.2 V/55 mA in the conditions of 0.33 15 C/4.2 V constant current/constant voltage (CC/CV) at room temperature, and discharged up to 2.5 V in the condition of 0.33 C to measure the capacity upon discharging.

[00214] The capacity retention was evaluated according to the following formula, and the results are shown in Table 3 20 below.

[00215] Capacity retention (%)=(discharge capacity after storage for N weeks/initial discharge capacity)×100 [00216] (where N is an integer of 1 or greater). [00217] [Table 3] Reference Reference54 Experimental Example 1 Experimental Example 2 High-temperature cycle capacity retention (%, 300 cycles) Capacity retention when stored for 8 weeks (%) Reference Example 1 78.7 87.5 Reference Example 2 80.4 89.2 Reference Example 3 82.1 90.9

[00218] Referring to Table 3 above, when the non-aqueous electrolyte having the characteristics according to the present disclosure is applied to a negative electrode containing a carbon-based active material (Reference Example 5 1) alone, it is determined that the performance deteriorates compared to Reference Examples 2 and 3, which are different in that only any one of the first additive and the second additive is used. The carbon-based active material has less or insignificant volume expansion compared to the silicon- 10 based active material, and accordingly, the polymer-type SEI film derived from the first additive rather acts as resistance, and it is believed that this resistance increase is further intensified when the first additive and the second additive are used together. 15 [00219] Accordingly, it is clearly understood that the effect of improving lifespan performance and storage performance of the present disclosure, in particular, the effect of improving high-temperature lifespan performance55 and high-temperature storage performance is achieved only when a negative electrode including a silicon-based active material is combined with the above-described non-aqueous electrolyte. 5

Claims (3)

1. 56 CLAIMS 1. A lithium secondary battery comprising: a negative electrode; a positive electrode positioned 5 opposite to the negative electrode; a separator disposed between the negative electrode and the positive electrode; and a non-aqueous electrolyte, wherein the negative electrode comprises a negative electrode active material, 10 the negative electrode active material comprises a silicon-based active material, the non-aqueous electrolyte comprises a lithium salt, an organic solvent, and an additive, the additive comprises a first additive and a second 15 additive, the first additive comprises a compound represented by Formula 1, and the second additive comprises at least one of lithium fluoromalonato(difluoro)borate (LiFMDFB), lithium 20 difluoro(oxalato)borate (LiDFOB), lithium difluorophosphate (LiDFP), or lithium difluorobis-(oxalate)phosphate (LiDFOP), [Formula 1]57 wherein in Formula 1, R each independently comprises halogen, a nitrile group, a propargyl group, an ester group, an ether group, a ketone group, a carboxy group, a substituted or unsubstituted alkyl group, a substituted or 5 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 10 combination of two or more thereof, and n is an integer selected from 0 to 6.
2. 2. The lithium secondary battery of claim 1, wherein the compound represented by Formula 1 comprises at least one of 15 a compound represented by Formula 2 or a compound represented by Formula 3: [Formula 2] [Formula 3] 20 wherein in Formulas 2 and 3, R is the same as defined58 in Formula 1.
3. 3. The lithium secondary battery of claim 1, wherein the compound represented by Formula 1 comprises at least one 5 selected from the group consisting of compounds represented by Formulas 4 to 12: [Formula 4] [Formula 5] 10 [Formula 6] [Formula 7]59 [Formula 8] [Formula 9] 5 [Formula 10] [Formula 11] [Formula 12] 10 .60 4. The lithium secondary battery of claim 1, wherein the non-aqueous electrolyte comprises the first additive in an amount of 0.01 wt% to 10 wt%. 5 5. The lithium secondary battery of claim 1, wherein the second additive comprises at least one of lithium fluoromalonato(difluoro)borate (LiFMDFB) or lithium difluoro(oxalato)borate (LiDFOB). 10 6. The lithium secondary battery of claim 1, wherein the non-aqueous electrolyte comprises the second additive in an amount of 0.01 wt% to 10 wt%. 7. The lithium secondary battery of claim 1, wherein the 15 first additive and the second additive are in a weight ratio of 10:90 to 90:10. 8. The lithium secondary battery of claim 1, wherein the lithium salt comprises at least one of LiCl, LiBr, LiI, LiBF4, 20 LiClO4, LiAlO4, LiAlCl4, LiPF6, LiSbF6, LiAsF6, LiB10Cl10, LiBOB (LiB(C2O4)2), LiCF3SO3, LiFSI (LiN(SO2F)2), LiCH3SO3, LiCF3CO2, LiCH3CO2, or LiBETI (LiN(SO2CF2CF3)2). 9. The lithium secondary battery of claim 1, wherein the 25 non-aqueous electrolyte comprises the lithium salt at a molar61 concentration of 0.5 M to 5.0 M. 10. The lithium secondary battery of claim 1, wherein the organic solvent comprises at least one of a cyclic carbonate- 5 based organic solvent, a linear carbonate-based organic solvent, a linear ester-based organic solvent, or a cyclic ester-based organic solvent. 11. The lithium secondary battery of claim 10, wherein the 10 organic solvent comprises a cyclic carbonate-based organic solvent and a linear carbonate-based organic solvent, the cyclic carbonate-based organic solvent comprises fluoroethylene carbonate, and the linear carbonate-based organic solvent comprises 15 diethyl carbonate. 12. The lithium secondary battery of claim 1, wherein the additive further comprises at least one third additive selected from vinylene carbonate, vinylethylene carbonate, 20 propane sultone, propene sultone, succinonitrile, adiponitrile, ethylene sulfate, lithium bis-(oxalato)borate (LiBOB), tris(trimethylsilyl)phosphate (TMSPa), or tris(trimethylsilyl)phosphite (TMSPi). 25 13. The lithium secondary battery of claim 1, wherein the62 silicon-based active material comprises a compound represented by SiOx, wherein 0≤x<2.