Nonaqueous electrolyte and lithium secondary battery comprising same

Abstract

The present invention relates to a nonaqueous electrolyte and a lithium secondary battery comprising same. The nonaqueous electrolyte comprises: a lithium salt; an organic solvent; and additives, wherein the organic solvent includes a cyclic carbonate-based organic solvent and a compound represented by chemical formula 1 below, the additives include a first additive, a second additive, and a third additive, the first additive comprising a compound in which two cyclic sulfur oxides are directly bonded or bonded via a linker, the second additive comprising a nitrogen-containing heteroaromatic compound in which at least one of a vinyl group and a propargyl group (*-C≡CH) is substituted, and the third additive comprising ethylene sulfate. [Chemical formula 1] In chemical formula 1, R1 is a fluorine atom, an alkyl group having 1 to 10 carbon atoms substituted with at least one fluorine, or an alkoxy group having 1 to 10 carbon atoms substituted with at least one fluorine, and R2 and R3 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

Description

Non-aqueous electrolyte and lithium secondary battery containing the same

[0001] The present invention relates to a non-aqueous electrolyte and a lithium secondary battery containing the same.

[0002] Recently, as the application areas of lithium-ion batteries have rapidly expanded to include not only power supply for electronic devices such as electrical, electronic, telecommunications, and computers, but also power storage for large-area devices such as automobiles and power storage systems, there is a growing demand for high-capacity, high-output, and high-stability secondary batteries.

[0003] In particular, with the growing interest in solving environmental problems and realizing a sustainable circular society, research on energy storage devices such as lithium-ion batteries and electric double-layer capacitors is being conducted extensively. Among these, lithium-ion batteries are receiving attention as battery systems that theoretically have the highest energy density within battery technology.

[0004] The aforementioned lithium secondary battery is largely composed of a positive electrode made of a transition metal oxide containing lithium, a negative electrode capable of storing lithium, an electrolyte that acts as a medium for transporting lithium ions, and a separator. Among these components, the electrolyte is known to have a significant impact on the battery's stability and safety, and as such, extensive research is being conducted on it.

[0005] In this regard, the electrolyte of a lithium secondary battery is generally a non-aqueous electrolyte containing a lithium salt, an organic solvent, etc., and the organic solvent used is a carbonate-based organic solvent. At this time, for example, LiPF6 can be used as the lithium salt, PF6 -In the case of anions, they are very susceptible to heat, so when the battery is exposed to high temperatures, there is a problem in that Lewis acids such as HF and PF5 are generated due to the thermal decomposition of lithium salts. Lewis acids such as HF and PF5 cause the decomposition of the organic solvent itself and destroy the solid electrolyte interface layer (SEI layer) formed on the surface of the negative electrode active material, which leads to increased resistance, reduced lifespan, and problems with storage performance in lithium secondary batteries.

[0006] Furthermore, to achieve high energy density in lithium secondary batteries, attempts are being made to control the transition metal content of lithium transition metal oxides used as cathode active materials, introduce silicon-based active materials as anode active materials, and increase the operating voltage. However, under these circumstances, excessive electrolyte side reactions occur during battery operation, and excessive gas is generated as a byproduct of these side reactions, which may lead to problems such as reduced lifespan, increased resistance, and decreased safety.

[0007] One objective of the present invention is to solve the above-mentioned problems by providing a non-aqueous electrolyte that minimizes gas generation that may occur during the operation of a secondary battery, thereby effectively protecting the negative electrode and enabling improved lifespan, reduced resistance, and enhanced durability of the secondary battery.

[0008] In addition, another objective of the present invention is to provide a lithium secondary battery comprising the aforementioned non-aqueous electrolyte.

[0009] [1] The present invention provides a non-aqueous electrolyte comprising a lithium salt, an organic solvent, and an additive, wherein the organic solvent comprises a cyclic carbonate-based organic solvent and a compound represented by the following chemical formula 1, the additive comprises a first additive, a second additive, and a third additive, wherein the first additive comprises a compound in which two cyclic sulfur oxides are directly bonded or bonded through a linker, the second additive comprises a nitrogen-containing heteroaromatic compound in which at least one of a vinyl group and a proparzyl group is substituted, and the third additive comprises ethylene sulfate.

[0010] [Chemical Formula 1]

[0011]

[0012] In the above chemical formula 1, R1 is a fluorine atom, a carbon-1 to carbon-10 alkyl group substituted with one or more fluorines, or a carbon-1 to carbon-10 alkoxy group substituted with one or more fluorines, and R2 and R3 are independently hydrogen, a carbon-1 to carbon-10 alkyl group, or a carbon-6 to carbon-20 aryl group.

[0013] [2] The present invention provides a non-aqueous electrolyte comprising at least one compound selected from the group consisting of compounds represented by the following chemical formulas 1-1 to 1-5, wherein the compound represented by chemical formula 1 is the compound represented by chemical formula 1.

[0014] [Chemical Formula 1-1]

[0015]

[0016] [Chemical Formula 1-2]

[0017]

[0018] [Chemical Formula 1-3]

[0019]

[0020] [Chemical Formula 1-4]

[0021]

[0022] [Chemical Formula 1-5]

[0023]

[0024] In the above chemical formulas 1-1 to 1-5, R2 and R3 are as defined in the above chemical formula 1.

[0025] [3] The present invention provides a non-aqueous electrolyte in which, in at least one of [1] and [2], the compound represented by Formula 1 comprises at least one selected from the group consisting of the compounds represented by Formula 1-A, Formula 1-B, Formula 1-C, Formula 1-D and Formula 1-E.

[0026] [Chemical Formula 1-A]

[0027]

[0028] [Chemical Formula 1-B]

[0029]

[0030] [Chemical Formula 1-C]

[0031]

[0032] [Chemical Formula 1-D]

[0033]

[0034] [Chemical Formula 1-E]

[0035]

[0036] [4] The present invention provides a non-aqueous electrolyte in which, in at least one of [1] to [3], the ratio of the volume of the compound represented by the following formula 1 to the volume of the cyclic carbonate-based organic solvent is 0.1 to 3.

[0037] [5] The present invention provides a non-aqueous electrolyte comprising 10 volume% to 50 volume% of the cyclic carbonate-based organic solvent in at least one of [1] to [4].

[0038] [6] The present invention provides a non-aqueous electrolyte comprising at least one selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and vinylene carbonate, wherein at least one of [1] to [5] above is a cyclic carbonate-based organic solvent.

[0039] [7] The present invention provides a non-aqueous electrolyte in which, in at least one of [1] to [6], the organic solvent comprises 5 volume% to 30 volume% of a compound represented by the chemical formula 1.

[0040] [8] The present invention provides a non-aqueous electrolyte in which, in at least one of [1] to [7], the organic solvent further comprises a linear carbonate-based organic solvent, and the linear carbonate-based organic solvent comprises at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate.

[0041] [9] The present invention provides a non-aqueous electrolyte comprising 20 volume% to 85 volume% of the linear carbonate-based organic solvent in the organic solvent of [8].

[0042]

[0010] The present invention provides a non-aqueous electrolyte comprising, in at least one of [1] to [9], a compound represented by the following chemical formula 2, wherein the first additive comprises a compound represented by the following chemical formula 2.

[0043] [Chemical Formula 2]

[0044] R a -L a -R L -L b -R b

[0045] In the above chemical formula 2, R a and R bis independently selected from the following formulas R-1 to R-3, and L a and L b are independently directly bonded or are alkylene groups having 1 to 5 carbon atoms, and R L It is selected from direct bonds, alkylene groups having 1 to 5 carbon atoms, and substituents represented by the following formulas L-1 to L-7.

[0046] [Chemical Formula R-1]

[0047]

[0048] [Chemical Formula R-2]

[0049]

[0050] [Chemical Formula R-3]

[0051]

[0052] [Chemical Formula L-1]

[0053]

[0054] [Chemical Formula L-2]

[0055]

[0056] [Chemical Formula L-3]

[0057]

[0058] [Chemical Formula L-4]

[0059]

[0060] [Chemical Formula L-5]

[0061]

[0062] [Chemical Formula L-6]

[0063]

[0064] [Chemical Formula L-7]

[0065]

[0066] In the above chemical formulas R-1 to R-3 and L-1 to L-7, * is a binding site, and R L1 and R L2 The groups are independently selected from hydrogen, fluorine (F), and alkyl groups having 1 to 3 carbon atoms.

[0067]

[0011] The present invention provides a non-aqueous electrolyte comprising, in

[0010] above, at least one compound represented by Chemical Formula 2 selected from the group consisting of compounds represented by Chemical Formulas 2-1 to 2-3 below.

[0068] [Chemical Formula 2-1]

[0069]

[0070] [Chemical Formula 2-2]

[0071]

[0072] [Chemical Formula 2-3]

[0073]

[0074]

[0012] The present invention provides a non-aqueous electrolyte comprising, in at least one of [1] to

[0011] , a second additive selected from the group consisting of compounds represented by the following chemical formulas 3-1 and 3-2.

[0075] [Chemical Formula 3-1]

[0076]

[0077] In the above chemical formula 3-1, Y 11 is nitrogen (N) or R Y11 is the substituted carbon (C), and Y 12 is oxygen (O), sulfur (S), R Y121 nitrogen (N) or R substituted Y122 and R Y123 is the substituted carbon (C), and Y 13 is nitrogen (N) or R Y13 is the substituted carbon (C), and Y 14is nitrogen (N) or R Y14 is the substituted carbon (C), and Y 15 is nitrogen (N) or R Y15 is the substituted carbon (C), and here, Y 11 and Y 15 At least one of them is nitrogen (N), and Y 11 , Y 12 , Y 13 , Y 14 , and Y 15 At least one of them is carbon (C), and R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a substituent represented by the following chemical formula 3-a, wherein R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 At least one of them is a substituent represented by the above chemical formula 3-a.

[0078] [Chemical Formula 3-2]

[0079]

[0080] In the above chemical formula 3-2, Y 21 is nitrogen (N) or R Y21 is the substituted carbon (C), and Y 22 is nitrogen (N) or R Y22 is the substituted carbon (C), and Y 23 is nitrogen (N) or R Y23 is the substituted carbon (C), and Y 24 is nitrogen (N) or R Y24 is the substituted carbon (C), and Y 25 is nitrogen (N) or R Y25 is the substituted carbon (C), and in this case, Y 21 , Y 22 , Y 23, Y 24 and Y 25 At least one of them is carbon (C), and R Y21 , R Y22 , R Y23 , R Y24 and R Y25 is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a substituent represented by the following chemical formula 3-a, wherein R Y21 , R Y22 , R Y23 , R Y24 and R Y25 At least one of them is a substituent represented by the above chemical formula 3-a.

[0081] [Chemical Formula 3-a]

[0082]

[0083] In the above chemical formula 3-a, L Y1 is selected from direct bonds, esters, ethers, and alkylene groups having 1 to 5 carbon atoms, and R Y1 is a directly bonded or C1 to C5 alkylene group, and R Y2 It is *-CH=CH2 or *-C≡CH, where * is the bonding site.

[0084]

[0013] The present invention provides a non-aqueous electrolyte comprising, in

[0012] above, at least one compound represented by Formula 3-1 selected from the group consisting of the following compounds represented by Formula 3-1-A, Formula 3-1-B, Formula 3-1-C, Formula 3-1-D, Formula 3-1-E and Formula 3-1-F.

[0085] [Chemical Formula 3-1-A]

[0086]

[0087] [Chemical Formula 3-1-B]

[0088]

[0089] [Chemical Formula 3-1-C]

[0090]

[0091] [Chemical Formula 3-1-D]

[0092]

[0093] [Chemical Formula 3-1-E]

[0094]

[0095] [Chemical Formula 3-1-F]

[0096]

[0097] In the above chemical formulas 3-1-A, 3-1-B, 3-1-C, 3-1-D, 3-1-E, and 3-1-F, R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 is as defined in Chemical Formula 3-1.

[0098]

[0014] The present invention provides a non-aqueous electrolyte comprising, in at least one of

[0012] and

[0013] , a compound represented by Formula 3-2 selected from the group consisting of compounds represented by Formula 3-2-A, Formula 3-2-B, Formula 3-2-C, Formula 3-2-D and Formula 3-2-E.

[0099] [Chemical Formula 3-2-A]

[0100]

[0101] [Chemical Formula 3-2-B]

[0102]

[0103] [Chemical Formula 3-2-C]

[0104]

[0105] [Chemical Formula 3-2-D]

[0106]

[0107] [Chemical Formula 3-2-E]

[0108]

[0109] In the above chemical formulas 3-2-A, 3-2-B, 3-2-C, 3-2-D, and 3-2-E, R Y21 , R Y22 , R Y23 , R Y24 and R Y25 is as defined in Chemical Formula 3-2.

[0110]

[0015] The present invention provides a non-aqueous electrolyte comprising, in at least one of

[0012] to

[0014] , at least one of the second additive selected from the group consisting of compounds represented by the following chemical formulas 3-1-A1 to 3-1-A4.

[0111] [Chemical Formula 3-1-A1]

[0112]

[0113] [Chemical Formula 3-1-A2]

[0114]

[0115] [Chemical Formula 3-1-A3]

[0116]

[0117] [Chemical Formula 3-1-A4]

[0118]

[0119]

[0016] The present invention provides a non-aqueous electrolyte satisfying the following formula 1 in at least one of [1] to

[0015] .

[0120] [Equation 1]

[0121] 0.001 ≤ (M2+M3) / M1 ≤ 2

[0122] In the above Equation 1, M1 is the weight percentage of the first additive included in the non-aqueous electrolyte, M2 is the weight percentage of the second additive included in the non-aqueous electrolyte, and M3 is the weight percentage of the third additive included in the non-aqueous electrolyte.

[0123]

[0017] The present invention provides a lithium secondary battery comprising: a cathode; an anode facing the cathode; a separator interposed between the cathode and the anode; and a non-aqueous electrolyte according to at least one of [1] to

[0016] .

[0124] The non-aqueous electrolyte of the present invention is characterized by comprising a cyclic carbonate-based organic solvent and a sulfonamide-based compound having a specific structural formula as organic solvents, and comprising a combination of a first additive, a second additive, and a third additive as additives. The first additive comprises a compound in which two cyclic sulfur oxides are directly bonded or bonded through a linker, the second additive comprises a nitrogen-containing heteroaromatic compound substituted with at least one of a vinyl group and a proparzyl group, and the third additive comprises ethylene sulfate. According to the present invention, gas generation due to the decomposition of the cyclic carbonate-based organic solvent can be minimized by the combination of these organic solvent components, destruction of the SEI film on the surface of the cathode active material can be prevented, and the oxidative stability, chemical stability, and electrochemical stability of the non-aqueous electrolyte can be improved. Meanwhile, although the sulfonamide-based compound has a low level of participation in electrode film formation, this problem can be resolved by the additives. Therefore, a lithium secondary battery to which the above-mentioned non-aqueous electrolyte is applied is desirable as it prevents an increase in resistance, improves lifespan performance, and can have excellent durability.

[0125] Terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0126] In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should be understood as not excluding in advance the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0127] Meanwhile, prior to describing the present invention, unless otherwise specifically stated in the present invention, "*" refers to a connected portion (bonding site) between identical or different atoms or terminal portions of a chemical formula.

[0128] In addition, in the description of "a to b carbon atoms" within this specification, "a" and "b" refer to the number of carbon atoms included in a specific functional group. That is, the functional group may include "a" to "b" carbon atoms. For example, "alkyl group having 1 to 5 carbon atoms" refers to an alkyl group containing 1 to 5 carbon atoms, namely CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, (CH3)2CHCH2-, CH3CH2CH2CH2CH2-, (CH3)2CHCH2CH2-, etc.

[0129] In addition, in this specification, alkyl groups or aryl groups may all be substituted or unsubstituted. Unless otherwise defined, the term "substitution" above means that at least one hydrogen bonded to a carbon is substituted with an element other than hydrogen, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl 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 cycloalkynyl group having 3 to 12 carbon atoms, a heterocycloalkyl group having 3 to 12 carbon atoms, a heterocycloalkynyl group having 2 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, and a group having 2 to It means that it is substituted with a heteroaryl group of 20 carbon atoms, a haloaryl group having 6 to 20 carbon atoms, etc.

[0130]

[0131] The present invention will be described in more detail below.

[0132]

[0133] Non-aqueous electrolytes

[0134] The present invention relates to a non-aqueous electrolyte.

[0135] Specifically, the non-aqueous electrolyte according to the present invention comprises a lithium salt, an organic solvent, and an additive, wherein the organic solvent comprises a cyclic carbonate-based organic solvent and a compound represented by the following chemical formula 1, and the additive comprises a first additive, a second additive, and a third additive, wherein the first additive comprises a compound in which two cyclic sulfates are directly bonded or bonded through a linker, the second additive comprises a nitrogen-containing heteroaromatic compound substituted with at least one of a vinyl group and a proparzyl group, and the third additive comprises ethylene sulfate.

[0136] [Chemical Formula 1]

[0137]

[0138] In the above chemical formula 1, R1 is a fluorine atom, a carbon-1 to carbon-10 alkyl group substituted with one or more fluorines, or a carbon-1 to carbon-10 alkoxy group substituted with one or more fluorines, and R2 and R3 are independently hydrogen, a carbon-1 to carbon-10 alkyl group, or a carbon-6 to carbon-20 aryl group.

[0139] The non-aqueous electrolyte of the present invention is characterized by comprising a cyclic carbonate-based organic solvent and a sulfonamide-based compound having a specific structural formula as organic solvents, and comprising a combination of a first additive, a second additive, and a third additive as additives. The first additive comprises a compound in which two cyclic sulfur oxides are directly bonded or bonded through a linker, the second additive comprises a nitrogen-containing heteroaromatic compound substituted with at least one of a vinyl group and a proparzyl group, and the third additive comprises ethylene sulfate. According to the present invention, gas generation due to the decomposition of the cyclic carbonate-based organic solvent can be minimized by the combination of these organic solvent components, destruction of the SEI film on the surface of the cathode active material can be prevented, and the oxidative stability, chemical stability, and electrochemical stability of the non-aqueous electrolyte can be improved. Meanwhile, although the sulfonamide-based compound has a low level of participation in electrode film formation, this problem can be resolved by the additives. Therefore, a lithium secondary battery to which the above-mentioned non-aqueous electrolyte is applied is desirable as it prevents an increase in resistance, improves lifespan performance, and can have excellent durability.

[0140]

[0141] (1) Lithium salt

[0142] As the lithium salt used in the present invention, various lithium salts commonly used in non-aqueous electrolytes for lithium secondary batteries may be used without limitation. For example, the lithium salt is Li as a cation. + It includes, and as anion, F - , Cl - , Br - , I - , NO3 - , N(CN)2 - , BF4 - , ClO4 - , AlO4 - , AlCl4 - , PF6 - , SbF6 - , AsF6 - , B 10 Cl 10 - , BF2C2O4 - , BC4O8 - , PF4C2O4 - , PF2C4O8 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , CF3SO3 - , C4F9SO3 - , CF3CF2SO3 - , (FSO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , CH3SO3 - , CF3(CF2)7SO3 - , CF3CO2 - , CH3CO2 - , SCN - and (CF3CF2SO2)2N - It may include at least one selected from a group consisting of

[0143] Specifically, the lithium salt is LiCl, LiBr, LiI, LiBF4, LiClO4, LiAlO4, LiAlCl4, LiPF6, LiSbF6, LiAsF6, LiB 10 Cl 10 It may include at least one selected from the group consisting of LiBOB (LiB(C2O4)2), LiCF3SO3, LiFSI (LiN(SO2F)2), LiCH3SO3, LiCF3CO2, LiCH3CO2, and LiBETI (LiN(SO2CF2CF3)2). Specifically, the lithium salt may include at least one selected from the group consisting of LiBF4, LiClO4, LiPF6, LiBOB (LiB(C2O4)2), LiCF3SO3, LiTFSI (LiN(SO2CF3)2), LiFSI (LiN(SO2F)2), and LiBETI (LiN(SO2CF2CF3)2).

[0144] The above lithium salt may be included in the above-mentioned non-aqueous electrolyte at a concentration of 0.5M to 5M, specifically 0.8M to 4M, and more specifically 0.8M to 2.0M. When the concentration of the above-mentioned lithium salt satisfies the above range, the lithium ion yield (Li + The transference number and the degree of dissociation of lithium ions are improved, which can enhance the output characteristics of the battery.

[0145]

[0146] (2) Organic solvent

[0147] The above organic solvent includes a cyclic carbonate-based organic solvent and a compound represented by the following chemical formula 1.

[0148] [Chemical Formula 1]

[0149]

[0150] In the above chemical formula 1, R1 is a fluorine atom, a carbon-1 to carbon-10 alkyl group substituted with one or more fluorines, or a carbon-1 to carbon-10 alkoxy group substituted with one or more fluorines, and R2 and R3 are independently hydrogen, a carbon-1 to carbon-10 alkyl group, or a carbon-6 to carbon-20 aryl group.

[0151] The non-aqueous electrolyte of the present invention is characterized by comprising a cyclic carbonate-based organic solvent and a sulfonamide-based compound having a specific structural formula as organic solvents. By combining these organic solvent components, gas generation due to the decomposition of the cyclic carbonate-based organic solvent can be minimized, the destruction of the SEI film on the surface of the negative electrode active material can be prevented, and the oxidation stability, chemical stability, and electrochemical stability of the non-aqueous electrolyte can be improved. Furthermore, the sulfonamide-based compound has low nucleophilicity of the solvent (low donor number), so it does not participate in the dissociation of lithium ions, thereby improving lithium ion transport characteristics and contributing to the improvement of output performance. Therefore, a lithium secondary battery to which the non-aqueous electrolyte is applied is desirable as it prevents an increase in resistance, improves lifespan performance, and possesses excellent durability. Meanwhile, the compound represented by Chemical Formula 1 has a low degree of contribution to electrode film formation, so there is a problem in that it is difficult to form a stable film; however, this problem can be resolved by using a combination of the first additive, the second additive, and the third additive described later.

[0152] The above-mentioned cyclic carbonate-based organic solvent may include at least one selected from the group consisting of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and vinylene carbonate; more specifically, it may include at least one selected from the group consisting of ethylene carbonate and fluoroethylene carbonate; and even more specifically, it may include ethylene carbonate. The above-mentioned ethylene carbonate enables prevention of decomposition according to the compound represented by Chemical Formula 1, thereby further improving the lithium mobility characteristics. Meanwhile, the above-mentioned ethylene carbonate is also desirable in that it does not impede the effect of preventing CH4 and CO2 gas generation resulting from the application of the compound represented by Chemical Formula 1.

[0153] If cyclic carbonates other than ethylene carbonate, specifically fluorine-substituted ethylene carbonates (fluoroethylene carbonates, etc.), are used, F in high voltage and high temperature environments - Defluoronation reactions in which fluoride is released are easily induced, and the acidity of the non-aqueous electrolyte increases due to acidic byproducts such as HF generated during this process. This can intensify metal leaching from the surface of the anode and promote the destruction of the coatings on the anode and cathode, thereby accelerating the degradation of the lithium secondary battery. In addition, fluorine-substituted ethylene carbonates may induce the generation of gases such as CO2, CO, and fluorinated hydrocarbons by accompanying irreversible decomposition reactions of CO or CF bonds during reduction or oxidative decomposition processes. Consequently, this can lead to pressure increase and expansion inside the cell during battery operation, thereby reducing stability. In this regard, it may be desirable for fluorine-substituted ethylene carbonates, such as fluoroethylene carbonates, not to be included in the non-aqueous electrolyte, or at least to be added in small amounts (e.g., 5% by weight or less of the non-aqueous electrolyte).

[0154] The above organic solvent may contain the cyclic carbonate-based organic solvent in an amount of 10 volume% or more, 12 volume% or more, 15 volume% or more, 18 volume% or more, 20 volume% or more, 22 volume% or more, or 24 volume% or more. The above organic solvent may contain the cyclic carbonate-based organic solvent in an amount of 50 volume% or less, 48 ​​volume% or less, 45 volume% or less, 42 volume% or less, 40 volume% or less, 38 volume% or less, 35 volume% or less, or 30 volume% or less. The above numerical ranges may be combined with one another without limitation. Specifically, the organic solvent may contain the cyclic carbonate-based organic solvent in an amount of 10 to 50 volume%, specifically 15 to 35 volume%, more specifically 20 to 30 volume%, and even more specifically 22 to 28 volume%, and when within the above range, the viscosity of the organic solvent is appropriately controlled, and the dissociation, movement, and delivery of the lithium salt can be carried out smoothly.

[0155] The compound represented by the above chemical formula 1 does not generate gases such as CO2 and CH4 due to its structural characteristics, has excellent electrochemical and chemical stability, and does not reduce the degree of dissociation of the lithium salt when used in the above-mentioned content or content ratio.

[0156] The compound represented by the above chemical formula 1 has a structure in which a fluorine or fluorine-containing functional group and N(R2)(R3) are combined via a sulfonate group (-SO2-). In particular, the sulfonate group is different from the carbonate functional group, which is the cause of gas generation, and is therefore particularly desirable for gas reduction effects.

[0157] In addition, the compound represented by Chemical Formula 1 above possesses structural stability of its own, and at the same time, has the characteristic of being less affinity for the lithium cation of the lithium salt but more affinity for the corresponding anion. This promotes the formation of a solvation structure between the lithium cation and ethylene carbonate, which can further enhance oxidation stability.

[0158] Meanwhile, the compound represented by Chemical Formula 1 has high structural stability, so decomposition reactions during initial activation or battery operation are minimized, but a very small amount may decompose during the initial activation process to form an SEI film. At this time, the SEI film derived from the compound represented by Chemical Formula 1 contains a Li2SO4-based compound, so it has excellent durability and can prevent rapid decomposition of the additive during initial activation, thereby preventing an increase in the resistance of the negative electrode film.

[0159] In the compound represented by the above chemical formula 1, R1 may be a fluorine atom (F), an alkyl group having 1 to 10 carbon atoms substituted with one or more fluorines, or an alkoxy group having 1 to 10 carbon atoms substituted with one or more fluorines; specifically, it may be a fluorine atom, an alkyl group having 1 to 5 carbon atoms substituted with one or more fluorines, or an alkoxy group having 1 to 5 carbon atoms substituted with one or more fluorines; more specifically, it may be a fluorine atom, an alkyl group having 1 to 3 carbon atoms substituted with one or more fluorines, or an alkoxy group having 1 to 3 carbon atoms substituted with one or more fluorines; more specifically, it may be a fluorine atom, CF3-*, CF3CF2-*, CF3O-*, or CF3CF2O-*; more specifically, it may be a fluorine atom, CF3-*, or CF3O-*; more specifically, it may be a fluorine atom or CF3-*; and more specifically, it may be a fluorine atom. In the above, "*" may indicate a connection site.

[0160] Additionally, R2 and R3 may independently be hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms; specifically, they may independently be an alkyl group having 1 to 10 carbon atoms; more specifically, they may independently be an alkyl group having 1 to 5 carbon atoms; even more specifically, they may independently be an alkyl group having 1 to 3 carbon atoms; even more specifically, they may independently be a methyl group or an ethyl group; and even more specifically, they may each be a methyl group.

[0161] The compound represented by the above chemical formula 1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas 1-1 to 1-5, more specifically may include at least one selected from the group consisting of compounds represented by the following chemical formulas 1-1 to 1-3, and even more specifically may include the compound represented by the following chemical formula 1-1.

[0162] [Chemical Formula 1-1]

[0163]

[0164] [Chemical Formula 1-2]

[0165]

[0166] [Chemical Formula 1-3]

[0167]

[0168] [Chemical Formula 1-4]

[0169]

[0170] [Chemical Formula 1-5]

[0171]

[0172] At this time, in the above chemical formulas 1-1 to 1-5, R2 and R3 are as defined in the above chemical formula 1.

[0173] The compound represented by the above chemical formula 1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas 1-A, 1-B, 1-C, 1-D, and 1-E, specifically, it may include at least one selected from the group consisting of compounds represented by the following chemical formulas 1-A, 1-B, and 1-C, and more specifically, it may include the compound represented by the following chemical formula 1-A.

[0174] [Chemical Formula 1-A]

[0175]

[0176] [Chemical Formula 1-B]

[0177]

[0178] [Chemical Formula 1-C]

[0179]

[0180] [Chemical Formula 1-D]

[0181]

[0182] [Chemical Formula 1-E]

[0183]

[0184] The organic solvent may contain the compound represented by Chemical Formula 1 in an amount of 5 volume% or more, 7 volume% or more, 8 volume% or more, 10 volume% or more, 12 volume% or more, or 15 volume% or more. The organic solvent may contain the compound represented by Chemical Formula 1 in an amount of 50 volume% or less, 45 volume% or less, 42 volume% or less, 40 volume% or less, 38 volume% or less, 35 volume% or less, 32 volume% or less, 30 volume% or less, 28 volume% or less, or 25 volume% or less. The above numerical ranges may be combined with one another without limitation. The above organic solvent may contain the compound represented by Chemical Formula 1 in an amount of 5 to 50 volume%, specifically 5 to 45 volume%, more specifically 5 to 30 volume%, more specifically 7 to 25 volume%, and more specifically 10 to 22 volume%. When within this range, the effect of preventing gas generation due to the decomposition of the organic solvent can be maximized without reducing the degree of dissociation of the lithium salt.

[0185] The ratio of the volume of the compound represented by the following chemical formula 1 to the volume of the above-mentioned cyclic carbonate-based organic solvent may be 0.1 to 3. When within this range, the viscosity of the organic solvent is controlled to an appropriate level, and the degree of dissociation of the lithium salt is improved, thereby improving ionic conductivity.

[0186] Specifically, the ratio of the volume of the compound represented by the following Chemical Formula 1 to the volume of the cyclic carbonate-based organic solvent may be 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, or 0.9 or more. The ratio of the volume of the compound represented by the following Chemical Formula 1 to the volume of the cyclic carbonate-based organic solvent may be 3 or less, 2.5 or less, 2 or less, 1.9 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.0 or less, or 0.8 or less. The above numerical ranges may be combined with one another without limitation. Specifically, the ratio of the volume of the compound represented by the following chemical formula 1 to the volume of the cyclic carbonate-based organic solvent may be 0.2 to 1.5, specifically 0.35 to 1.2, and more specifically 0.4 to 0.8. When within the above range, the viscosity of the organic solvent is adequately secured and the ionic conductivity of the lithium salt can be improved. Furthermore, due to the combination of these organic solvent components, gas generation resulting from the decomposition of the cyclic carbonate-based organic solvent can be minimized, the destruction of the SEI film on the surface of the negative electrode active material can be prevented, and the oxidation stability, chemical stability, and electrochemical stability of the non-aqueous electrolyte can be improved.

[0187]

[0188] The above organic solvent may further include a linear carbonate-based organic solvent.

[0189] In addition, the linear carbonate-based organic solvent is an organic solvent having low viscosity and low dielectric constant, and specifically may include at least one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), and ethylpropyl carbonate (EPC); more specifically, in terms of further improving the oxidation stability of the organic solvent, it may include at least one selected from the group consisting of ethylmethyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC), and more specifically, it may include ethylmethyl carbonate (EMC).

[0190] The above organic solvent may contain the above linear carbonate-based organic solvent in an amount of 20 volume% to 85 volume%, specifically 40 volume% to 78 volume%, more specifically 50 volume% to 70 volume%, and even more specifically 54 volume% to 66 volume%. Within this range, it is possible to implement a non-aqueous electrolyte with excellent oxidation stability while appropriately controlling the viscosity of the organic solvent. The above linear carbonate-based organic solvent may be included, for example, as the remainder after excluding the volume of the above cyclic carbonate-based organic solvent and the compound represented by Chemical Formula 1 from the above organic solvent.

[0191] When the above organic solvent further comprises the above linear carbonate-based organic solvent, the ratio of the volume of the compound represented by Formula 1 to the volume of the above linear carbonate-based organic solvent may be 0.05 or more, 0.06 or more, 0.08 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.27 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, or 1.2 or more. The ratio of the volume of the compound represented by Formula 1 to the volume of the linear carbonate-based organic solvent may be 2.5 or less, 2.0 or less, 1.8 or less, 1.7 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.0 or less, 0.8 or less, 0.6 or less, or 0.5 or less. The above numerical ranges may be combined with one another without limitation. For example, the ratio of the volume of the compound represented by Formula 1 to the volume of the linear carbonate-based organic solvent may be 0.05 to 2, preferably 0.05 to 1.5. When within this range, it is possible to implement a non-aqueous electrolyte with excellent oxidation stability while appropriately controlling the viscosity of the organic solvent.

[0192]

[0193] If the above organic solvent further comprises the above linear carbonate-based organic solvent, the ratio of the total volume of the cyclic carbonate-based organic solvent and the compound represented by Formula 1 to the volume of the above linear carbonate-based organic solvent may be 0.3 or more, 0.35 or more, 0.5 or more, 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 0.95 or more, or 1.0 or more. The ratio of the total volume of the cyclic carbonate-based organic solvent and the compound represented by Formula 1 to the volume of the above linear carbonate-based organic solvent may be 2.5 or less, 2.4 or less, 2.3 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.25 or less, or 1.2 or less. When within the above ranges, it is possible to realize a non-aqueous electrolyte having excellent oxidation stability while appropriately controlling the viscosity of the organic solvent.

[0194]

[0195] Meanwhile, the above organic solvent may be used without limitation by adding organic solvents commonly used in non-aqueous electrolytes as needed. For example, the above organic solvent may additionally include at least one organic solvent selected from linear ester-based organic solvents, cyclic ester-based organic solvents, ether-based organic solvents, glycine-based solvents, and nitrile-based organic solvents.

[0196] The above linear ester-based organic solvent may specifically include at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.

[0197] In addition, the above-mentioned cyclic ester-based organic solvent may specifically include at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone, and ε-caprolactone.

[0198] As the above ether-based solvent, any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methylpropyl ether, ethyl propyl ether, 1,3-dioxolane (DOL), and 2,2-bis(trifluoromethyl)-1,3-dioxolane (TFDOL), or a mixture of two or more of these may be used, but is not limited thereto.

[0199] The above-mentioned glyme-based solvent has a high dielectric constant and low surface tension compared to linear carbonate-based organic solvents and is a solvent with low reactivity with metals. It may include at least one selected from the group consisting of dimethoxyethane (glyme, DME), diethoxyethane, diglyme, triglyme, and tetraglyme (TEGDME), but is not limited thereto.

[0200] The above nitrile-based solvent may be one or more selected from the group consisting of acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile, but is not limited thereto.

[0201]

[0202] (3) Additives

[0203] The above-mentioned non-aqueous electrolyte contains additives.

[0204] The above additive may include a first additive, a second additive, and a third additive.

[0205] The first additive may include a compound in which two cyclic sulfur oxides are directly bonded or bonded through a linker. The second additive may include a nitrogen-containing heteroaromatic compound substituted with at least one of a vinyl group and a proparzyl group. The third additive may include ethylene sulfate.

[0206] The first additive comprises a compound in which two cyclic sulfates are directly bonded or bonded through a linker (a substituent having two bonding sites that bond the cyclic sulfates). The first additive undergoes a ring-opening reaction during activation or battery charging and discharging, thereby enabling the formation of a flexible, highly covering, and highly durable polymer-type electrode film.

[0207] Meanwhile, during the charging, discharging, and storage of lithium secondary batteries, issues such as the desorption of reactive oxygen from the cathode active material, structural collapse of the cathode active material due to the desorption of reactive oxygen, and the leaching of transition metals may arise. The reactive oxygen reacts with the organic solvent of the electrolyte to generate byproducts such as CO, CO2, and H2O. Among these, H2O decomposes the lithium salt to produce HF, and this HF promotes the leaching of transition metals and desorbs oxygen again, which can accelerate the degradation of lifespan and storage performance. In particular, this problem is exacerbated during high-voltage operation. At this time, the second additive acts as a Lewis base capable of capturing HF, which is a Lewis acid, thereby blocking the generation of reactive oxygen caused by HF. In addition, the compound represented by the above chemical formula 3 contains unsaturated hydrocarbons (substituents represented by chemical formula 3-a), such as vinyl groups or proparzyl groups (*-C≡CH), within its structure, which can facilitate the formation of a highly durable anode film.

[0208] However, while the first additive and the second additive each have independent advantages, their combination may make it difficult for the first additive to perform its function. Specifically, since the first additive and the second additive react with each other to form unwanted byproducts, this may interfere with the film-forming function of the aforementioned first additive.

[0209] In this regard, the non-aqueous electrolyte of the present invention is characterized by using a third additive in combination with a first additive and a second additive. The third additive includes ethylene sulfate, and since the reaction rate of ethylene sulfate with the second additive is significantly faster than that of the first additive, the reaction of byproduct formation caused by the reaction of the first additive and the second additive can be suppressed. Therefore, the combined use of the first additive, the second additive, and the third additive enables the performance of the respective functions of the first additive and the second additive, thereby compensating for the disadvantages associated with the application of the aforementioned sulfonamide-based compounds. Furthermore, it is possible to form an electrode film that is flexible, highly durable, and has excellent coverage capabilities, as well as to prevent the leaching of transition metals from the anode and the destruction of the SEI film on the cathode by scavenging HF, PF5, etc., thereby enabling the realization of a lithium secondary battery with excellent lifespan and output performance, and excellent safety due to minimized gas generation.

[0210]

[0211] The first additive may include a compound in which two cyclic sulfates are directly bonded or bonded through a linker.

[0212] Specifically, the first additive may include a compound represented by the following chemical formula 2.

[0213] [Chemical Formula 2]

[0214] R a -L a -R L -L b -R b

[0215] In the above chemical formula 2, R a and R b is independently selected from the following formulas R-1 to R-3, and L a and L b are independently directly bonded or are alkylene groups having 1 to 5 carbon atoms, and R L It is selected from direct bonds, alkylene groups having 1 to 5 carbon atoms, and substituents represented by the following formulas L-1 to L-7.

[0216] [Chemical Formula R-1]

[0217]

[0218] [Chemical Formula R-2]

[0219]

[0220] [Chemical Formula R-3]

[0221]

[0222] [Chemical Formula L-1]

[0223]

[0224] [Chemical Formula L-2]

[0225]

[0226] [Chemical Formula L-3]

[0227]

[0228] [Chemical Formula L-4]

[0229]

[0230] [Chemical Formula L-5]

[0231]

[0232] [Chemical Formula L-6]

[0233]

[0234] [Chemical Formula L-7]

[0235]

[0236] In the above chemical formulas R-1 to R-3 and L-1 to L-7, * is a binding site, and R L1 and R L2 The groups are independently selected from hydrogen, fluorine (F), and alkyl groups having 1 to 3 carbon atoms.

[0237] The compound represented by the above chemical formula 2 has a structure in which two cyclic sulfur oxides are bonded together, and each of these cyclic sulfur oxides is opened to form an electrode film with wide coverage.

[0238] In the above chemical formula 2, R a and R b can be independently selected from the above formulas R-1 to R-3. L a and L b The groups may be independently directly bonded or have 1 to 5 carbon atoms, and specifically, may be independently directly bonded or be methylene groups.

[0239] R L The group may be selected from a direct bond, an alkylene group having 1 to 5 carbon atoms, and a substituent represented by the formulas L-1 to L-7, and specifically, it may be a direct bond, a substituent represented by the formula L-4, or a substituent represented by the formula L-7.

[0240] In the above chemical formula L-7, R L1 and R L2 The groups can be independently selected from hydrogen, fluorine (F), and alkyl groups having 1 to 3 carbon atoms, specifically, they can be independently hydrogen or fluorine, and more specifically, they can be independently hydrogen.

[0241] Specifically, the compound represented by the above chemical formula 2 may include at least one selected from the group consisting of compounds represented by the following chemical formulas 2-1 to 2-3.

[0242] [Chemical Formula 2-1]

[0243]

[0244] [Chemical Formula 2-2]

[0245]

[0246] [Chemical Formula 2-3]

[0247]

[0248] The first additive may be included in the non-aqueous electrolyte in an amount of 0.001% to 10% by weight. Specifically, the first additive may be included in the non-aqueous electrolyte in an amount of 0.001% or more, 0.01% or more, 0.05% or more, 0.1% or more, 0.5% or more, 0.7% or more, 1% or more, or 1.2% or more. Additionally, the first additive may be included in the non-aqueous electrolyte in an amount of 10% or less by weight, 9% or less by weight, 8% or less by weight, 7% or less by weight, 6% or less by weight, 5% or less by weight, 4% or less by weight, 3% or less by weight, or 2.5% or less by weight. When the first additive is included within the above content range, the coverage ability of the film is improved, and an electrode film with excellent ion conductivity and durability is realized. This is desirable in that it improves the lifespan performance of the lithium secondary battery while preventing side reactions caused by the use of excessive additives, thereby preventing an increase in resistance.

[0249]

[0250] The second additive above comprises a nitrogen-containing heteroaromatic compound substituted with at least one of a vinyl group and a proparzyl group (*-C≡CH).

[0251] Specifically, it may include at least one selected from the group consisting of compounds represented by the following chemical formulas 3-1 and 3-2.

[0252] [Chemical Formula 3-1]

[0253]

[0254] In the above chemical formula 3-1, Y 11 is nitrogen (N) or R Y11 is the substituted carbon (C), and Y 12 is oxygen (O), sulfur (S), R Y121 nitrogen (N) or R substituted Y122 and R Y123 is the substituted carbon (C), and Y 13 is nitrogen (N) or R Y13 is the substituted carbon (C), and Y 14 is nitrogen (N) or R Y14 is the substituted carbon (C), and Y 15 is nitrogen (N) or R Y15 is the substituted carbon (C), and here, Y 11 and Y 15 At least one of them is nitrogen (N), and Y 11 , Y 12 , Y 13 , Y 14 , and Y 15 At least one of them is carbon (C), and R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a substituent represented by the following chemical formula 3-a, wherein R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 At least one of them is a substituent represented by the above chemical formula 3-a.

[0255] [Chemical Formula 3-2]

[0256]

[0257] In the above chemical formula 3-2, Y 21 is nitrogen (N) or R Y21 is the substituted carbon (C), and Y 22 is nitrogen (N) or RY22 is the substituted carbon (C), and Y 23 is nitrogen (N) or R Y23 is the substituted carbon (C), and Y 24 is nitrogen (N) or R Y24 is the substituted carbon (C), and Y 25 is nitrogen (N) or R Y25 is the substituted carbon (C), and in this case, Y 21 , Y 22 , Y 23 , Y 24 and Y 25 At least one of them is carbon (C), and R Y21 , R Y22 , R Y23 , R Y24 and R Y25 is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a substituent represented by the following chemical formula 3-a, wherein R Y21 , R Y22 , R Y23 , R Y24 and R Y25 At least one of them is a substituent represented by the above chemical formula 3-a.

[0258] [Chemical Formula 3-a]

[0259]

[0260] In the above chemical formula 3-a, L Y1 is selected from direct bonds, esters, ethers, and alkylene groups having 1 to 5 carbon atoms, and R Y1 is a directly bonded or C1 to C5 alkylene group, and R Y2 It is *-CH=CH2 or *-C≡CH, where * is the bonding site.

[0261] In the above chemical formula 3-1, R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15☐ can be independently selected from hydrogen, alkyl groups having 1 to 3 carbon atoms, and substituents represented by the following chemical formula 3-a. Specifically, in the above chemical formula 3-1, R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 can be independently selected from hydrogen, a methyl group, and a substituent represented by the following chemical formula 3-a. In this case, R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 At least one of them may be a substituent represented by the above chemical formula 3-a. Specifically, R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 One of them may be a substituent represented by the above chemical formula 3-a, and the remainder that is not a substituent represented by the above chemical formula 3-a may independently be hydrogen or an alkyl group having 1 to 3 carbon atoms, specifically hydrogen or a methyl group, more specifically hydrogen.

[0262] In the above chemical formula 3-2, R Y21 , R Y22 , R Y23 , R Y24 and R Y25 can be independently selected from hydrogen, alkyl groups having 1 to 3 carbon atoms, and substituents represented by the following chemical formula 3-a. Specifically, R Y21 , R Y22 , R Y23 , R Y24 and R Y25 can be independently selected from hydrogen, a methyl group, and a substituent represented by the following chemical formula 3-a. In this case, R Y21, R Y22 , R Y23 , R Y24 and R Y25 At least one of them may be a substituent represented by the above chemical formula 3-a. Specifically, R Y21 , R Y22 , R Y23 , R Y24 and R Y25 Any one of them may not be a substituent represented by the above formula 3-a, and the others may independently be hydrogen or an alkyl group having 1 to 3 carbon atoms, specifically hydrogen or a methyl group, more specifically hydrogen. In this case, hydrogen or an alkyl group having 1 to 3 carbon atoms does not cause steric hindrance, so it does not impede the anodic film-forming effect of the substituent represented by the above formula 3-a or the HF scavenging effect of the nitrogen-containing heteroaromatic compound of formula 3-1 and / or formula 3-2.

[0263] In the above chemical formula 3-a, L Y1 ... can be selected from direct bonds, esters, ethers, and C1 to C5 alkylene groups. Specifically, L Y1 It can be a direct bond or an ester. More specifically, L Y1 It may be an ester. The above L Y1 In the case of this ester (*-C(=O)O-*), the bonding positions of the two bonding sites (*) are not particularly restricted, but the bonding site adjacent to oxygen is R Y1 It is bonded to, and the bonding site adjacent to the carbonyl carbon is R Y1 A bonding site that is not bonded to, specifically Y 11 , Y 12 , Y 13 , Y 14 , or Y 15 ; Y 21 , Y 22 , Y 23 , Y 24 or Y 25 It can be combined with ;.

[0264] RY1 may be a direct bond or an alkylene group having 1 to 5 carbon atoms. Specifically, R Y1 It may be a direct bond or an alkylene group having 1 to 3 carbon atoms.

[0265] R Y2 It can be *-CH=CH2 or *-C≡CH, and specifically *-C≡CH.

[0266]

[0267] The compound represented by the above chemical formula 3-1 may include at least one selected from the group consisting of compounds represented by the following chemical formulas 3-1-A, 3-1-B, 3-1-C, 3-1-D, 3-1-E, and 3-1-F, and specifically may include the compound represented by the following chemical formula 3-1-A.

[0268] [Chemical Formula 3-1-A]

[0269]

[0270] [Chemical Formula 3-1-B]

[0271]

[0272] [Chemical Formula 3-1-C]

[0273]

[0274] [Chemical Formula 3-1-D]

[0275]

[0276] [Chemical Formula 3-1-E]

[0277]

[0278] [Chemical Formula 3-1-F]

[0279]

[0280] In the above chemical formulas 3-1-A, 3-1-B, 3-1-C, 3-1-D, 3-1-E, and 3-1-F, R Y11 , R Y121, R Y122 , R Y123 , R Y13 , R Y14 and R Y15 is as defined in Chemical Formula 3-1.

[0281] The compound represented by the above chemical formula 3-2 may include at least one selected from the group consisting of compounds represented by the following chemical formulas 3-2-A, 3-2-B, 3-2-C, 3-2-D, and 3-2-E.

[0282] [Chemical Formula 3-2-A]

[0283]

[0284] [Chemical Formula 3-2-B]

[0285]

[0286] [Chemical Formula 3-2-C]

[0287]

[0288] [Chemical Formula 3-2-D]

[0289]

[0290] [Chemical Formula 3-2-E]

[0291]

[0292] In the above chemical formulas 3-2-A, 3-2-B, 3-2-C, 3-2-D, and 3-2-E, R Y21 , R Y22 , R Y23 , R Y24 and R Y25 is as defined in Chemical Formula 3-2.

[0293]

[0294] Specifically, the second additive may include at least one selected from the group consisting of compounds represented by the following chemical formulas 3-1-A1 to 3-1-A4, and more specifically, may include a compound represented by the chemical formula 3-1-A1.

[0295] [Chemical Formula 3-1-A1]

[0296]

[0297] [Chemical Formula 3-1-A2]

[0298]

[0299] [Chemical Formula 3-1-A3]

[0300]

[0301] [Chemical Formula 3-1-A4]

[0302]

[0303] The second additive may be included in the non-aqueous electrolyte in an amount of 0.001% to 10% by weight. Specifically, the second additive may be included in the non-aqueous electrolyte in an amount of 0.001% or more by weight, 0.01% or more by weight, or 0.05% or more by weight. Additionally, the second additive may be included in the non-aqueous electrolyte in an amount of 10% or less by weight, 9% or less by weight, 8% or less by weight, 7% or less by weight, 6% or less by weight, 5% or less by weight, 4% or less by weight, 3% or less by weight, 2.5% or less by weight, 2% or less by weight, or 1% or less by weight.

[0304]

[0305] The third additive may be included in the non-aqueous electrolyte in an amount of 0.001% to 10% by weight. Specifically, the third additive may be included in the non-aqueous electrolyte in an amount of 0.001% or more by weight, 0.01% or more by weight, 0.05% or more by weight, 0.1% or more by weight, 0.5% or more by weight, 0.7% or more by weight, or 1% or more by weight. Additionally, the third additive may be included in the non-aqueous electrolyte in an amount of 10% or less by weight, 9% or less by weight, 8% or less by weight, 7% or less by weight, 6% or less by weight, 5% or less by weight, 4% or less by weight, 3% or less by weight, 2.5% or less by weight, 2% or less by weight, or 1.5% or less by weight.

[0306]

[0307] With respect to the content of the first additive, second additive, and third additive, the non-aqueous electrolyte may satisfy Formula 1 below.

[0308] [Equation 1]

[0309] 0.001 ≤ (M2+M3) / M1 ≤ 2

[0310] In the above Equation 1, M1 is the weight percentage of the first additive included in the non-aqueous electrolyte, M2 is the weight percentage of the second additive included in the non-aqueous electrolyte, and M3 is the weight percentage of the third additive included in the non-aqueous electrolyte.

[0311] When the above Equation 1 is satisfied, the effects of the first additive, the second additive, and the third additive are harmoniously expressed, and side reactions caused by unnecessary interactions between the additives are prevented, thereby increasing the durability of the electrode film.

[0312] Specifically, the range of (M2+M3) / M1 may be 0.04 to 1.5, specifically 0.3 to 1.2, more specifically 0.5 to 1.1, and even more specifically 0.5 to 0.6.

[0313]

[0314] The above additive may further include an auxiliary additive together with the first additive, the second additive, and the third additive.

[0315] The above auxiliary additive may be included in the non-aqueous electrolyte to prevent the decomposition of the non-aqueous electrolyte in a high-power environment from causing cathode collapse, or to provide low-temperature high-rate discharge characteristics, high-temperature stability, prevention of overcharging, and suppression of battery expansion at high temperatures.

[0316] Specifically, the above auxiliary additive may include at least one selected from the group consisting of lithium difluorophosphate (LiDFP), vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, propane sultone, propene sultone, succinonitrile, adiponitrile, LiBOB (Lithium bis-(oxalato)borate), LiBF4 (Lithium tetrafluoroborate), LiDFOB (Lithium difluoro(oxalato)borate), LiDFOP (Lithium difluoro bis(oxalato) phosphate), TMSPa (Tris(trimethylsilyl) Phosphate), and TMSPi (Tris(trimethylsilyl) Phosphite).

[0317] The above auxiliary additive may be included in the above non-aqueous electrolyte in an amount of 0.1% to 15% by weight, more specifically 0.3% to 5% by weight.

[0318]

[0319] lithium secondary battery

[0320] In addition, the present invention provides a lithium secondary battery comprising the aforementioned non-aqueous electrolyte.

[0321] Specifically, the lithium secondary battery according to the present invention comprises a negative electrode; a positive electrode facing the negative electrode; a separator interposed between the negative electrode and the positive electrode; and the aforementioned non-aqueous electrolyte.

[0322] The above lithium secondary battery can be manufactured by housing an electrode assembly comprising the above negative electrode; a positive electrode facing the above negative electrode; and a separator interposed between the above negative electrode and the positive electrode in a battery case, and then injecting the aforementioned non-aqueous electrolyte.

[0323]

[0324] As the non-aqueous electrolyte has been described above, the cathode, anode, and separator will be described below.

[0325]

[0326] (1) Cathode

[0327] The above cathode can be opposite to the above anode.

[0328] The above cathode includes a cathode active material.

[0329] The above-mentioned negative electrode active material is a material capable of reversibly inserting / extracting lithium ions, and may include at least one selected from the group consisting of carbon-based active materials, (quasi)metal-based active materials, and lithium metal, and specifically may include at least one selected from carbon-based active materials and (quasi)metal-based active materials. The above-mentioned negative electrode active material may include at least one selected from the group consisting of carbon-based active materials and silicon-based active materials.

[0330] The above carbon-based active material may include at least one selected from the group consisting of artificial graphite, natural graphite, hard carbon, soft carbon, carbon black, graphene, and fibrous carbon, and preferably may include at least one selected from the group consisting of artificial graphite and natural graphite.

[0331] Average particle size (D of the above carbon-based active material) 50 ) can be 10㎛ to 30㎛, preferably 15㎛ to 25㎛, in terms of ensuring structural stability during charging and discharging and reducing adverse reactions with the electrolyte.

[0332] Specifically, the above (quasi)metallic active material may include at least one (quasi)metal selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, V, Ti, and Sn; an alloy of lithium with at least one (quasi)metal selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, V, Ti, and Sn; an oxide of at least one (quasi)metal selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, V, Ti, and Sn; lithium titanium oxide (LTO); lithium vanadium oxide; etc.

[0333] More specifically, the above (quasi)metallic active material may include a silicon-based active material.

[0334] The above silicon-based active material is silicon (Si) and silicon oxide (SiO₂). x (0 <x<2)로 표시될 수 있음) 및 실리콘-탄소 복합체(Si / C Composite)로 이루어진 군에서 선택된 적어도 1종을 포함할 수 있다.

[0335] Average particle size (D) of the above silicon-based active material 50 ) can be 1㎛ to 30㎛, preferably 2㎛ to 15㎛, in terms of reducing adverse reactions with the electrolyte while ensuring structural stability during charging and discharging.

[0336]

[0337] The above cathode may include a cathode current collector; and a cathode active material layer disposed on at least one surface of the cathode current collector. In this case, the cathode active material may be included in the cathode active material layer.

[0338] The above-mentioned negative current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. Specifically, the above-mentioned negative current collector may be copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface treated with carbon, nickel, titanium, silver, etc., or aluminum-cadmium alloy.

[0339] The above-mentioned cathode current collector can typically have a thickness of 3 to 500 μm.

[0340] The above-mentioned negative current collector may form fine irregularities on its surface to strengthen the bonding force of the negative active material. For example, the above-mentioned negative current collector can be used in various forms such as a film, sheet, foil, net, porous body, foam, nonwoven fabric, etc.

[0341]

[0342] The above negative electrode active material layer may be disposed on at least one surface of the negative electrode current collector, specifically on one or both surfaces of the negative electrode current collector.

[0343] The above-mentioned negative electrode active material may be included in the negative electrode active material layer in an amount of 60% to 99% by weight, preferably 75% to 95% by weight.

[0344] The explanation regarding other positive active materials has been previously provided and will be omitted.

[0345] The above cathode active material layer may further include a binder and / or a conductive material together with the cathode active material.

[0346] The binder is used to improve the performance of the battery by enhancing the adhesion between the negative electrode active material layer and the negative electrode current collector, and may include, for example, at least one selected from the group consisting of polyvinylidenefluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride (PVDF), polyacrylonitrile, polymethylmethacrylate, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, and materials in which hydrogens thereof are substituted with Li, Na, or Ca, etc., and may also include various copolymers thereof. there is.

[0347] The above binder may be included in the cathode active material layer in an amount of 0.5% to 10% by weight, preferably 1% to 5% by weight.

[0348] The above conductive material is not particularly limited as long as it is conductive without causing chemical changes in the battery, and for example, graphite such as natural graphite or artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, channel black, Farnes black, lamp black, thermal black; conductive fibers such as carbon fibers or metal fibers; conductive tubes such as carbon nanotubes; fluorocarbons; metal powders such as aluminum or nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives may be used.

[0349] The above conductive material may be included in the above negative electrode active material layer in an amount of 0.5% to 10% by weight, preferably 1% to 5% by weight.

[0350] The thickness of the above negative electrode active material layer may be 10㎛ to 200㎛, preferably 20㎛ to 150㎛.

[0351] The above cathode can be manufactured by coating a cathode slurry comprising a cathode active material, a binder, a conductive material, and / or a solvent for forming a cathode slurry on at least one surface of a cathode current collector, and then drying and rolling.

[0352] The solvent for forming the cathode slurry may include, for example, at least one selected from the group consisting of distilled water, NMP (N-methyl-2-pyrrolidone), ethanol, methanol, and isopropyl alcohol, preferably distilled water, in order to facilitate the dispersion of the cathode active material, binder, and / or conductive material. The solid content of the cathode slurry may be 30% to 80% by weight, specifically 40% to 70% by weight.

[0353]

[0354] (2) bipolar

[0355] The above anode may include an anode active material.

[0356] The above-mentioned cathode active material is a compound capable of reversible intercalation and deintercalation, and is not particularly limited as long as it is a cathode active material used in the field. Specifically, the above-mentioned cathode active material is a layered compound such as lithium cobalt oxide (LiCoO2) or lithium nickel oxide (LiNiO2), or a compound substituted with one or more transition metals; lithium iron oxide such as LiFe3O4; lithium iron phosphate such as LiFePO4; and a compound with the chemical formula Li 1+c1 Mn 2-c1Lithium manganese oxides such as O4 (0≤c1≤0.33), LiMnO3, LiMn2O3, LiMnO2, etc.; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, V2O5, Cu2V2O7, etc.; chemical formula LiNi 1-c2 M c2 Ni-site type lithium nickel oxide represented by O2 (wherein M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, satisfying 0.01≤c2≤0.3); chemical formula LiMn 2-c3 M c3 Lithium manganese composite oxides represented by O2 (wherein M is at least one selected from the group consisting of Co, Ni, Fe, Cr, Zn and Ta, satisfying 0.01≤c3≤0.1) or Li2Mn3MO8 (wherein M is at least one selected from the group consisting of Fe, Co, Ni, Cu and Zn); etc., but are not limited to these. The anode may also be a Li-metal anode.

[0357] More specifically, the positive electrode active material may include at least one selected from the group consisting of lithium cobalt oxide (LiCoO2), high-nickel lithium nickel-cobalt-manganese oxide, over-lithium manganese-rich oxide, and lithium iron phosphate.

[0358] The above high-nickel containing lithium nickel-cobalt-manganese oxide can be represented by the following chemical formula A.

[0359] [Chemical Formula A]

[0360] Li 1+x (Ni a Co b Mn c M d )O2

[0361] In the above chemical formula A, M is one or more selected from W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and Mo, and 1+x, a, b, c, and d are each atomic fractions of independent elements, where 0≤x≤0.2, 0.50≤a<1, 0 <b≤0.25, 0<c≤0.25, 0≤d≤0.1, a+b+c+d=1이다. 바람직하게는, 상기 a, b, c 및 d는 각각 0.70≤a≤0.95, 0.025≤b≤0.20, 0.025≤c≤0.20, 0≤d≤0.05일 수 있다. 또한, 상기 a, b, c 및 d는 각각 0.80≤a≤0.95, 0.025≤b≤0.15, 0.025≤c≤0.15, 0≤d≤0.05일 수 있다. 또한, 상기 a, b, c 및 d는 각각 0.85≤a≤0.90, 0.05≤b≤0.10, 0.05≤c≤0.10, 0≤d≤0.03일 수 있다.

[0362] The above-mentioned lithium manganese-rich oxide may include a compound represented by the following chemical formula B.

[0363] [Chemical Formula B]

[0364] Li 1+s [Ni t Co u Mn v M 1 w ]O 2+z

[0365] In the above chemical formula B, M 1... is one or more selected from W, Cu, Fe, V, Cr, Ti, Zr, Zn, Al, In, Ta, Y, La, Sr, Ga, Sc, Gd, Sm, Ca, Ce, Nb, Mg, B, and Mo, and 0.05≤s≤1, 0≤t≤0.5, 0≤u≤0.3, 0.5≤v<1.0, 0≤w≤0.2, 0≤z≤1. Preferably, in the above formula B, 0.05≤s≤1.0, 0.1≤t≤0.5, 0≤u≤0.1, 0.5≤v<1.0, 0≤w≤0.2, 0≤z≤1. More preferably, in the above formula B, 0.10≤s≤0.50, 0.1≤t≤0.5, 0≤u≤0.1, 0.6≤v<1.0, 0≤w≤0.1, and 0≤z≤0.50.

[0366] The above lithium iron phosphate may include a compound represented by the following chemical formula C.

[0367] [Chemical Formula C]

[0368] Li 1+e Fe 1-g M 2 g (PO 4-f )X f

[0369] In the above chemical formula C, M 2 is one or more elements selected from Co, Ni, Mn, Al, Mg, Ti, and V, X is F, S, or N, and 0≤g≤0.5; -0.5≤e≤+0.5; 0≤f≤0.1. The above chemical formula C can specifically be represented as LiFePO4 (g=0, e=0, and f=0).

[0370] The above positive electrode may include a positive current collector and a positive active material layer disposed on at least one surface of the positive current collector.

[0371] The above positive current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. Specifically, the above positive current collector may include at least one selected from the group consisting of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, and aluminum-cadmium alloy, preferably aluminum.

[0372] The thickness of the above positive current collector can typically be 3 to 500 μm.

[0373] The above positive current collector may form fine irregularities on its surface to strengthen the bonding force of the positive active material. For example, the above positive current collector can be used in various forms such as a film, sheet, foil, net, porous body, foam, nonwoven fabric, etc.

[0374] The positive active material layer may be disposed on at least one surface of the positive current collector. Specifically, the positive active material layer may be disposed on one or both surfaces of the positive current collector.

[0375] The above positive active material layer may include the aforementioned positive active material.

[0376] The above positive active material may be included in the above positive active material layer in an amount of 80% to 99% by weight, specifically 85% to 98% by weight.

[0377] The above positive active material layer may optionally further include a binder and / or a conductive material together with the aforementioned positive active material.

[0378] The above binder is a component that assists in the binding of active materials and conductive materials, and in binding to current collectors, and specifically may include at least one selected from the group consisting of polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene ter polymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, and fluororubber, preferably polyvinylidene fluoride.

[0379] The above binder may be included in the positive active material layer in an amount of 1% to 20% by weight, preferably 1.2% to 10% by weight, in order to sufficiently secure binding strength between components such as the positive active material.

[0380] The above conductive material can be used to assist and enhance conductivity in a secondary battery, and is not particularly limited as long as it is conductive without causing chemical changes. Specifically, the above cathode conductive material may include at least one selected from the group consisting of graphite such as natural graphite or artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, channel black, Farnes black, lamp black, thermal black; conductive fibers such as carbon fibers or metal fibers; conductive tubes such as carbon nanotubes; fluorocarbons; metal powders such as aluminum or nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives, and preferably may include carbon nanotubes for the purpose of enhancing conductivity.

[0381] The above conductive material may be included in the above positive active material layer in an amount of 1% to 20% by weight, preferably 1.2% to 10% by weight, in order to sufficiently ensure electrical conductivity.

[0382] The thickness of the above positive active material layer may be 5㎛ to 500㎛, preferably 20㎛ to 200㎛.

[0383] The above anode can be manufactured by coating an anode slurry comprising an anode active material and optionally a binder, a conductive material, and a solvent for forming an anode slurry onto the above anode current collector, and then drying and rolling.

[0384]

[0385] (3) Separator

[0386] The above separator may be interposed between the anode and the cathode.

[0387] As the above separator, a conventional porous polymer film used as a separator, such as a polyolefin-based polymer film made of ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer, and ethylene / methacrylate copolymer, may be used alone or in a laminate thereof, or a conventional porous nonwoven fabric, such as a nonwoven fabric made of high-melting-point glass fiber, polyethylene terephthalate fiber, etc., may be used, but is not limited thereto. In addition, a coated separator containing a ceramic component or a polymer material may be used to ensure heat resistance or mechanical strength, and may optionally be used in a single-layer or multi-layer structure.

[0388]

[0389] The external shape of the lithium secondary battery of the present invention is not particularly limited, but can be a cylindrical shape using a can, a prismatic shape, a pouch shape, or a coin shape.

[0390]

[0391] The present invention will be explained in more detail below through specific embodiments. However, the following embodiments are merely examples to aid in understanding the invention and do not limit the scope of the invention. It is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of this description, and it is natural that such variations and modifications fall within the scope of the appended claims.

[0392]

[0393] Examples and Comparative Examples

[0394] Example 1

[0395] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0396] A non-aqueous electrolyte was prepared by dissolving LiPF6 to a volume of 1.2 M in an organic solvent mixed with ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a compound represented by chemical formula 1-A in a volume ratio of 20:65:15, and then adding a compound represented by chemical formula 2-3 as a first additive, a compound represented by chemical formula 3-1-A1 as a second additive, and ethylene sulfate (ESa) as a third additive.

[0397] In the non-aqueous electrolyte, the first additive was added at 2% by weight, the second additive was added at 0.1% by weight, and the third additive was added at 1% by weight.

[0398]

[0399] (Secondary battery manufacturing)

[0400] Anode active material (Li[Ni 0.6 Co 0.1 Mn 0.3An anode slurry (solid content 75.5 wt%) was prepared by adding [O2], a conductive material (carbon nanotube), and a binder (polyvinylidene fluoride) in a weight ratio of 97.74:0.70:1.56. The anode slurry was applied to an anode current collector (Al thin film, thickness: 15 μm) and dried, and then a roll press was performed to form an anode active material layer (thickness: 136.6 μm), which was used as the anode.

[0401] A cathode active material (natural graphite), a conductive material (carbon black), and a binder (SBR-CMC) were added to water, a solvent, in a weight ratio of 96.15:1.55:2.30 to prepare a cathode slurry (solid content: 26 wt%). The cathode slurry was applied to a copper (Cu) thin film (thickness: 15 μm) serving as a cathode current collector and dried, and then a roll press was performed to form a cathode active material layer (thickness: 179.8 μm), which was used as the cathode.

[0402] An electrode assembly was manufactured by interposing a porous separator polypropylene between the anode and cathode manufactured above, then housed in a battery case, and a lithium secondary battery was manufactured by injecting the electrolyte for the lithium secondary battery manufactured above.

[0403]

[0404] Example 2

[0405] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0406] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that a compound represented by Chemical Formula 2-1 was added to the non-aqueous electrolyte in an amount of 2 wt% instead of a compound represented by Chemical Formula 2-3 as the first additive.

[0407]

[0408] (Secondary battery manufacturing)

[0409] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0410]

[0411] Example 3

[0412] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0413] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that a compound represented by Chemical Formula 2-2 was added to the non-aqueous electrolyte in an amount of 2 wt% instead of a compound represented by Chemical Formula 2-3 as the first additive.

[0414]

[0415] (Secondary battery manufacturing)

[0416] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0417]

[0418] Example 4

[0419] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0420] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that a mixture of ethylene carbonate (EC), ethylmethyl carbonate (EMC), and a compound represented by Formula 1-A in a volume ratio of 20:75:5 was used as the organic solvent.

[0421]

[0422] (Secondary battery manufacturing)

[0423] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0424]

[0425] Example 5

[0426] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0427] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that a mixture of ethylene carbonate (EC), ethylmethyl carbonate (EMC), and a compound represented by Formula 1-A in a volume ratio of 20:50:30 was used as the organic solvent.

[0428]

[0429] (Secondary battery manufacturing)

[0430] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0431]

[0432] Example 6

[0433] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0434] A lithium secondary battery was manufactured in the same manner as in Example 1, except that a second additive was added at 0.25 wt% and a third additive was added at 1 wt% in the non-aqueous electrolyte.

[0435]

[0436] (Secondary battery manufacturing)

[0437] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0438]

[0439] Example 7

[0440] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0441] A lithium secondary battery was manufactured in the same manner as in Example 1, except that a second additive was added at 0.1 wt% and a third additive was added at 2 wt% in the non-aqueous electrolyte.

[0442]

[0443] (Secondary battery manufacturing)

[0444] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0445]

[0446] Comparative Example 1

[0447] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0448] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a volume ratio of 20:80 was used as the organic solvent; and the first additive, the second additive, and the third additive were not included in the non-aqueous electrolyte.

[0449]

[0450] (Secondary battery manufacturing)

[0451] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0452]

[0453] Comparative Example 2

[0454] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0455] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a volume ratio of 20:80 was used as the organic solvent.

[0456]

[0457] (Secondary battery manufacturing)

[0458] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0459]

[0460] Comparative Example 3

[0461] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0462] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that the first additive, the second additive, and the third additive were not included in the non-aqueous electrolyte.

[0463]

[0464] (Secondary battery manufacturing)

[0465] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0466]

[0467] Comparative Example 4

[0468] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0469] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that the first additive was not included in the non-aqueous electrolyte.

[0470]

[0471] (Secondary battery manufacturing)

[0472] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0473]

[0474] Comparative Example 5

[0475] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0476] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that the second additive was not included in the non-aqueous electrolyte.

[0477]

[0478] (Secondary battery manufacturing)

[0479] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0480]

[0481] Comparative Example 6

[0482] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0483] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that the third additive was not included in the non-aqueous electrolyte.

[0484]

[0485] (Secondary battery manufacturing)

[0486] A lithium secondary battery was manufactured in the same manner as in Example 1, except that the non-aqueous electrolyte for lithium secondary batteries used above was used.

[0487]

[0488] Experimental Example 1. Evaluation of High-Temperature Cycle Characteristics

[0489] The lithium secondary batteries of the examples and comparative examples prepared above were charged to 4.4V and 0.05C at 45℃ under CC / CV and 0.33C conditions using an electrochemical charge / discharger, and then discharged to 2.5V under CC and 0.33C conditions, with 200 charge / discharge cycles performed as one cycle.

[0490]

[0491] (1) Evaluation of capacity retention rate

[0492] The capacity retention rate was calculated using the formula below, and the results are shown in Table 1 below.

[0493]

[0494] Capacity Retention Rate (%) = {(Discharge Capacity after 200 Cycles) / (Discharge Capacity after 1 Cycle)} × 100

[0495]

[0496] (2) Evaluation of resistance growth rate

[0497] After one cycle of charging and discharging, the discharge capacity after one cycle was measured using an electrochemical charge / discharger, and the SOC was adjusted to 50%. Then, a pulse of 2.5C was applied for 10 seconds, and the initial resistance was calculated through the difference between the voltage before and after the pulse application.

[0498] After 200 cycles of charging and discharging, the resistance after 200 cycles was calculated using the same method as above, and the resistance increase rate was calculated. The results are shown in Table 1 below.

[0499]

[0500] Resistance increase rate (%) = {(Resistance after 200 cycles - Resistance after 1 cycle) / (Resistance after 1 cycle)} × 100 =

[0501]

[0502] (3) Evaluation of gas generation amount

[0503] After 200 cycles of charge and discharge, the amount of gas generated was measured using gas chromatography-mass spectrometry (GC-MS).

[0504]

[0505] Capacitance Retention Rate (%) Resistance Increase Rate (%) Gas Generation Amount (μL) Example 1 94.7 18.9 2150 Example 2 94.5 19.1 2270 Example 3 94.7 19.3 2200 Example 4 92.0 25.2 2425 Example 5 92.1 25.1 2460 Example 6 92.2 25.3 2500 Example 7 92.1 25.1 2480 Comparative Example 1 50.1 55.9 5580 Comparative Example 2 62.1 39.5 5600 Comparative Example 3 69.1 44.9 5800 Comparative Example 4 67.5 40.1 5450 Comparative Example 5 62.5 40.2 5430 Comparative Example 6 68.7 44.8 5650

[0506]

[0507] Referring to Table 1, it can be seen that the lithium secondary batteries of the embodiments using the non-aqueous electrolyte according to the present invention have significantly improved cycle charge / discharge performance at high temperatures compared to the comparative example.

[0508]

[0509] Experimental Example 2. Evaluation of High-Temperature Storage Characteristics

[0510] The lithium secondary batteries of the examples and comparative examples prepared above were charged to 4.4V and 0.05C at 25℃ under CC / CV and 0.33C conditions, and discharged to 2.5V at CC and 0.33C conditions to perform initial charge and discharge, and then charged to 4.4V and 0.05C at 25℃ under CC / CV and 0.33C conditions, and then stored at 60℃ for 12 weeks.

[0511]

[0512] (1) Evaluation of capacity retention rate

[0513] After storage, the above secondary batteries were charged to 4.4V and 0.05C at 25℃ under CC / CV and 0.33C conditions, and discharged to 2.5V at CC and 0.33C. The capacity retention rate was evaluated according to the following formula, and the results are shown in Table 2 below.

[0514]

[0515] Capacity Retention Rate (%) = (Discharge Capacity after 12 Weeks of Storage / Initial Discharge Capacity) × 100

[0516]

[0517] (2) Evaluation of resistance growth rate

[0518] During the initial charge / discharge, the capacity was checked at room temperature, charged to SOC 50 based on the discharge capacity, and discharged for 10 seconds with a current of 2.5C. The resistance was measured using the difference in voltage drop at that time and set as the initial resistance. After storing at 60℃ for 12 weeks, the resistance was measured in the same way and set as the final resistance. The resistance increase rate was then calculated using the following formula. The results are shown in Table 2 below.

[0519]

[0520] Resistance Increase Rate (%) = (Final Resistance - Initial Resistance) / (Initial Resistance) × 100

[0521]

[0522] (3) Evaluation of gas generation amount

[0523] After storage under the above conditions, the amount of gas generated was measured using gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 2 below.

[0524]

[0525] Capacity Retention Rate (%) Resistance Increase Rate (%) Gas Generation Amount (μL) Example 1 95.12 1.125 20 Example 2 94.82 1.425 50 Example 3 94.92 1.525 35 Example 4 91.92 6.026 05 Example 5 91.82 6.226 00 Example 6 92.72 5.825 80 Example 7 92.52 5.926 50 Comparative Example 1 51.97 0.256 05 Comparative Example 2 72.14 7.85 825 Comparative Example 3 65.55 5.15 365 Comparative Example 4 70.84 9.55 485 Comparative Example 5 69.55 0.55 850 Comparative Example 6 67.84 8.75 565

[0526]

[0527] Referring to Table 2, it can be seen that the lithium secondary batteries of the embodiments using the non-aqueous electrolyte according to the present invention have significantly improved storage performance at high temperatures compared to the comparative example.

Claims

1. Contains a lithium salt, an organic solvent, and additives, The above organic solvent comprises a cyclic carbonate-based organic solvent and a compound represented by the following chemical formula 1, and The above additive includes a first additive, a second additive, and a third additive, and The first additive comprises a compound in which two cyclic sulfates are directly bonded or bonded through a linker, and The second additive comprises a nitrogen-containing heteroaromatic compound substituted with at least one of a vinyl group and a proparzyl group (*-C≡CH), and The above third additive is a non-aqueous electrolyte containing ethylene sulfate: [Chemical Formula 1] In the above chemical formula 1, R1 is a fluorine atom, a carbon-1 to carbon-10 alkyl group substituted with one or more fluorines, or a carbon-1 to carbon-10 alkoxy group substituted with one or more fluorines, and R2 and R3 are independently hydrogen, a carbon-1 to carbon-10 alkyl group, or a carbon-6 to carbon-20 aryl group.

2. In Claim 1, A non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 1-1 to 1-5, wherein the compound represented by the above chemical formula 1: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] [Chemical Formula 1-4] [Chemical Formula 1-5] In the above chemical formulas 1-1 to 1-5, R2 and R3 are as defined in the above chemical formula 1.

3. In Claim 1, A non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 1-A, 1-B, 1-C, 1-D, and 1-E: [Chemical Formula 1-A] [Chemical Formula 1-B] [Chemical Formula 1-C] [Chemical Formula 1-D] [Chemical Formula 1-E] .

4. In Claim 1, A non-aqueous electrolyte in which the ratio of the volume of the compound represented by the following chemical formula 1 to the volume of the above-mentioned cyclic carbonate-based organic solvent is 0.1 to 3.

5. In Claim 1, The above organic solvent is a non-aqueous electrolyte comprising 10 volume% to 50 volume% of the above cyclic carbonate-based organic solvent.

6. In Claim 1, The above-mentioned cyclic carbonate-based organic solvent is a non-aqueous electrolyte comprising at least one selected from the group consisting of ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, and vinylene carbonate.

7. In Claim 1, The above organic solvent is a non-aqueous electrolyte containing 5 to 30 volume% of a compound represented by the above chemical formula 1.

8. In Claim 1, The above organic solvent further comprises a linear carbonate-based organic solvent, and The above linear carbonate-based organic solvent is a non-aqueous electrolyte comprising at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate.

9. In Claim 8, The above organic solvent is a non-aqueous electrolyte comprising 20 volume% to 85 volume% of the above linear carbonate-based organic solvent.

10. In Claim 1, The above first additive is a non-aqueous electrolyte comprising a compound represented by the following chemical formula 2: [Chemical Formula 2] R a -L a -R L -L b -R b In the above chemical formula 2, R a and R b The are independently selected from the following chemical formulas R-1 to R-3, and L a and L b are independently directly bonded or are alkylene groups having 1 to 5 carbon atoms, and R L It is selected from direct bonds, alkylene groups having 1 to 5 carbon atoms, and substituents represented by the following formulas L-1 to L-7. [Chemical Formula R-1] [Chemical Formula R-2] [Chemical Formula R-3] [Chemical Formula L-1] [Chemical Formula L-2] [Chemical Formula L-3] [Chemical Formula L-4] [Chemical Formula L-5] [Chemical Formula L-6] [Chemical Formula L-7] In the above chemical formulas R-1 to R-3 and L-1 to L-7, * is a binding site, and R L1 and R L2 The groups are independently selected from hydrogen, fluorine (F), and alkyl groups having 1 to 3 carbon atoms.

11. In Claim 10, A non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 2-1 to 2-3, wherein the compound represented by the above chemical formula 2: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] .

12. In Claim 1, The above second additive is a non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 3-1 and 3-2: [Chemical Formula 3-1] In the above chemical formula 3-1, Y 11 is nitrogen (N) or R Y11 is the substituted carbon (C), and Y 12 is oxygen (O), sulfur (S), R Y121 nitrogen (N) or R substituted Y122 and R Y123 is the substituted carbon (C), and Y 13 is nitrogen (N) or R Y13 is the substituted carbon (C), and Y 14 is nitrogen (N) or R Y14 is the substituted carbon (C), and Y 15 is nitrogen (N) or R Y15 is the substituted carbon (C), and here, Y 11 and Y 15 At least one of them is nitrogen (N), and Y 11 , Y 12 , Y 13 , Y 14 , and Y 15 At least one of them is carbon (C), and R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a substituent represented by the following chemical formula 3-a, wherein R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 At least one of them is a substituent represented by the above chemical formula 3-a, and [Chemical Formula 3-2] In the above chemical formula 3-2, Y 21 is nitrogen (N) or R Y21 is the substituted carbon (C), and Y 22 is nitrogen (N) or R Y22 is the substituted carbon (C), and Y 23 is nitrogen (N) or R Y23 is the substituted carbon (C), and Y 24 is nitrogen (N) or R Y24 is the substituted carbon (C), and Y 25 is nitrogen (N) or R Y25 is the substituted carbon (C), and in this case, Y 21 , Y 22 , Y 23 , Y 24 and Y 25 At least one of them is carbon (C), and R Y21 , R Y22 , R Y23 , R Y24 and R Y25 is independently selected from hydrogen, an alkyl group having 1 to 3 carbon atoms, and a substituent represented by the following chemical formula 3-a, wherein R Y21 , R Y22 , R Y23 , R Y24 and R Y25 At least one of them is a substituent represented by the above chemical formula 3-a, and [Chemical Formula 3-a] In the above chemical formula 3-a, L Y1 is selected from direct bonds, esters, ethers, and alkylene groups having 1 to 5 carbon atoms, and R Y1 is a directly bonded or C1 to C5 alkylene group, and R Y2 It is *-CH=CH2 or *-C≡CH, where * is the bonding site.

13. In Claim 12, A non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 3-1, 3-1-B, 3-1-C, 3-1-D, 3-1-E, and 3-1-F: [Chemical Formula 3-1-A] [Chemical Formula 3-1-B] [Chemical Formula 3-1-C] [Chemical Formula 3-1-D] [Chemical Formula 3-1-E] [Chemical Formula 3-1-F] In the above chemical formulas 3-1-A, 3-1-B, 3-1-C, 3-1-D, 3-1-E, and 3-1-F, R Y11 , R Y121 , R Y122 , R Y123 , R Y13 , R Y14 and R Y15 is as defined in Chemical Formula 3-1.

14. In Claim 12, A non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 3-2, 3-2-A, 3-2-B, 3-2-C, 3-2-D, and 3-2-E: [Chemical Formula 3-2-A] [Chemical Formula 3-2-B] [Chemical Formula 3-2-C] [Chemical Formula 3-2-D] [Chemical Formula 3-2-E] In the above chemical formulas 3-2-A, 3-2-B, 3-2-C, 3-2-D, and 3-2-E, R Y21 , R Y22 , R Y23 , R Y24 and R Y25 is as defined in Chemical Formula 3-2.

15. In Claim 12, The above second additive is a non-aqueous electrolyte comprising at least one selected from the group consisting of compounds represented by the following chemical formulas 3-1-A1 to 3-1-A4: [Chemical Formula 3-1-A1] [Chemical Formula 3-1-A2] [Chemical Formula 3-1-A3] [Chemical Formula 3-1-A4] .

16. In Claim 1, Non-aqueous electrolyte satisfying Equation 1 below: [Equation 1] 0.001 ≤ (M2+M3) / M1 ≤ 2 In the above Equation 1, M1 is the weight percentage of the first additive included in the non-aqueous electrolyte, M2 is the weight percentage of the second additive included in the non-aqueous electrolyte, and M3 is the weight percentage of the third additive included in the non-aqueous electrolyte.

17. Cathode; An anode facing the above cathode; A separator interposed between the above cathode and the above anode; and A lithium secondary battery comprising a non-aqueous electrolyte according to claim 1.

Images