Nonaqueous electrolyte and lithium secondary battery comprising same

Abstract

The present invention provides a nonaqueous electrolyte comprising a lithium salt, an organic solvent and an additive, wherein the organic solvent comprises a cyclic carbonate-based organic solvent and a sulfonamide-based compound represented by chemical formula 1, the cyclic carbonate-based organic solvent comprises ethylene carbonate, and the additive comprises a cyclic sulfate represented by chemical formula 2. Detailed descriptions of chemical formula 1 and chemical formula 2 are the same as those described in the present specification.

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] 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.

[0007] In addition, another objective of the present invention is to provide a lithium secondary battery comprising the aforementioned non-aqueous electrolyte.

[0008] [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 cyclic carbonate-based organic solvent comprises ethylene carbonate, and the additive comprises a compound represented by the following chemical formula 2.

[0009] [Chemical Formula 1]

[0010]

[0011] 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.

[0012] [Chemical Formula 2]

[0013] R a -L a -R L -L b -R b

[0014] 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.

[0015]

[0016] 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.

[0017] [2] The present invention provides 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 cyclic carbonate-based organic solvent in [1] is 0.1 to 3.

[0018] [3] 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] and [2].

[0019] [4] The present invention provides a non-aqueous electrolyte in which the cyclic carbonate-based organic solvent is ethylene carbonate, in at least one of [1] to [3].

[0020] [5] The present invention provides a non-aqueous electrolyte in which, in at least one of [1] to [4], the organic solvent comprises 5 volume% to 30 volume% of a compound represented by the chemical formula 1.

[0021] [6] The present invention provides a non-aqueous electrolyte comprising, in at least one of [1] to [5], a compound represented by Formula 1, selected from the group consisting of compounds represented by Formulas 1-1 to 1-5.

[0022] [Chemical Formula 1-1]

[0023]

[0024] [Chemical Formula 1-2]

[0025]

[0026] [Chemical Formula 1-3]

[0027]

[0028] [Chemical Formula 1-4]

[0029]

[0030] [Chemical Formula 1-5]

[0031]

[0032] In the above chemical formulas 1-1 to 1-5, R2 and R3 are as defined in the above chemical formula 1.

[0033] [7] The present invention provides a non-aqueous electrolyte comprising, in at least one of [1] to [6], a compound represented by Formula 1 selected from the group consisting of the following compounds represented by Formula 1-A, Formula 1-B, Formula 1-C, Formula 1-D and Formula 1-E.

[0034] [Chemical Formula 1-A]

[0035]

[0036] [Chemical Formula 1-B]

[0037]

[0038] [Chemical Formula 1-C]

[0039]

[0040] [Chemical Formula 1-D]

[0041]

[0042] [Chemical Formula 1-E]

[0043] .

[0044] [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.

[0045] [9] The present invention provides 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, in the linear carbonate-based organic solvent of [8].

[0046]

[0010] The present invention provides a non-aqueous electrolyte comprising 20 volume% to 85 volume% of the linear carbonate-based organic solvent in at least one of [8] and [9].

[0047]

[0011] The present invention provides a non-aqueous electrolyte in which, in at least one of [8] to

[0010] , the ratio of the volume of the compound represented by Formula 1 to the volume of the linear carbonate-based organic solvent is 0.05 to 1.5.

[0048]

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

[0011] , a compound represented by Formula 2, which is selected from the group consisting of compounds represented by Formulas 2-1 to 2-3 below.

[0049] [Chemical Formula 2-1]

[0050]

[0051] [Chemical Formula 2-2]

[0052]

[0053] [Chemical Formula 2-3]

[0054] .

[0055]

[0013] 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 at least one of [1] to

[0012] a non-aqueous electrolyte.

[0056]

[0014] The present invention provides a lithium secondary battery according to

[0013] , wherein the negative electrode comprises a negative electrode active material, and the negative electrode active material comprises at least one selected from the group consisting of a carbon-based active material and a silicon-based active material.

[0057]

[0015] The present invention relates to at least one of

[0013] and

[0014] , wherein the silicon-based active material is silicon (Si) and silicon oxide (SiO₂). x , 0 <x<2) 및 실리콘-탄소 복합체로 이루어진 군에서 선택된 적어도 1종의 실리콘계 입자를 포함하는 리튬 이차전지를 제공한다.

[0058] The non-aqueous electrolyte of the present invention is characterized by comprising a cyclic carbonate-based organic solvent (including ethylene carbonate) and a sulfonamide-based compound having a specific structural formula as an organic solvent, and comprising a cyclic sulfur oxide of a specific chemical formula as an additive. According to the present invention, the combination of these organic solvent components can minimize gas generation due to the decomposition of the cyclic carbonate-based organic solvent, prevent the destruction of the SEI film on the surface of the negative electrode active material, and improve the oxidative stability, chemical stability, and electrochemical stability of the non-aqueous electrolyte. Meanwhile, the sulfonamide-based compound has the disadvantage of moving to the anode along with anions during charging due to its high binding affinity with anions, causing the formation of an excessive anion-degradable film on the anode film and forming a low-molecular-weight sulfone-based organic film with high solubility; however, this problem can be resolved by the additive. Accordingly, 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064]

[0065] The present invention will be described in more detail below.

[0066]

[0067] Non-aqueous electrolytes

[0068] The present invention relates to a non-aqueous electrolyte.

[0069] 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, the cyclic carbonate-based organic solvent comprises ethylene carbonate, and the additive comprises a compound represented by the following chemical formula 2.

[0070] [Chemical Formula 1]

[0071]

[0072] 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.

[0073] [Chemical Formula 2]

[0074] R a -L a -R L -L b -R b

[0075] 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.

[0076]

[0077] 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.

[0078]

[0079] (1) Lithium salt

[0080] 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

[0081] 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).

[0082] The above lithium salt may be included in the above 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 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.

[0083]

[0084] (2) Organic solvent

[0085] The above organic solvent comprises a cyclic carbonate-based organic solvent and a compound represented by the following chemical formula 1. In this case, the cyclic carbonate-based organic solvent comprises ethylene carbonate.

[0086] [Chemical Formula 1]

[0087]

[0088] 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.

[0089] The non-aqueous electrolyte of the present invention is characterized by comprising a cyclic carbonate-based organic solvent (including ethylene carbonate) and a sulfonamide-based compound having a specific structural formula as an organic solvent. Through the combination of 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. 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 sulfonamide-based compound has the disadvantage of moving to the anode together with anions during charging due to its high binding affinity with anions, causing the formation of an excessive anion-degrading film on the anode film and forming a low-molecular-weight sulfonate-based organic film with high solubility; however, this disadvantage can be overcome by using a compound represented by Chemical Formula 2, which will be described later, as an additive.

[0090] The above-mentioned cyclic carbonate-based organic solvent may include ethylene carbonate. The above-mentioned ethylene carbonate is preferably used in terms of dissociation of lithium salts and improvement of mobility. In addition, the above-mentioned ethylene carbonate can prevent decomposition according to the compound represented by Chemical Formula 1, thereby further improving the mobility characteristics of lithium. Meanwhile, the above-mentioned ethylene carbonate is also preferred in that it does not impede the effect of preventing CH4, CO2 gas generation resulting from the application of the compound represented by Chemical Formula 1. More specifically, the above-mentioned cyclic carbonate-based organic solvent may consist of ethylene carbonate.

[0091] If cyclic carbonates other than ethylene carbonates, specifically fluorine-substituted ethylene carbonates (such as fluoroethylene carbonates), are used, the reduction of CO2 may be inhibited due to their higher reducing power compared to CO2. In this regard, it may be desirable that fluorine-substituted ethylene carbonates, such as fluoroethylene carbonates, are not included in the non-aqueous electrolyte, or at least be added in small amounts (e.g., 5% by weight or less of the non-aqueous electrolyte).

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] [Chemical Formula 1-1]

[0101]

[0102] [Chemical Formula 1-2]

[0103]

[0104] [Chemical Formula 1-3]

[0105]

[0106] [Chemical Formula 1-4]

[0107]

[0108] [Chemical Formula 1-5]

[0109]

[0110] 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.

[0111] 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.

[0112] [Chemical Formula 1-A]

[0113]

[0114] [Chemical Formula 1-B]

[0115]

[0116] [Chemical Formula 1-C]

[0117]

[0118] [Chemical Formula 1-D]

[0119]

[0120] [Chemical Formula 1-E]

[0121] .

[0122] 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 30 volume%, more specifically 7 to 25 volume%, and more specifically 15 to 22 volume%. When within the above 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.

[0123] 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.

[0124] Specifically, the ratio of the volume of the compound represented by 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 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 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 0.7 to 1.1. When within this 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.

[0125]

[0126] The above organic solvent may further include a linear carbonate-based organic solvent.

[0127] 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) and diethyl carbonate (DEC).

[0128] 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.

[0129] 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.

[0130]

[0131] 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.

[0132]

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139]

[0140] (3) Additives

[0141] The above-mentioned non-aqueous electrolyte further includes additives.

[0142] The above additive includes a compound represented by the following chemical formula 2.

[0143] [Chemical Formula 2]

[0144] R a -L a -R L -L b -R b

[0145] 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.

[0146]

[0147] 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.

[0148] The compound represented by Chemical Formula 2 above has a structure in which two cyclic sulfur oxides are bonded directly or through a linker, and is desirable in that it can reduce the generation of hydrocarbon gas due to initial decomposition compared to materials composed of a single cyclic sulfur oxide, such as ESa and PS. In particular, in the case of the sulfonamide compound represented by Chemical Formula 1, there is a problem in that it moves to the anode and forms a low molecular weight sulfone-based organic film due to its high bonding affinity with anions, but the compound represented by Chemical Formula 2 above can uniformly form a film with a high molecular weight on the anode and cathode, so this problem can be prevented.

[0149] 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.

[0150] 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.

[0151] 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.

[0152] 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.

[0153] [Chemical Formula 2-1]

[0154]

[0155] [Chemical Formula 2-2]

[0156]

[0157] [Chemical Formula 2-3]

[0158] .

[0159] The compound represented by Chemical Formula 2 above may be included in the non-aqueous electrolyte in an amount of 0.001% to 10% by weight. Specifically, the compound represented by Chemical Formula 2 above 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, or 0.5% or more by weight. Additionally, the compound represented by Chemical Formula 2 above 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, or 2% or less by weight. It is desirable for the compound represented by Chemical Formula 2 to be included within the above content ranges, in that it can restore the film that deteriorates due to long-term operation of the battery while minimizing the increase in initial film resistance.

[0160]

[0161] The above additive may further include an auxiliary additive together with the compound represented by Chemical Formula 2.

[0162] 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.

[0163] 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, ethylene sulfate, LiBOB (Lithium bis-(oxalato)borate), LiBF4 (Lithium tetrafluoroborate), LiDFOB (Lithium difluoro(oxalato)borate), LiDFOP (Lithium difluoro bis(oxalato) phosphate), TMSPa (Tris(trimethylsilyl) Phosphate), TMSPi (Tris(trimethylsilyl) Phosphite), and compounds represented by the following chemical formula 3.

[0164] [Chemical Formula 3]

[0165]

[0166] 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.

[0167]

[0168] lithium secondary battery

[0169] In addition, the present invention provides a lithium secondary battery comprising the aforementioned non-aqueous electrolyte.

[0170] 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.

[0171] 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.

[0172]

[0173] As the non-aqueous electrolyte has been described above, the cathode, anode, and separator will be described below.

[0174]

[0175] (1) Cathode

[0176] The above cathode can be opposite to the above anode.

[0177] The above cathode includes a cathode active material.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] 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.

[0182] More specifically, the above (quasi)metallic active material may include a silicon-based active material.

[0183] 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.

[0184] 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.

[0185]

[0186] 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.

[0187] 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.

[0188] The above-mentioned cathode current collector can typically have a thickness of 3 to 500 μm.

[0189] 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.

[0190]

[0191] 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.

[0192] 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.

[0193] The explanation regarding other positive active materials has been previously provided and will be omitted.

[0194] The above cathode active material layer may further include a binder and / or a conductive material together with the cathode active material.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] The thickness of the above negative electrode active material layer may be 10㎛ to 200㎛, preferably 20㎛ to 150㎛.

[0200] 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.

[0201] 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.

[0202]

[0203] (2) bipolar

[0204] The above anode may include an anode active material.

[0205] 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.

[0206] 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.

[0207] The above high-nickel containing lithium nickel-cobalt-manganese oxide can be represented by the following chemical formula A.

[0208] [Chemical Formula A]

[0209] Li 1+x (Ni a Co b Mn c M d )O2

[0210] 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.

[0211] The above-mentioned lithium manganese-rich oxide may include a compound represented by the following chemical formula B.

[0212] [Chemical Formula B]

[0213] Li 1+s [Ni t Co u Mn v M 1 w ]O 2+z

[0214] 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.

[0215] The above lithium iron phosphate may include a compound represented by the following chemical formula C.

[0216] [Chemical Formula C]

[0217] Li 1+e Fe 1-g M 2 g (PO 4-f )X f

[0218] 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).

[0219] 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.

[0220] 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.

[0221] The thickness of the above positive current collector can typically be 3 to 500 μm.

[0222] 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.

[0223] 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.

[0224] The above positive active material layer may include the aforementioned positive active material.

[0225] 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.

[0226] The above positive active material layer may optionally further include a binder and / or a conductive material together with the aforementioned positive active material.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] The thickness of the above positive active material layer may be 5㎛ to 500㎛, preferably 20㎛ to 200㎛.

[0232] 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.

[0233]

[0234] (3) Separator

[0235] The above separator may be interposed between the anode and the cathode.

[0236] 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.

[0237]

[0238] 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.

[0239]

[0240] 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.

[0241]

[0242] Examples and Comparative Examples

[0243] Example 1

[0244] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0245] A non-aqueous electrolyte for a lithium secondary battery was prepared by dissolving LiPF6 in an organic solvent mixed in a volume ratio of 20:40:20:20 with ethylene carbonate (EC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and a compound represented by Chemical Formula 1-A in a volume ratio of 20:40:20:20, so that the concentration was 1.2 M, and then adding 0.5 wt% of vinylene carbonate (VC) and 1.0 wt% of a compound represented by Chemical Formula 2-1 to the non-aqueous electrolyte.

[0246]

[0247] (Secondary battery manufacturing)

[0248] Anode active material (Li) in the solvent N-methyl-2-pyrrolidone (NMP) 1.2 [Ni 0.13 Co 0.13 Mn 0.54 An anode slurry (solid content 72 wt%) was prepared by adding ]O2), a conductive material (carbon nanotubes), and a binder (polyvinylidene fluoride) in a weight ratio of 97.0:0.5:2.5. The anode slurry was applied to an anode current collector (Al thin film) and dried, and then a roll press was performed to produce an anode.

[0249] A cathode slurry (solid content: 54 wt%) was prepared by adding a cathode active material (graphite:Si = 99:1 weight ratio), a binder (SBR-CMC), and a conductive material (carbon nanotubes) to water, a solvent, in a weight ratio of 96.0:0.5:3.5. The cathode slurry was coated onto a copper (Cu) thin film serving as a cathode current collector and dried, after which a roll press was performed to manufacture the cathode.

[0250] 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.

[0251]

[0252] Example 2

[0253] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0254] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that 1.0 wt% of a compound represented by Chemical Formula 2-2 was added to the non-aqueous electrolyte instead of 1.0 wt% of a compound represented by Chemical Formula 2-1.

[0255]

[0256] (Secondary battery manufacturing)

[0257] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0258]

[0259] Example 3

[0260] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0261] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that 1.0 wt% of a compound represented by Chemical Formula 2-3 was added to the non-aqueous electrolyte instead of 1.0 wt% of a compound represented by Chemical Formula 2-1.

[0262]

[0263] (Secondary battery manufacturing)

[0264] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0265]

[0266] Example 4

[0267] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0268] 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 at a content of 0.3 wt% instead of 1.0 wt%.

[0269]

[0270] (Secondary battery manufacturing)

[0271] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0272]

[0273] Example 5

[0274] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0275] 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 at a content of 3.0 wt% instead of 1.0 wt%.

[0276]

[0277] (Secondary battery manufacturing)

[0278] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0279]

[0280] Example 6

[0281] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0282] 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), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and a compound represented by Formula 1-A in a volume ratio of 20:40:30:10 was used as the organic solvent.

[0283]

[0284] (Secondary battery manufacturing)

[0285] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0286]

[0287] Example 7

[0288] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0289] 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), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and a compound represented by Formula 1-A in a volume ratio of 20:40:10:20 was used as the organic solvent.

[0290]

[0291] (Secondary battery manufacturing)

[0292] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0293]

[0294] Example 8

[0295] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0296] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2-1 was not added to the non-aqueous electrolyte, and the compound represented by Chemical Formula 2-2 was added to the non-aqueous electrolyte at a content of 1.0 wt%.

[0297] [Chemical Formula 2-2]

[0298]

[0299]

[0300] (Secondary battery manufacturing)

[0301] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0302]

[0303] Example 9

[0304] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0305] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2-1 was not added to the non-aqueous electrolyte, and the compound represented by Chemical Formula 2-3 was added to the non-aqueous electrolyte at a content of 1.0 wt%.

[0306] [Chemical Formula 2-3]

[0307] .

[0308]

[0309] (Secondary battery manufacturing)

[0310] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0311]

[0312] Comparative Example 1

[0313] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0314] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that 1,3-propanesulfone (PS) was added to the non-aqueous electrolyte at a content of 1.0 wt% instead of 1.0 wt% of the compound represented by Chemical Formula 2-1.

[0315]

[0316] (Secondary battery manufacturing)

[0317] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0318]

[0319] Comparative Example 2

[0320] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0321] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that 1,3-propanesulfone (PS) was added to the non-aqueous electrolyte at a content of 1.0 wt% instead of 1.0 wt% of the compound represented by Chemical Formula 2-1, and that a mixture of ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) in a volume ratio of 20:40:40 was used as the organic solvent.

[0322]

[0323] (Secondary battery manufacturing)

[0324] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0325]

[0326] Comparative Example 3

[0327] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0328] 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), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) in a volume ratio of 20:40:40 was used as the organic solvent.

[0329]

[0330] (Secondary battery manufacturing)

[0331] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0332]

[0333] Comparative Example 4

[0334] (Manufacture of non-aqueous electrolytes for lithium secondary batteries)

[0335] A non-aqueous electrolyte for a lithium secondary battery was prepared in the same manner as in Example 1, except that as an organic solvent, a mixture of fluoroethylene carbonate (FEC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), and a compound represented by Formula 1-A in a volume ratio of 20:40:20:20 was used.

[0336] (Secondary battery manufacturing)

[0337] A lithium secondary battery was manufactured using the same method as in Example 1, except that the non-aqueous electrolyte for a lithium secondary battery manufactured above was used.

[0338]

[0339] Experimental Example 1. Evaluation of High-Temperature Cycle Characteristics

[0340] The lithium secondary batteries of the examples and comparative examples prepared above were charged to 4.4V and 1 / 20 C at 45°C 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 300 charge / discharge cycles performed as one cycle.

[0341]

[0342] (1) Evaluation of capacity retention rate

[0343] The capacity retention rate was calculated using the formula below, and the results are shown in Table 1 below.

[0344]

[0345] Capacity Retention Rate (%) = {(Discharge Capacity after 300 Cycles / Discharge Capacity after 1 Cycle)} × 100

[0346]

[0347] (2) Evaluation of resistance growth rate

[0348] 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.

[0349] After 300 cycles of charging and discharging, the resistance after 300 cycles was calculated using the same method as above, and the resistance increase rate was calculated. The results are shown in Table 1 below.

[0350]

[0351] Resistance increase rate (%) = {(Resistance after 300 cycles - Resistance after 1 cycle) / Resistance after 1 cycle)} × 100 =

[0352]

[0353] (3) Evaluation of gas generation amount

[0354] After 300 charge-discharge cycles, the amount of gas generated was measured using gas chromatography-mass spectrometry (GC-MS).

[0355]

[0356] Capacity Retention Rate (%) Resistance Increase Rate (%) Gas Generation Amount (μL) Example 1 94.8 25.26 500 Example 2 94.2 25.8 6800 Example 3 93.3 26.1 7500 Example 4 90.3 27.7 8900 Example 5 91.1 29.38 100 Example 6 90.1 31.3 9800 Example 7 89.3 29.9 7800 Example 8 92.1 26.9 7500 Example 9 90.9 27.5 8100 Comparative Example 1 80.3 43.5 10800 Comparative Example 2 75.3 48.3 14800 Comparative Example 3 79.1 55.3 11500 Comparative Example 4 77.2 59.5 28600

[0357]

[0358] 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.

[0359]

[0360] Experimental Example 2. Evaluation of High-Temperature Storage Characteristics

[0361] The lithium secondary batteries of the examples and comparative examples prepared above were charged to 4.4V and 1 / 20C at 25℃ under CC / CV and 0.33C conditions and discharged to 2.5V at 0.33C conditions to perform initial charge and discharge, and then charged to 4.4V and 1 / 20C at 25℃ under CC / CV and 0.33C conditions, and then stored at 60℃ for 12 weeks.

[0362]

[0363] (1) Evaluation of capacity retention rate

[0364] After storage, the above secondary batteries were charged to 4.4V and 1 / 20C at 25℃ under CC / CV and 0.33C conditions, and discharged to 2.5V at 0.33C. The capacity retention rate was evaluated according to the following formula, and the results are shown in Table 2 below.

[0365]

[0366] Capacity Retention Rate (%) = (Discharge Capacity after 12 Weeks of Storage / Initial Discharge Capacity) × 100

[0367]

[0368] (2) Evaluation of resistance growth rate

[0369] During the initial charge / discharge, the capacity was checked at room temperature, then charged to SOC 50 based on the discharge capacity, and discharged for 10 seconds with a current of 3C. The resistance was measured using the difference in voltage drop during this process and set as the initial resistance. After storing at 60℃ for 12 weeks, the resistance was measured in the same manner 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.

[0370]

[0371] Resistance Increase Rate (%) = (Final Resistance - Initial Resistance) / (Initial Resistance) × 100

[0372]

[0373] (3) Evaluation of gas generation amount

[0374] 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.

[0375]

[0376] Capacity Retention Rate (%) Resistance Increase Rate (%) Gas Generation Amount (μL) Example 1 93.5 33.5 7600 Example 2 93.0 35.8 7800 Example 3 92.4 36.18 100 Example 4 91.9 38.5 9200 Example 5 92.0 37.9 9000 Example 6 90.0 39.9 9300 Example 7 91.4 41.28 900 Example 8 92.1 35.18 300 Example 9 93.1 34.1 7900 Comparative Example 1 77.6 58.9 14800 Comparative Example 2 75.8 60.1 18600 Comparative Example 3 72.3 57.8 15500 Comparative Example 4 70.3 60.6 34000

[0377]

[0378] 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-mentioned cyclic carbonate-based organic solvent includes ethylene carbonate, and The above additive is a non-aqueous electrolyte comprising a compound represented by the following chemical formula 2: [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. [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. 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.

2. 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.

3. 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.

4. In Claim 1, The above-mentioned cyclic carbonate-based organic solvent is a non-aqueous electrolyte composed of ethylene carbonate.

5. 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.

6. 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.

7. 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] .

8. In Claim 1, The above organic solvent is a non-aqueous electrolyte further comprising a linear carbonate-based organic solvent.

9. In Claim 8, 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.

10. 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.

11. In Claim 8, A non-aqueous electrolyte in which the ratio of the volume of the compound represented by Chemical Formula 1 to the volume of the linear carbonate-based organic solvent is 0.05 to 1.

5.

12. In Claim 1, 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] .

13. 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.

14. In Claim 13, The above cathode includes a cathode active material, and A lithium secondary battery comprising at least one type selected from the group consisting of carbon-based active materials and silicon-based active materials, wherein the above-mentioned negative electrode active material.

15. In Claim 14, The above silicon-based active material is silicon (Si) and silicon oxide (SiO₂). x , 0 <x<2) 및 실리콘-탄소 복합체로 이루어진 군에서 선택된 적어도 1종의 실리콘계 입자를 포함하는 리튬 이차전지.

Images