Lithium secondary battery

Abstract

The present invention relates to a lithium secondary battery with improved high-temperature cycle characteristics and, more specifically, to a lithium secondary battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the positive electrode comprises lithium iron phosphate as a positive electrode active material, the loading amount of the positive electrode is 32 mg / cm2 to 60 mg / cm2, and the electrolyte comprises a lithium salt, a first organic solvent, a second organic solvent, a first additive and a second additive, wherein the first organic solvent is a cyclic lactone compound, the second organic solvent is a carbonate organic solvent, the first additive is lithium nitrate (LiNO3) and the second additive is an imidazole compound.

Description

Lithium secondary battery Cross-citation with related application(s) This application claims the benefit of priority to Korean Patent Application No. 10-2023-0167270, filed November 27, 2023, and Korean Patent Application No. 10-2024-0165718, filed November 19, 2024, the entire contents of which are incorporated herein by reference. Technical field The present invention relates to a lithium secondary battery, and more particularly, to a lithium secondary battery with improved high-temperature cycle characteristics. Recently, lithium secondary batteries are being used in various fields including mobile electronic devices such as mobile phones, PDAs, and laptop computers. In particular, as interest in environmental issues grows, research on lithium secondary batteries with high energy density and discharge voltage as a power source for electric vehicles that can replace vehicles that use fossil fuels such as gasoline and diesel vehicles, which are one of the main causes of air pollution, is being actively conducted, and some are in the commercialization stage. Meanwhile, in order to use the lithium secondary battery as a power source for an electric vehicle, it must be able to stably maintain high output at high temperatures and high voltages. To this end, the lithium secondary battery is considering using carbon materials, lithium metal, sulfur compounds, silicon compounds, tin compounds, etc. as the main components of the negative active material, and lithium-containing cobalt oxide (LiCoO) as the main positive active material. 2 ) or lithium nickel oxide is used. However, in the case of the lithium-containing cobalt oxide, the energy density and output characteristics are reaching their practical limits, and especially when used in high-energy density applications, due to its structural instability, it causes structural transformation at a high temperature charging state, oxygen release within the structure, and an exothermic reaction with the electrolyte within the battery, which causes a secondary battery explosion. In the case of the lithium nickel-based oxide, since the output rapidly decreases in a low SOC range (for example, SOC 30% or less), there is a disadvantage in that the usable SOC range is greatly limited, and thus there are limitations in applying it to fields such as electric vehicles where output characteristics are particularly important. In particular, the lithium nickel-based oxide has low structural stability, and when exposed to high temperatures or high voltage, there is a problem that the transition metal in the positive electrode active material is eluted or a side reaction with the electrolyte is induced, which rapidly deteriorates the battery performance. Recently, to solve these problems, a method of using lithium iron phosphate with an olivine structure that has excellent high-temperature safety instead of lithium nickel oxide is being studied. However, since the lithium iron phosphate having the above olivine structure has a lower theoretical capacity than the lithium nickel-based oxide used previously, it has a disadvantage in that the energy density is relatively lower than that of the lithium nickel-based oxide when designing an electrode under the same conditions. To solve these problems, high-loading electrodes that increase the amount of electrode active material applied per area (loading amount) when applying lithium iron phosphate have recently been attempted. However, since these high-loading electrodes have a high degree of active material coating and are designed to increase the density of the electrode, the degree of electrode compression is very large, and accordingly, the porous structure inside the electrode is insufficient, which has the disadvantage of reducing electrolyte impregnation. If the electrolyte impregnation is reduced in this way, the "charge transfer", which is the reaction between lithium ions and electrons, is reduced, which can lead to an increase in battery resistance. Accordingly, there is a demand for the development of a new secondary battery configuration that can improve electrolyte impregnation properties and enhance charge mobility when manufacturing secondary batteries using high-loading electrodes. The present invention is intended to solve the above problems, and to provide a lithium secondary battery which, when applying a high-loading cathode, forms a stable film on the electrode surface by using an electrolyte with improved impregnation properties by a specific composition, thereby increasing the charge transfer phenomenon, thereby suppressing an increase in resistance during high-temperature storage, and ensuring excellent cycle capacity retention. [1] The present invention relates to a lithium secondary battery comprising a cathode, an anode, a separator and an electrolyte, wherein the cathode comprises lithium iron phosphate as a cathode active material, and the loading amount of the cathode is 32 mg / cm 2 60 mg / cm 2 , wherein the electrolyte comprises a lithium salt; a first organic solvent; a second organic solvent; a first additive; and a second additive, wherein the first organic solvent is a cyclic lactone compound, the second organic solvent is a carbonate-based organic solvent, and the first additive is lithium nitrate (LiNO 3 ), and the second additive is an imidazole-based compound. A lithium secondary battery is provided. [2] The present invention provides a lithium secondary battery, wherein, in the above [1], the lithium iron phosphate comprises a compound represented by the following chemical formula 1. [Chemical Formula 1] Li 1+a Fe x M y (PO 4-b )X' b In the above [chemical formula 1], M is one selected from the group consisting of Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn and Y, X' is one or more elements selected from the group consisting of F, S and N, -0.5≤a≤0.5, 0 <x≤1, 0≤y≤1 및 0≤b≤0.3이다. [3] In the present invention, in the above [1] or [2], the lithium iron phosphate is lithium iron phosphate (LiFePO 4 ) or lithium manganese iron phosphate (LiFeMnPO 4 ) provides a lithium secondary battery. [4] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [3], the positive electrode active material further includes lithium nickel cobalt manganese oxide represented by the following chemical formula 2: [Chemical formula 2] Li 1+a1 Ni x1 Co y1 M 1 z M 2 w O 2 In the above [chemical formula 2], M 1 is Mn, Al or a combination of these, and M 2 is one selected from the group consisting of Al, Zr, W, Ti, Mg, Ca and Sr, and 0≤a1≤0.5, 0.55 <x1<1.0, 0<y1≤0.4, 0<z≤0.4, 0≤w≤0.1 이다. [5] The present invention, in at least one of the above [1] to [4], the lithium nickel cobalt manganese oxide is Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , Li(Ni) 0.7 Mn 0.2 Co 0.1 )O 2 , Li(Ni0.8 Mn 0.1 Co 0.1 )O 2 , Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 , Li(Ni 0.86 Mn 0.07 Co 0.05 Al 0.02 )O 2 and Li(Ni 0.90 Mn 0.05 Co 0.05 )O 2 A lithium secondary battery is provided, wherein the lithium secondary battery is one selected from the group consisting of: [6] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [5], the lithium iron phosphate and lithium nickel cobalt manganese oxide are included in a weight ratio of 30:70 to 80:20. [7] The present invention, in at least one of the above [1] to [6], the loading amount of the anode is 40 mg / cm 2 60 mg / cm 2 It provides a lithium secondary battery. [8] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [7], the cyclic lactone compound includes gamma-butyrolactone. [9] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [6], the carbonate-based organic solvent is a cyclic carbonate-based organic solvent.

[0010] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [9], the first organic solvent and the second organic solvent are included in a volume ratio of 50:50 to 99:1.

[0011] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to

[0010] , the first organic solvent and the second organic solvent are included in a volume ratio of 80:20 to 99:1.

[0012] The present invention provides a lithium secondary battery, wherein, in at least one of the above [1] to

[0011] , the first additive is included in an amount of 0.05 wt% to 3.0 wt% based on the total weight of the electrolyte.

[0013] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [2], the imidazole compound is a compound represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, R is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, R 1 Inland R 3 are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms, or -CN.

[0014] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to [3], the imidazole compound is a compound represented by the following chemical formula 3A. [Chemical Formula 3A] .

[0015] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to

[0013] , the first additive and the second additive are included in a weight ratio of 1:0.05 to 1:2.

[0016] The present invention provides a lithium secondary battery, wherein in at least one of the above [1] to

[0015] , the negative electrode includes a carbon-based active material, a silicon-based active material, or a mixture of a carbon-based active material and a silicon-based active material. A lithium secondary battery according to the present invention comprises an organic solvent containing a cyclic lactone compound as a main solvent and lithium nitrate (LiNO) as two additives. 3) and an electrolyte including an imidazole compound, the electrolyte impregnation property for the positive electrode of the high loading can be improved, and a film having low resistance can be formed on the surface of the positive electrode of the high loading, thereby improving the charge mobility on the surface of the positive electrode of the high loading. Therefore, the lithium secondary battery of the present invention can have improved cycle characteristics and high-temperature storage characteristics. The terms and words used in this specification and claims are only used to describe exemplary embodiments, and should not be construed as limited to their usual or dictionary meanings, and should be interpreted as having meanings and concepts that are consistent with the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term in order to describe his own invention in the best manner. For example, in this specification, the terms “comprise,” “include,” or “have” should be understood to specify the presence of a feature, number, step, component, or combination thereof, but not to exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof. In addition, in the description of "carbon atoms a to b" in the present specification, "a" and "b" mean 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, "alkylene group having 1 to 5 carbon atoms" means an alkylene group including 1 to 5 carbon atoms, i.e., -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 (CH 2 )CH-, -CH 2 CH 2 CH 2 CH 2 CH 2- and -CH(CH 2 )CH 2 CH 2 - means back. In addition, in the present specification, the term "alkylene group" means a branched or unbranched aliphatic hydrocarbon group or a functional group in which one hydrogen atom is missing from carbon atoms located at both ends of the aliphatic hydrocarbon group. In one embodiment, the alkylene group can be substituted or unsubstituted. The alkylene group includes, but is not limited to, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a tert-butylene group, a pentylene group, a 3-pentylene group, and the like, and each of these can be optionally substituted in other embodiments. Additionally, in this specification, unless otherwise defined, “substitution” means that at least one hydrogen bonded to carbon is replaced with another element such as fluorine. In addition, in this specification, the "loading amount" means the amount of active material per unit area obtained by measuring the positive electrode active material layer including lithium iron phosphate of an olivine structure formed on a current collector, and is expressed as "mg / cm 2 " is expressed as. At this time, in this specification, "loading amount" means the total sum of the loading amounts on both sides of the anode. Hereinafter, the present invention will be described in detail. A lithium secondary battery according to the present invention comprises at least one of the configurations disclosed below, and may comprise any combination between technically possible configurations among the configurations below. Lithium secondary battery The present invention relates to a lithium secondary battery. Specifically, the present invention provides a lithium secondary battery including a positive electrode, a negative electrode, a separator, and an electrolyte. The above positive electrode may include lithium iron phosphate as a positive electrode active material. The loading amount of the above anode is 32 mg / cm 2 60 mg / cm2 It could be. The above electrolyte may include a lithium salt; a first organic solvent; a second organic solvent; a first additive; and a second additive. The first organic solvent may include a cyclic lactone compound. The second organic solvent may include a carbonate-based organic solvent. The above first additive is lithium nitrate (LiNO 3 ) may be included. The second additive may include an imidazole compound. (1) Bipolar The positive electrode of the present invention may include lithium iron phosphate as a positive electrode active material. Specifically, the lithium iron phosphate may include a compound represented by the following chemical formula 1. [Chemical Formula 1] Li 1+a Fe x M y (PO 4-b )X' b In the above [chemical formula 1], M is one selected from the group consisting of Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn and Y, X' is one or more elements selected from the group consisting of F, S, and N, -0.5≤a≤0.5, 0 <x≤1, 0≤y≤1 및 0≤b≤0.3이다. Lithium iron phosphate represented by the chemical formula 1 above is a representative example of lithium iron phosphate (LiFePO). 4 , LFP) or lithium manganese iron phosphate (LiFeMnPO) 4 , LFMP) may be included. The lithium iron phosphate represented by the above chemical formula 1 can use primary particles of nanometer size for high input / output of lithium ions, and it is also possible to use these primary particles by assembling them into secondary particles, which are aggregates thereof. For example, when using primary particles as the lithium iron phosphate, the particle size may be 50 to 2000 nm, more specifically, 200 to 1100 nm. In addition, when using these primary particles by assembling them into secondary particles, which are aggregates thereof, the average particle diameter (D50) of the secondary particles may be 0.5 ㎛ to 30 ㎛. The lithium iron phosphate represented by the above chemical formula 1 may have an amorphous layer of carbon or metal oxide coated on its surface. In this case, since the amorphous layer of carbon or metal oxide coated on the surface is not crystalline, lithium ions are inserted and deintercalated into the lithium iron phosphate of the core portion through the amorphous layer of the shell. The amorphous layer of carbon or metal oxide coated on the surface allows lithium ions to pass through and also has excellent electron conductivity, so it can act as a current path to the lithium iron phosphate core, which is an active material, and thus can enable charging and discharging at a high rate. In addition, when the surface of the lithium iron phosphate is coated with an amorphous layer of carbon or metal oxide, safety can be further increased in that unnecessary reactions between the core material and the electrolyte can be controlled. In addition, lithium iron phosphate represented by the chemical formula 1 is PO 4 Since phosphorus and oxygen form strong covalent bonds within the tetrahedral structure, structural stability and thermal stability can be secured even in volume changes due to charge and discharge. However, lithium iron phosphate represented by the chemical formula 1 has a disadvantage in that its electrical conductivity is relatively low compared to nickel-based lithium transition metal oxides because the oxygen structure is tightly packed, making it difficult for lithium ions to move and electrons to flow smoothly. Accordingly, in the present invention, the positive electrode may additionally include lithium nickel cobalt manganese oxide represented by the following chemical formula 2, which has high electrical conductivity, together with the lithium iron phosphate, in order to increase electrical conductivity. [Chemical formula 2] Li 1+a1 Ni x1 Co y1 M 1 z M 2 w O 2 In the above [chemical formula 2], M 1 is Mn, Al or a combination of these, and M 2 is one selected from the group consisting of Al, Zr, W, Ti, Mg, Ca and Sr, and 0≤a1≤0.5, 0.55 <x1<1.0, 0<y1≤0.4, 0<z≤0.4, 0≤w≤0.1 이다. In the chemical formula 2, the 1+a1 represents the molar ratio of lithium in the lithium nickel cobalt manganese oxide, and may be 0≤a1≤0.5, preferably 0≤a1≤0.2, and more preferably 0≤a1≤0.1. When the molar ratio of lithium satisfies the above range, the layered crystal structure of the lithium nickel cobalt manganese oxide can be stably formed. When the a1 exceeds 0.5, there is a concern that the initial discharge capacity of the battery may decrease or the Li byproduct on the surface of the positive electrode active material may increase too much, which may lead to severe gas generation during high-temperature operation. The above x1 represents the molar ratio of nickel among the total metals excluding lithium in lithium nickel cobalt manganese oxide, which is 0.55. <x1<1.0, 구체적으로는 0.6≤x1≤0.98, 보다 더 구체적으로는 0.6≤x1≤0.95일 수 있다. 상기 x가 상기 범위를 만족할 때 우수한 용량 특성을 구현할 수 있다. The above y1 represents the molar ratio of cobalt among all metals excluding lithium in lithium nickel cobalt manganese oxide, and is 0. <y1≤0.4, 구체적으로 0<y1≤0.3, 바람직하게는 0.01≤y1≤0.3일 수 있다. The above z is M of all metals except lithium in lithium nickel cobalt manganese oxide. 1 It represents the molar ratio of elements, 0 <z≤0.4, 바람직하게는 0<z≤0.3, 더 바람직하게는 0.01≤z≤0.3일 수 있다. The above w is M of all metals except lithium in lithium nickel cobalt manganese oxide. 2 It represents the molar ratio of elements, 0 <w≤0.1, 바람직하게는 0<z≤0.05일 수 있다. These lithium nickel cobalt manganese oxides are Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , Li(Ni) 0.7 Mn 0.2 Co 0.1 )O 2 , Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 , Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 , Li(Ni 0.86 Mn 0.07 Co 0.05 Al 0.02 )O 2 and Li(Ni 0.90 Mn 0.05 Co 0.05 )O 2 It can be any one selected from the group consisting of . When lithium nickel cobalt manganese oxide is added to the positive electrode of the present invention, the lithium iron phosphate and lithium nickel cobalt manganese oxide may be included in a weight ratio of 30:70 to 80:20, specifically, may be included in a weight ratio of 50:50 to 80:20, or may be included in a weight ratio of 60:40 to 70:30. When the mixing ratio of lithium iron phosphate and lithium nickel cobalt manganese oxide having the above olivine structure satisfies the above range, the high temperature and high voltage safety of the battery can be secured while improving the electrical conductivity. Specifically, when the content ratio of lithium iron phosphate having an olivine structure to the lithium nickel cobalt manganese oxide is less than 80 weight ratio, excellent capacity characteristics and electrical conductivity can be secured, and when the content ratio of the olivine structure to the lithium nickel cobalt manganese oxide is 30 weight ratio or more, high temperature and high voltage stability can be secured. Meanwhile, the present invention has a loading amount of 32 mg / cm of a cathode including lithium iron phosphate represented by the chemical formula 1 and lithium nickel cobalt manganese oxide represented by the chemical formula 2 as cathode active materials for designing a high capacity electrode. 2 Ideal (cross-sectional loading: 16 mg / cm 2 ) and specifically 32 mg / cm 2 60 mg / cm 2 may be, more preferably 40 mg / cm 2 60 mg / cm 2 If the loading amount of the above anode satisfies the above range, high energy density and high capacity characteristics can be implemented. The above positive electrode may include a positive electrode current collector; and a positive electrode composite layer disposed on at least one surface of the positive electrode current collector. In this case, the positive electrode composite layer may include the lithium iron phosphate described above as a positive electrode active material. The thickness of the above positive electrode collector can typically have a thickness of 3 to 500 μm. The above-mentioned positive electrode current collector may form fine irregularities on the surface to strengthen the bonding strength of the positive electrode active material. For example, the above-mentioned positive electrode current collector may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven fabric, etc. The above positive electrode composite layer is disposed on at least one surface of the positive electrode current collector. Specifically, the positive electrode composite layer may be disposed on one surface or both surfaces of the positive electrode current collector. In addition, lithium iron phosphate represented by the chemical formula 1 may be included in the positive electrode composite layer at 80 to 99 wt% in consideration of sufficient capacity, etc. Meanwhile, the positive electrode composite layer may further include a binder and / or a conductive material together with the positive electrode active material described above. The above binder serves to improve the adhesion between positive electrode active material particles and the adhesive strength between the positive electrode active material and the current collector. Examples of such binders include: a fluorine resin binder such as polyvinylidene fluoride (PVDF); a rubber binder including styrene butadiene rubber (SBR), acrylonitrile-butadiene rubber, and styrene-isoprene rubber; a cellulose binder including carboxyl methyl cellulose (CMC), starch, hydroxy propyl cellulose, and regenerated cellulose; a polyalcohol binder including polyvinyl alcohol; a polyolefin binder including polyethylene and polypropylene; a polyimidazole binder; a polyester binder; and a silane binder, one of which alone or a mixture of two or more thereof may be used. The above binder may be included in the positive electrode composite layer at 0.1 to 15 wt%, preferably 0.1 to 10 wt%. Next, the conductive material is used to provide conductivity to the electrode, and in the battery to be formed, as long as it does not cause a chemical change and has electronic conductivity, it can be used without special restrictions. Specific conductive materials that can be used include carbon black such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; conductive fibers such as carbon fibers or metal fibers; conductive powders such as fluorinated carbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene derivatives. The above-mentioned challenging agent can be added in an amount of 1 to 30 wt% in the positive electrode composite layer. The above positive electrode can be manufactured by coating a positive electrode slurry containing a positive electrode active material and optionally a binder, a conductive material, and a solvent for forming a positive electrode slurry on the positive electrode current collector, and then drying and rolling. Alternatively, a positive electrode can be manufactured by mixing a positive electrode active material and optionally a binder, a conductive material, etc. to manufacture a film, and then laminating the film on a positive electrode current collector. The solvent for forming the positive electrode slurry may include at least one selected from the group consisting of distilled water, N-methyl pyrrolidone, ethanol, methanol and isopropyl alcohol, preferably N-methyl pyrrolidone, in terms of facilitating dispersion of the positive electrode active material, binder and / or conductive agent. (2) Cathode Next, let's explain the cathode. The above negative electrode may include a negative electrode active material. As the above negative active material, a carbon-based active material, a silicon-based active material, or a mixture of a carbon-based active material and a silicon-based active material can be used. As the carbon-based active material, various carbon-based active materials used in the art, for example, graphite-based materials such as natural graphite, artificial graphite, and Kish graphite; high-temperature calcined carbon such as pyrolytic carbon, mesophase pitch based carbon fiber, carbon microbeads, mesophase pitches, and petroleum or coal tar pitch derived cokes, soft carbon, and hard carbon, etc. can be used. The shape of the carbon-based active material is not particularly limited, and materials of various shapes such as amorphous, plate-like, flaky, spherical, or fibrous can be used. Specifically, the carbon-based active material may be either natural graphite or artificial graphite, and natural graphite and artificial graphite may be used together to increase adhesion to the current collector and suppress desorption of the active material. In addition, the silicon-based active material may be, for example, metal silicon (Si), silicon oxide (SiO). x, here 0 <x<2) 실리콘 탄화물(SiC) 및 Si-Y 합금(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si은 아님)로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 상기 원소 Y로는 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db (dubnium), Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. The average particle diameter (D) of the above silicon-based active material 50 ) may be 1 ㎛ to 30 ㎛, preferably 2 ㎛ to 15 ㎛, in order to reduce side reactions with the electrolyte while ensuring structural stability during charging and discharging. In addition, the negative electrode of the present invention may include at least one selected from the carbon-based active material and the silicon-based active material as the negative electrode active material. Specifically, the negative electrode of the present invention may include the carbon-based active material and the silicon-based active material. At this time, the weight ratio of the silicon-based active material and the carbon-based active material may be 1:99 to 30:70, specifically 3:97 to 15:85. When the mixing ratio of the silicon-based active material and the carbon-based active material satisfies the above range, the capacity characteristics can be improved while the volume expansion of the silicon-based active material is suppressed, thereby ensuring excellent cycle performance. The above negative electrode may include a negative electrode current collector; and a negative electrode composite layer disposed on at least one surface of the negative electrode current collector. In this case, the negative electrode active material may be included in the negative electrode composite layer. The above negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery. Specifically, the negative electrode current collector may be made of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., an aluminum-cadmium alloy, etc. The above negative electrode collector may typically have a thickness of 3 to 500 μm. The above negative electrode current collector may form fine irregularities on the surface to strengthen the bonding strength of the negative electrode active material. For example, the above negative electrode current collector may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, a non-woven fabric, etc. The above negative electrode composite layer is disposed on at least one surface of the negative electrode current collector. Specifically, the negative electrode composite layer may be disposed on one surface or both surfaces of the negative electrode current collector. The above negative active material may be included in the negative electrode composite layer at 60 wt% to 99 wt% in order to sufficiently express the capacity in the secondary battery while minimizing the effect of volume expansion / contraction on the battery. The above negative electrode composite layer may further include a conductive material and / or a binder together with the above negative electrode active material. The conductive agent is a component for further improving the conductivity of the negative electrode active material, and is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and for example, carbon black such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; conductive fibers such as carbon fibers or metal fibers; conductive powders such as fluorinated carbon powder, aluminum powder, 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, etc. can be used. The above-mentioned challenging agent may be added to the cathode composite layer in an amount of 10 wt% or less, preferably 5 wt% or less. The above binder is a component that assists in bonding between the conductive material, the active material, and the current collector, and typically includes a fluorine resin binder such as polyvinylidene fluoride (PVDF); a rubber binder including styrene butadiene rubber (SBR), acrylonitrile-butadiene rubber, and styrene-isoprene rubber; a cellulose binder including carboxymethyl cellulose (CMC), starch, hydroxy propyl cellulose, and regenerated cellulose; a polyalcohol binder including polyvinyl alcohol; a polyolefin binder including polyethylene and polypropylene; a polyimidazole binder; a polyester binder; and a silane binder. The above binder may be included in the cathode composite layer at 0.1 to 15 wt%, preferably 0.1 to 10 wt%. The above negative electrode can be manufactured by coating a negative electrode slurry including a negative electrode active material and optionally a binder, a conductive material, and a solvent for forming a negative electrode slurry on the negative electrode current collector, and then drying and rolling. Alternatively, the negative electrode can be manufactured by mixing a negative electrode active material and optionally a binder, a conductive material, etc. to manufacture a film, and then laminating the film on the negative electrode current collector. The solvent for forming the negative electrode slurry may include at least one selected from the group consisting of distilled water, N-methyl pyrrolidone, ethanol, methanol and isopropyl alcohol, preferably distilled water, in terms of facilitating dispersion of the negative electrode active material, binder and / or conductive agent. (3) Membrane The above separator separates the negative electrode and the positive electrode and provides a passage for lithium ions to move. If it is a separator commonly used in lithium secondary batteries, it can be used without any special restrictions. In particular, it is preferable that it have low resistance to the movement of ions in a non-aqueous electrolyte and excellent non-aqueous electrolyte wetting ability. Specifically, the separator may be a porous polymer film, for example, a porous polymer film made of a polyolefin polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, an ethylene / methacrylate copolymer, or a laminated structure of two or more layers thereof. In addition, a conventional porous nonwoven fabric, for example, a nonwoven fabric made of high-melting-point glass fibers, polyethylene terephthalate fibers, or the like may be used. In addition, a coated separator containing a ceramic component or a polymer material to secure heat resistance or mechanical strength may be used, and may optionally be used in a single-layer or multi-layer structure. (4) Electrolyte Next, the electrolyte of the present invention may include a lithium salt; a first organic solvent; a second organic solvent; a first additive; and a second additive, and specific examples of each component are as described below. (4-1) Lithium salt First, the lithium salt can be used without limitation as an electrolyte for lithium secondary batteries, for example, Li as a cation. + , and the anion is F - , Cl - , Br - , I - , N(CN) 2 - , BF 4 - , ClO 4 - , B 10 Cl 10 - , AlCl 4 - , AlO 2 - , PF 6 - , CF 3 SO 3 - , CH 3 CO 2 - , CF 3 CO 2 - , AsF 6 - , SbF 6 - , CH 3 SO 3 - , (CF 3 CF 2 SO 2 ) 2 N - , (CF 3 SO 2 ) 2 N - , (FSO 2 ) 2 N - , BF 2 C 2 O 4 - , BC 4 O 8 - , PF 4 C 2 O 4 -, PF 2 C 4 O 8 - , (CF 3 ) 2 PF 4 - , (CF 3 ) 3 PF 3 - , (CF 3 ) 4 PF 2 - , (CF 3 ) 5 PF - , (CF 3 ) 6 P - , C 4 F 9 SO 3 - , CF 3 CF 2 SO 3 - , CF 3 CF 2 (CF 3 ) 2 CO - , (CF 3 SO 2 ) 2 CH - , CF 3 (CF 2 ) 7 SO 3 - and SCN - Any one selected from the group consisting of may be mentioned. Specifically, the lithium salt is LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiB 10 Cl 10 , LiAlCl 4 , LiAlO 2 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2, LiAsF 6 , LiSbF 6 , LiCH 3 SO 3 , LiN(SO 2 F) 2 (Lithium bis(fluorosulfonyl)imide, LiFSI), LiN(SO 2 CF 2 CF 3 ) 2 (lithium bis(pentafluoroethanesulfonyl)imide, LiBETI) and LiN(SO 2 CF 3 ) 2 It may include a single substance or a mixture of two or more substances selected from the group consisting of (lithium bis(trifluoromethane sulfonyl)imide, LiTFSI), specifically LiBF 4 , LiPF 6 , LiN(SO 2 F) 2 (Lithium bis(fluorosulfonyl)imide, LiFSI), LiN(SO 2 CF 2 CF 3 ) 2 (lithium bis(pentafluoroethanesulfonyl)imide, LiBETI) and LiN(SO 2 CF 3 ) 2 (lithium bis(trifluoromethane sulfonyl)imide, LiTFSI) may include any one selected from the group consisting of: (lithium bis(trifluoromethane sulfonyl)imide, LiTFSI). In addition to these, lithium salts commonly used in electrolytes of lithium secondary batteries may be used without limitation. The above lithium salt may be appropriately changed within a normally usable range, but in order to obtain an optimal effect of forming a film for preventing corrosion of the electrode surface, it may be included in the electrolyte at a concentration of 0.8 M to 3.0 M, specifically, at a concentration of 1.0 M to 2.0 M, and preferably at a concentration of 1.0 M to 1.8 M. When the concentration of the lithium salt is within the above range, the viscosity of the electrolyte can be controlled to achieve optimal impregnation, and the mobility of lithium ions can be improved, thereby obtaining the effect of improving the capacity characteristics and cycle characteristics of a lithium secondary battery. (4-2) First organic solvent Next, the first organic solvent is described. The first organic solvent may include a cyclic lactone compound. The above cyclic lactone compound is a compound having high dielectric constant and ionic conductivity, and can improve the charge transfer reduction phenomenon caused when operating a high-loading electrode. The above cyclic lactone compound may include gamma-butyrolactone. The first organic solvent may be included in an amount of 39 wt% to 80 wt% based on the total weight of the electrolyte, specifically, in an amount of 48 wt% to 80 wt%, and more preferably, in an amount of 52 wt% to 70 wt%. When the content of the first organic solvent of the present invention satisfies the above range, the lithium ion transfer characteristics can be improved, thereby achieving a battery resistance reduction effect. (4-3) Second organic solvent Next, the second organic solvent is explained. The above second organic solvent may include a carbonate-based organic solvent so that decomposition due to oxidation reactions, etc. during the charging and discharging process of the secondary battery can be minimized and the desired characteristics can be exhibited together with an additive. Specifically, it is preferable that the carbonate-based organic solvent include one selected from the group consisting of a cyclic carbonate-based organic solvent having high ionic conductivity and high dielectric constant and a linear carbonate-based organic solvent having low viscosity and low dielectric constant, and specifically may include a cyclic carbonate-based organic solvent. The above cyclic carbonate-based organic solvent may specifically include one or two or more organic solvents selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), and among these, ethylene carbonate capable of maintaining a stable SEI film passivation ability may be mentioned. In addition, the linear carbonate organic solvent may be one or two or more organic solvents selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate, and among these, dimethyl carbonate (DMC) having a small molecular size and low viscosity characteristics may be exemplified. When the cyclic carbonate and linear carbonate are mixed and used as the second organic solvent, in order to secure low viscosity characteristics, the cyclic carbonate-based organic solvent and the linear carbonate-based organic solvent may be mixed and used in a volume ratio of about 1:99 to 50:50, or may be mixed and used in a volume ratio of 20:80 to 40:60. Meanwhile, in the present invention, the first organic solvent and the second organic solvent may be included in a volume ratio of 50:50 to 99:1, specifically, may be included in a volume ratio of 70:30 to 99:1, and more specifically, may be included in a volume ratio of 70:30 to 90:10. When the mixing ratio of the first organic solvent and the second organic solvent satisfies the above range, a high ion transfer characteristic effect can be achieved, and battery performance with low resistance characteristics can be secured. That is, when the volume ratio of the first organic solvent is 50 or more, the ion transfer characteristic effect can be secured, and when the volume ratio is 99 or less, a stable film can be formed, thereby improving the battery life characteristics. (4-4) First additive Next, the first additive will be described. The above first additive is lithium nitrate (LiNO 3 ) may be included. Lithium nitrate (LiNO) included as the first additive 3 ) can form an inorganic film containing lithium-nitrogen and lithium-oxygen bonds on the cathode surface during the activation step. Since this inorganic film increases surface energy and acts as an ion transporter capable of uniformly transporting lithium ions, it can improve the electrode impregnation property of the electrolyte and induce a more effective charge transfer reaction. In addition, lithium nitrate (LiNO) included as the first additive 3 ) forms a coordination bond with a transition metal dissolved from the positive electrode under a high-temperature environment, or forms a coordination bond with a Lewis acid generated by a decomposition product of a lithium salt, thereby inhibiting the deposition of transition metal ions on the negative electrode surface, thereby preventing reversible lithium loss, and thus improving the deterioration of cycle characteristics. Meanwhile, the first additive may be included in the electrolyte at a specific content. Specifically, the first additive may be included in an amount of 0.05 wt% to 3.0 wt% based on the total weight of the electrolyte, specifically in an amount of 0.05 wt% to 2.0 wt%, more specifically in an amount of 0.1 wt% to 2.0 wt%, and preferably in an amount of 0.1 wt% to 1.5 wt%. When the content of the first additive of the present invention satisfies the above range, an inorganic film including lithium-nitrogen and lithium-oxygen bonds is uniformly formed on the surface of the negative electrode, so that the negative electrode can operate as an effective ion transporter instead of operating as a resistor. That is, when the first additive is included in an amount of 0.05 wt% or more, an increase in battery resistance can be suppressed, thereby preventing battery performance degradation, and when it is included in an amount of 3.0 wt% or less, side reactions can be suppressed, thereby preventing unnecessary activation gases and the like from being generated, thereby preventing degradation of high-temperature cycle and high-temperature storage characteristics. In addition, it is preferable that the first additive content and the anode loading amount in the electrolyte satisfy the following equation 1. [Formula 1] 0.0001≤ ≤0.050 In the above equation 1, A is the total amount of electrolyte (g) injected into the lithium secondary battery, B is lithium nitrate (LiNO) contained in the above-mentioned electrolyte. 3 ) is the content (weight%), C is the loading of the anode (g / cm 2 ) and D is the total area of ​​the positive electrode surface (cm 2 )am. When the content of the first additive in the electrolyte of the present invention satisfies the above formula 1, the electrolyte impregnation property for the negative electrode can be increased, and an effective inorganic film that can improve ion transfer characteristics can be formed, thereby ensuring excellent battery performance. (4-5) Second additive Next, the second additive will be described. In the present invention, an imidazole compound may be included as a second additive. The above imidazole compound may include a compound represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, R is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, R 1 Inland R 3 are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms, or -CN. Specifically, the compound represented by the chemical formula 3 has a structure in which the unshared electron pair of the nitrogen element included in the structure acts as a Lewis base, thereby producing HF and PF, which are decomposition products of the lithium salt. 5 At the same time as removing Lewis acids such as , it is possible to stabilize lithium salt anions and suppress Lewis acid generation. As a result, the deterioration behavior of the film on the surface of the positive or negative electrode caused by Lewis acids can be suppressed, and additional electrolyte decomposition caused by this can be prevented. As a result, self-discharge of the secondary battery can be alleviated, and high-temperature performance characteristics can be improved. In addition, the compound represented by the chemical formula 3 contains a propargyl functional group that is easily reduced on the cathode surface within its structure, so that it can form an SEI film having a high passivation ability on the cathode surface, thereby preventing additional reduction and decomposition reactions of the electrolyte caused by the instability of the SEI film, and improving the high-temperature durability of the cathode itself, thereby suppressing the self-discharge reaction of the cathode. In particular, the propargyl group included in the compound represented by the chemical formula 1 can be adsorbed on the surface of metallic impurities included in the cathode, thereby suppressing the elution of the impurities, thereby suppressing the deposition of metal ions on the cathode surface, thereby preventing internal short circuit. In the above chemical formula 3, R may be a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms, and specifically, may be an unsubstituted alkylene group having 1 or 2 carbon atoms. In addition, in the chemical formula 3, R 1 may be hydrogen, an alkyl group having 1 carbon atom, or -CN, or may be hydrogen, an alkyl group having 1 carbon atom, or -CN, and specifically may be hydrogen or -CN. In addition, in the chemical formula 3, R 2 may be hydrogen, an alkyl group having 1 carbon atom, or -CN, or may be hydrogen, an alkyl group having 1 carbon atom, or -CN, and specifically may be hydrogen or -CN. In addition, in the chemical formula 3, R 3 may be hydrogen, an alkyl group having 1 carbon atom, or -CN, or may be hydrogen, an alkyl group having 1 carbon atom, or -CN, and specifically may be hydrogen or -CN. Preferably, the compound represented by the chemical formula 3 may be a compound represented by the following chemical formula 3A. [Chemical Formula 3A] Meanwhile, in the electrolyte of the present invention, the first additive and the second additive may be included in a weight ratio of 1:0.05 to 1:2, may be included in a weight ratio of 1:0.1 to 1:2, and more preferably may be included in a weight ratio of 1:0.1 to 1:1. When the composition ratio of the first additive and the second additive satisfies the above range, a stable film can be formed on the surfaces of the positive and negative electrodes, thereby improving the cycle characteristics and OCV when driving at high voltage, and improving the high-temperature storage characteristics. That is, when the second additive is included in a weight ratio of 2 or less, a uniform film can be formed on the surface of the negative electrode, thereby preventing it from acting as a resistor, and delaying the decomposition reaction of the electrolyte itself. On the other hand, when the second additive is included in a relatively large amount, the film thickness increases due to the increase in the content of the second additive that is reduced and decomposed on the surface of the negative electrode, so that it can act as a resistor, and also, the second additive that remains without being decomposed after activation can deteriorate the performance of the electrolyte. (4-6) Other additives Meanwhile, the lithium secondary battery of the present invention may additionally include other additives in the electrolyte as needed to prevent the electrolyte from being decomposed and causing cathode collapse in a high-power environment, or to further improve low-temperature high-rate discharge characteristics, high-temperature stability, overcharge prevention, and high-temperature battery expansion suppression effects. When other additives are included, the other additives may be named a third additive. These other additives may include, as representative examples, any one of other additives selected from the group consisting of cyclic carbonate compounds, sultone compounds, phosphate compounds, borate compounds, nitrile compounds, benzene compounds, amine compounds, silane compounds, and lithium salt compounds. The above cyclic carbonate compound may be vinylene carbonate (VC). The above sultone compound may be any one compound selected from the group consisting of 1,3-propane sultone (PS), 1,4-butane sultone, ethene sultone, 1,3-propene sultone (PRS), 1,4-butene sultone, and 1-methyl-1,3-propene sultone. The above phosphate compound may include at least one compound selected from the group consisting of lithium difluoro(bisoxalato)phosphate, lithium difluorophosphate, tris(trimethylsilyl)phosphate, tris(2,2,2-trifluoroethyl)phosphate, and tris(trifluoroethyl)phosphate. The above borate compounds include tetraphenylborate and lithium oxalyldifluoroborate. The above nitrile compound may include any one compound selected from the group consisting of succinonitrile, adiponitrile, acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile. The benzene compound may include fluorobenzene, the amine compound may include triethanolamine or ethylene diamine, and the silane compound may include tetravinylsilane. The above lithium salt compound is a compound different from the lithium salt included in the electrolyte, LiPO 2 F 2 , LiODFB, LiBOB (lithium bisoxalate borate (LiB(C 2 O 4 ) 2 ) and LiBF 4 and at least one compound selected from the group consisting of LiDFOP. The above other additives may be used in combination of two or more, and may be included in an amount of less than 10 wt%, specifically 0.01 wt% or more and less than 8.0 wt%, and preferably 0.05 wt% to 5.0 wt%, based on the total weight of the electrolyte. When the content of the above other additives satisfies the above range, side reactions caused by unreacted additives can be suppressed, and the effects of improving low-temperature output and high-temperature storage characteristics and high-temperature life characteristics of the battery can be further enhanced. The lithium secondary battery according to the present invention as described above can be usefully used in portable devices such as mobile phones, laptop computers, and digital cameras, and electric vehicles such as hybrid electric vehicles (HEVs). There is no particular limitation on the external shape of the lithium secondary battery of the present invention, but it may be in the shape of a cylinder, a square, a pouch, or a coin using a can. The lithium secondary battery according to the present invention can be used not only as a battery cell used as a power source for a small device, but can also be preferably used as a unit battery in a medium- to large-sized battery module including a plurality of battery cells. Hereinafter, the present invention will be described in detail by way of examples in order to specifically explain the present invention. However, the examples according to the present invention may be modified in various different forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided in order to more completely explain the present invention to a person having average knowledge in the art. [Example] Example 1. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6Dissolve to make 1.0 M, then add lithium nitrate (LiNO) as the first additive. 3 ) 0.05 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:2), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Polar manufacturing) Cathode active material (LiFePO 4 ), a conductive agent (carbon black) and a binder (polyvinylidene fluoride, PVDF) were added to a solvent, N-methyl-2-pyrrolidone (NMP), in a weight ratio of 96:1:3 to prepare a positive electrode active material slurry (solid content 67 wt%). The positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 15 ㎛, dried, and roll pressed to prepare a positive electrode (double-sided loading: 48 mg / cm2, single-sided loading: 24 mg / cm2). (Cathode manufacturing) A slurry of negative active material (artificial graphite), CMC-SBR as a binder, and carbon black as a conductive material were added to distilled water as a solvent in a weight ratio of 96:3.5:0.5 to prepare a slurry of negative active material (solid content: 53 wt%). The slurry of the negative active material was applied to a negative current collector (Cu thin film) having a thickness of 8 ㎛, dried, and roll pressed to prepare a negative electrode. (Secondary battery manufacturing) An electrode assembly was manufactured by a conventional method of sequentially laminating the positive and negative electrodes manufactured by the above-described method together with a polyethylene porous film, and then this was placed in a pouch-type secondary battery case, and the lithium secondary battery electrolyte manufactured as described above was injected to manufacture a lithium secondary battery. Example 2. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 0.1 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:1), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 3. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 1.5 wt% and 0.15 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.1), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 4. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3) 3.0 wt% and 0.15 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.05) were added, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 5. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 1.0 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.1) were added, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 6. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3) 1.0 wt% and 0.2 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.2), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 7. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 99:1 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 1.0 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.1) were added, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 8. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 50:50 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3) 1.0 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.1) were added, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 9. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 4.0 wt% and 0.4 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.1) were added, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 10. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3) 1.0 wt% and 3.0 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:3), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 11. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 40:60 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 0.1 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:1), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to manufacture an electrolyte for a lithium secondary battery of the present invention. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Example 12. (Polar manufacturing) Cathode active material (LiFePO 4), a conductive agent (carbon black) and a binder (polyvinylidene fluoride, PVDF) were added to a solvent, N-methyl-2-pyrrolidone (NMP), in a weight ratio of 96:1:3 to prepare a positive electrode active material slurry (solid content 67 wt%). The positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 15 ㎛, dried, and roll pressed to prepare a positive electrode (double-sided loading: 32 mg / cm2, single-sided loading: 16 mg / cm2). (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the above-mentioned manufactured positive electrode was applied. Example 13. (Polar manufacturing) Cathode active material (LiFePO 4 ), a conductive agent (carbon black) and a binder (polyvinylidene fluoride, PVDF) were added to a solvent, N-methyl-2-pyrrolidone (NMP), in a weight ratio of 96:1:3 to prepare a positive electrode active material slurry (solid content 67 wt%). The positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 15 ㎛, dried, and roll pressed to prepare a positive electrode (double-sided loading: 60 mg / cm2, single-sided loading: 30 mg / cm2). (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the above-mentioned manufactured positive electrode was applied. Comparative example 1. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3) was added at 1.0 wt%, the second additive was not included, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to prepare an electrolyte. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the manufactured electrolyte was injected. Comparative example 2. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 After dissolving to make 1.0 M, 1.0 wt% of an imidazole compound represented by the chemical formula 3A was added as a second additive without including the first additive, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to prepare an electrolyte. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Comparative Example 1, except that the manufactured electrolyte was injected. Comparative example 3. (Electrolyte manufacturing) LiPF in an organic solvent containing ethylene carbonate and ethyl methyl carbonate in a volume ratio of 20:80 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 1.0 wt% and 0.1 wt% of an imidazole compound represented by the chemical formula 3A as a second additive (weight ratio of the first additive and the second additive = 1:0.1), and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to prepare an electrolyte. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Comparative Example 1, except that the manufactured electrolyte was injected. Comparative example 4. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0M, then use LiBF as the first additive 4 An electrolyte was prepared by adding 1.0 wt% of an imidazole compound represented by the chemical formula 3A as a first additive (weight ratio of the first additive and the second additive = 1:1) and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) as other additives. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Comparative Example 1, except that the manufactured electrolyte was injected. Comparative Example 5. (Electrolyte manufacturing) LiPF in an organic solvent containing gamma-butyrolactone and ethylene carbonate in a volume ratio of 70:30 6 Dissolve to make 1.0 M, then use lithium nitrate (LiNO) as the first additive. 3 ) 0.1 wt% and lithium bis(trifluoromethane sulfonyl)imide (LiN(SO)) as a second additive. 2 CF 3 ) 2 , LiTFSI) 0.1 wt% (weight ratio of the first additive and the second additive = 1:1) was added, and 3.0 wt% of vinylene carbonate (VC) and 1.0 wt% of ethylene sulfate (Esa) were added as other additives to prepare an electrolyte. (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Comparative Example 1, except that the manufactured electrolyte was injected. Comparative example 6. (Polar manufacturing) Cathode active material (LiFePO 4), a conductive agent (carbon black) and a binder (polyvinylidene fluoride, PVDF) were added to a solvent, N-methyl-2-pyrrolidone (NMP), in a weight ratio of 96:1:3 to prepare a positive electrode active material slurry (solid content 67 wt%). The positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 15 ㎛, dried, and roll pressed to prepare a positive electrode (double-sided loading: 62 mg / cm2, single-sided loading: 31 mg / cm2). (Secondary battery manufacturing) A lithium secondary battery was manufactured in the same manner as in Example 1, except that the above-mentioned manufactured positive electrode was applied. [Experimental example] Experimental Example 1. Evaluation of high temperature (45℃) cycle characteristics The lithium secondary batteries manufactured in the above examples and comparative examples were each charged to 64% SOC at a high temperature (55°C) at a C rate of 0.1, and then subjected to an aging (48 hours) and degassing process to perform an activation process. After the activation process was completed, each lithium secondary battery was charged to 3.8 V under constant current / constant voltage conditions at 0.1 C rate at room temperature (25°C), and discharged to 2.5 V under constant current conditions at 0.33 C rate to confirm the initial capacity. Then, each lithium secondary battery was charged to 3.8 V under constant current / constant voltage conditions at a high temperature (45°C) at a 0.33 C rate, and discharged to 2.5 V under constant current conditions at a 0.33 C rate for 100 cycles, which was considered one cycle, and then the discharge capacity was measured. The lithium secondary battery operation was performed using a PNE-0506 charger / discharger (manufacturer: PNE solution). The high temperature cycle capacity retention rate was calculated using the 100th discharge rate of the obtained initial capacity dash, and the results are shown in Table 1 below. High temperature cycle capacity retention (%) Example 191.2 Example 291.3 Example 392.0 Example 491.8 Example 591.5 Example 691.4 Example 790.8 Example 890.6 Example 989.1 Example 1089.2 Example 1189.3 Example 1290.6 Example 1390.2 Comparative Example 187.9 Comparative Example 286.5 Comparative Example 388.0 Comparative Example 486.9 Comparative Example 585.9 Comparative Example 686.0 Referring to Table 1 above, it can be confirmed that the capacity retention rate (%) after high-voltage, high-temperature cycling of the lithium secondary batteries manufactured in Examples 1 to 13 of the present invention is improved compared to the lithium secondary batteries of Comparative Examples 1 to 6. Although the present invention has been described above with reference to preferred embodiments thereof, it will be understood by those skilled in the art or having ordinary knowledge in the art that various modifications and changes may be made to the present invention without departing from the spirit and technical scope of the present invention as set forth in the claims below. Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be determined by the claims.

Claims

1. In a lithium secondary battery including a positive electrode, a negative electrode, a separator, and an electrolyte, The above positive electrode contains lithium iron phosphate as a positive electrode active material, The loading amount of the above anode is 32 mg / cm 2 60 mg / cm 2 And, The electrolyte comprises a lithium salt; a first organic solvent; a second organic solvent; a first additive; and a second additive. The above first organic solvent is a cyclic lactone compound, The above second organic solvent is a carbonate-based organic solvent, The above first additive is lithium nitrate (LiNO 3 ) and, A lithium secondary battery, wherein the second additive is an imidazole compound.

2. In paragraph 1, A lithium secondary battery, wherein the lithium iron phosphate comprises a compound represented by the following chemical formula 1: [Chemical Formula 1] Li 1+a Fe x M y (PO 4-b )X b In the above [chemical formula 1], M is one selected from the group consisting of Al, Mg, Ni, Co, Mn, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn and Y, X is one or more elements selected from the group consisting of F, S, and N, -0.5≤a≤0.5, 0 <x≤1, 0≤y≤1 및 0≤b≤0.3이다.

3. In paragraph 2, The above lithium iron phosphate is lithium iron phosphate (LiFePO 4 ) or lithium manganese iron phosphate (LiFeMnPO 4 ) lithium secondary battery.

4. In paragraph 1, A lithium secondary battery wherein the positive electrode further comprises lithium nickel cobalt manganese oxide represented by the following chemical formula 2: [Chemical formula 2] Li 1+a1 Ni x1 Co y1 M 1 z M 2 w O 2 In the above [chemical formula 2], M 1 is Mn, Al or a combination of these, and M 2 is one selected from the group consisting of Al, Zr, W, Ti, Mg, Ca and Sr, and 0≤a1≤0.5, 0.55 <x1<1.0, 0<y1≤0.4, 0<z≤0.4, 0≤w≤0.1 이다.

5. In paragraph 4, The above lithium nickel cobalt manganese oxide is Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 , Li(Ni) 0.7 Mn 0.2 Co 0.1 )O 2 , Li(Ni 0.8 Mn 0.1 Co 0.1 )O 2 , Li(Ni 0.8 Co 0.15 Al 0.05 )O 2 , Li(Ni 0.86 Mn 0.07 Co 0.05 Al 0.02 )O 2 and Li(Ni 0.90 Mn 0.05 Co 0.05 )O 2 A lithium secondary battery, wherein the lithium secondary battery is one selected from the group consisting of:

6. In paragraph 4, A lithium secondary battery, wherein the lithium iron phosphate and lithium nickel cobalt manganese oxide are contained in a weight ratio of 70:30 to 80:

20.

7. In paragraph 1, The loading amount of the above anode is 40 mg / cm 2 60 mg / cm 2 A lithium secondary battery.

8. In paragraph 1, A lithium secondary battery, wherein the above cyclic lactone compound is gamma-butyrolactone.

9. In paragraph 1, A lithium secondary battery, wherein the above carbonate-based organic solvent is a cyclic carbonate-based organic solvent.

10. In paragraph 1, A lithium secondary battery, wherein the first organic solvent and the second organic solvent are included in a volume ratio of 50:50 to 99:

1.

11. In paragraph 1, A lithium secondary battery, wherein the first organic solvent and the second organic solvent are included in a volume ratio of 70:30 to 99:

1.

12. In paragraph 1, A lithium secondary battery, wherein the first additive is included in an amount of 0.05 wt% to 3.0 wt% based on the total weight of the electrolyte.

13. In paragraph 1, The above imidazole compound is a lithium secondary battery represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R is a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, R 1 Inland R 3 are each independently hydrogen, an alkyl group having 1 to 3 carbon atoms, or -CN.

14. In paragraph 13, The above imidazole compound is a lithium secondary battery represented by the following chemical formula 3A: [Chemical Formula 3A] .

15. In paragraph 1, A lithium secondary battery, wherein the first additive and the second additive are included in a weight ratio of 1:0.05 to 1:

2.

16. In paragraph 1, A lithium secondary battery, wherein the negative electrode comprises a carbon-based active material, a silicon-based active material, or a mixture of a carbon-based active material and a silicon-based active material.

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