Non-aqueous electrolyte solution and power storage device comprising same

Abstract

The present invention relates to a non-aqueous electrolyte solution and a power storage device comprising same, the non-aqueous electrolyte solution being capable of simultaneously implementing excellent ion conductivity and electrochemical stability by including an additive having a specific structure. A lithium secondary battery employing the non-aqueous electrolyte solution, according to the present invention, can implement excellent output performance and has both improved lifespan characteristics and high-temperature stability.

Description

Non-aqueous electrolyte and storage device containing the same

[0001] The present disclosure relates to a non-aqueous electrolyte containing an additive of a specific structure and a storage device containing the same.

[0002] Since the characteristics of a lithium secondary battery are determined by the complex reactions of the positive electrode and electrolyte, negative electrode and electrolyte, the use of electrolyte is one of the important variables that improves the performance of a lithium secondary battery.

[0003] Recently, with the simultaneous demand for miniaturization and larger capacity in lithium secondary batteries, the performance requirements for electrolytes used in these batteries are also gradually increasing. Accordingly, active research is being conducted on organic electrolytes that exhibit high ionic conductivity and dielectric constant, and facilitate high voltage and miniaturization. However, organic electrolytes can cause side reactions between the electrodes and electrolyte, which can reduce the lifespan of lithium secondary batteries. Furthermore, their physical properties change significantly with temperature, leading to deterioration in battery performance in low- or high-temperature environments.

[0004] To address this, the development of additives that can suppress side reactions with the electrode and maintain stability even under temperature changes is required. However, additives for non-aqueous electrolytes developed to date have limitations, such as reduced ionic conductivity and output characteristics, even if stability is improved. Furthermore, when using layered, high-capacity cathode materials with high nickel content or lithium metal as the anode material, stability improvements are limited.

[0005] One aspect of the present invention aims to provide a non-aqueous electrolyte capable of simultaneously achieving excellent ionic conductivity and electrochemical stability, and a storage device including the same.

[0006] The present invention provides a non-aqueous electrolyte solution comprising a non-aqueous organic solvent; an electrolyte salt; and one or more additives selected from a compound represented by the following chemical formula 1.

[0007] [Chemical Formula 1]

[0008]

[0009] R1 to R3 are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C3-C12)cycloalkyl, (C2-C12)heterocycloalkyl, (C6-C12)aryl, (C2-C12)heteroaryl, (C1-C10)alkoxy, (C6-C12)aryloxy, (C2-C10)alkenyloxy, (C2-C10)alkynyloxy, or (C1-C10)alkylcarbonate;

[0010] The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkenyloxy, alkynyloxy and alkylcarbonate of the above R1 to R3 may contain one or more halogen elements;

[0011] R4 can be (C1-C10)alkylene, (C2-C10)alkenylene, (C2-C10)alkynylene, (C3-C12)cycloalkylene, (C2-C12)heterocycloalkylene, (C6-C12)arylene, (C2-C12)heteroarylene, (C1-C10)alkyleneoxy, (C2-C10)alkenyleneoxy, (C2-C10)alkynyleneoxy, (C3-C12)cycloalkyleneoxy, (C6-C12)aryleneoxy, (C2-C12)heteroaryleneoxy, or a combination thereof;

[0012] Y - is *-SO3 - , *-OSO3 - , *-OPO3H - , *-CO2 - or *-OCO2 - and;

[0013] M + is an alkali metal ion, ammonium (NH4 +), Nitrosil (NO + ), triethylamine (Et3N + ), diazanium (N2H5 + ), hydronium (H3O + ), phosphonium (PH4 + ), diphosphonium (P2H5 + ), silyllium (SiH3 + ), or pyridinium;

[0014] X - is a halide ion, cyanide (CN - ), thiocyanate (SCN - ), cyanate (OCN - ), acetate (CH3COO - ), nitrate (NO3 - ), nitrite (NO2) - ), azide (N3 - ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6) - ), trifluoromethanesulfonate (CF3SO3 - ), tetrafluorozirconate (ZrF4 - ), tetrafluoroaluminate (AlF4 - ), difluorophosphate (PO2F2 - ), bisfluorosulfonylimide (FSI) - ) or bistrifluoromethanesulfonylimide (TFSI) - )am.

[0015] The compound represented by the above chemical formula 1 can be represented by the following chemical formula 2.

[0016] [Chemical Formula 2]

[0017]

[0018] (In the above chemical formula 2, R1 to R4, M + and X - is the same as the definition in the above chemical formula 1.)

[0019] The compound represented by the above chemical formula 1 can be represented by the following chemical formula 3.

[0020] [Chemical Formula 3]

[0021]

[0022] (In the above chemical formula 3, R1 to R4 and X - is the same as the definition in the above chemical formula 1.)

[0023] The above R1 to R3 are each independently (C6-C12)aryl, (C6-C12)aryloxy, or (C2-C12)heteroaryl, and R4 is (C1-C4)alkylene, or (C2-C4)alkenylene; X - is F-, nitrate (NO3 - ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6) - ), trifluoromethanesulfonate (CF3SO3 - ) tetrafluorozirconate (ZrF4 - ), tetrafluoroaluminate (AlF4 - ), difluorophosphate (PO2F2 - ), bisfluorosulfonylimide (FSI) - ) or bistrifluoromethanesulfonylimide (TFSI) - ) may be.

[0024] The above additive may be included in an amount of 0.001 to 10 mass% based on the total weight of the non-aqueous electrolyte.

[0025] The above non-aqueous organic solvent may be one or more selected from linear carbonate solvents, cyclic carbonate solvents, linear ester solvents, cyclic ester solvents, ether solvents, ketone solvents, alcohol solvents, and aprotic solvents.

[0026] The above non-aqueous organic solvent may be a combination of a linear carbonate solvent and a cyclic carbonate solvent.

[0027] The above electrolyte salt may be a lithium salt.

[0028] The non-aqueous electrolyte according to one embodiment may further include one or more auxiliary additives selected from a fluorine-containing cyclic carbonate compound, a vinyl-containing cyclic carbonate compound, a vinylene carbonate compound, a cyclic sulfate compound, a sultone compound, a fluorine-containing lithium phosphate compound, a lithium borate compound, a lactone compound, and a sulfonyl imide compound.

[0029] The above auxiliary additive may be included in an amount of 0.01 to 10 wt% based on the total weight of the non-aqueous electrolyte.

[0030] In addition, another aspect of the present invention provides a storage device comprising a positive electrode; a negative electrode; and the non-aqueous electrolyte described above.

[0031] The active material of the positive electrode may include a composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel; or a lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel, and manganese.

[0032] The active material of the above negative electrode may include one or more selected from carbon materials, tin, tin compounds, silicon, silicon compounds, and lithium titanate.

[0033] The active material of the above negative electrode may be lithium metal.

[0034] The above storage device may be a lithium secondary battery.

[0035] In addition, another aspect of the present invention provides a compound represented by the following chemical formula 1.

[0036] [Chemical Formula 1]

[0037]

[0038] (In the above chemical formula 1, R1 to R4, Y - , M + and X -is the same as the definition in the above chemical formula 1.)

[0039] A lithium secondary battery employing a non-aqueous electrolyte according to the present invention can simultaneously improve life characteristics and high-temperature stability while realizing excellent output performance.

[0040] Specifically, the additive included in the non-aqueous electrolyte according to one embodiment has structural characteristics such as high ionic conductivity and solubility, which can maximize battery performance. In addition, it can independently remove hydrofluoric acid and moisture within the electrolyte, effectively suppress side reactions between the battery and the electrolyte, and significantly improve battery life and stability by forming a solid electrolyte interface (SEI) film on the surfaces of the negative and positive electrodes, thereby suppressing the decomposition of organic solvents occurring at a specific voltage. In particular, it can impart excellent stability even to layered, high-capacity cathode materials with a high nickel content.

[0041] In addition, the non-aqueous electrolyte according to the aspect can improve stability by suppressing the formation of dendrites formed on the surface of lithium metal even when a lithium metal negative electrode is adopted as a next-generation battery.

[0042] Figure 1 is a cross-sectional view schematically showing a lithium secondary battery according to one embodiment.

[0043] Figures 2 to 17 are infrared spectroscopy (FT-IR) results of compounds (chemical formulae 5 to 20) according to Examples 1 to 15.

[0044] Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0045] As used herein, the singular forms may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0046] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0047] The term “includes” in this specification is an open-ended description equivalent to expressions such as “comprises,” “contains,” “has,” or “characterizes,” and does not exclude additional elements, materials, or processes not listed.

[0048] One aspect of the present invention provides a non-aqueous electrolyte capable of simultaneously realizing excellent ionic conductivity and electrochemical stability by including a compound of a specific structure as an additive.

[0049] Specifically, the non-aqueous electrolyte according to one aspect may include a non-aqueous organic solvent; an electrolyte salt; and one or more additives selected from a compound represented by the following chemical formula 1.

[0050] [Chemical Formula 1]

[0051]

[0052] (In the above chemical formula 1,

[0053] R1 to R3 are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C12)alkynyl, (C3-C12)cycloalkyl, (C2-C12)heterocycloalkyl, (C6-C12)aryl, (C2-C12)heteroaryl, (C1-C10)alkoxy, (C6-C12)aryloxy, (C2-C10)alkenyloxy, (C2-C10)alkynyloxy, or (C1-C10)alkylcarbonate;

[0054] The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkenyloxy, alkynyloxy and alkylcarbonate of the above R1 to R3 may contain one or more halogen elements;

[0055] R4 can be (C1-C10)alkylene, (C2-C10)alkenylene, (C2-C10)alkynylene, (C3-C12)cycloalkylene, (C2-C12)heterocycloalkylene, (C6-C12)arylene, (C2-C12)heteroarylene, (C1-C10)alkyleneoxy, (C2-C10)alkenyleneoxy, (C2-C10)alkynyleneoxy, (C3-C12)cycloalkyleneoxy, (C6-C12)aryleneoxy, (C2-C12)heteroaryleneoxy, or a combination thereof;

[0056] Y - is *-SO3 - , *-OSO3 - , *-OPO3H - , *-CO2 - or *-OCO2 - and;

[0057] M + is an alkali metal ion, ammonium (NH4 + ), Nitrosil (NO + ), triethylamine (Et3N + ), diazanium (N2H5 + ), hydronium (H3O + ), phosphonium (PH4 + ), diphosphonium (P2H5 + ), silyllium (SiH3 +), or pyridinium;

[0058] X - is a halide ion, cyanide (CN - ), thiocyanate (SCN - ), cyanate (OCN - ), acetate (CH3COO - ), nitrate (NO3 - ), nitrite (NO2) - ), azide (N3 - ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6) - ), trifluoromethanesulfonate (CF3SO3 - ), tetrafluorozirconate (ZrF4 - ), tetrafluoroaluminate (AlF4 - ), difluorophosphate (PO2F2 - ), bisfluorosulfonylimide (FSI) - ) or bistrifluoromethanesulfonylimide (TFSI) - )am.

[0059] A non-aqueous electrolyte according to one aspect can have excellent ionic conductivity and solubility due to the above-described structural features, for example, a compound having both a cationic portion and an anionic portion and an ionic functional group introduced into the cationic portion and anionic portion of the compound, can independently remove hydrofluoric acid and moisture within the electrolyte, and can effectively suppress side reactions between the battery and the electrolyte, thereby improving stability.

[0060] Here, the alkali metal ion is Li + , Na + , K + can mean, and the halide ion is F - , Cl - , Br - , I - can mean .

[0061] For example, in the above chemical formula 1, R1 to R3 are each independently hydrogen, halogen, (C1-C7)alkyl, (C2-C7)alkenyl, (C2-C7)alkynyl, (C3-C12)cycloalkyl, (C2-C12)heterocycloalkyl, (C6-C12)aryl, (C2-C12)heteroaryl, (C1-C7)alkoxy, (C6-C12)aryloxy, (C2-C7)alkenyloxy or (C2-C7)alkynyloxy, or (C1-C7)alkylcarbonate; R4 can be (C1-C7)alkylene, (C2-C7)alkenylene, (C2-C7)alkynylene, (C3-C12)cycloalkylene, (C2-C12)heterocycloalkylene, (C6-C12)arylene, (C2-C12)heteroarylene, (C1-C7)alkyleneoxy, (C2-C7)alkenyleneoxy, (C2-C7)alkynyleneoxy, (C3-C12)cycloalkyleneoxy, (C6-C12)aryleneoxy, (C2-C12)heteroaryleneoxy or a combination thereof.

[0062] For example, in the above chemical formula 1, R1 to R3 are each independently hydrogen, halogen, (C1-C4)alkyl, (C2-C4)alkenyl, (C2-C4)alkynyl, (C3-C12)cycloalkyl, (C2-C12)heterocycloalkyl, (C6-C12)aryl, (C2-C12)heteroaryl, (C1-C4)alkoxy, (C6-C12)aryloxy, (C2-C4)alkenyloxy, (C2-C4)alkynyloxy, or (C1-C4)alkylcarbonate; R4 can be (C1-C4)alkylene, (C2-C4)alkenylene, (C2-C4)alkynylene, (C3-C12)cycloalkylene, (C2-C12)heterocycloalkylene, (C6-C12)arylene, (C2-C12)heteroarylene, (C1-C4)alkyleneoxy, (C2-C4)alkenyleneoxy, (C2-C4)alkynyleneoxy, (C3-C12)cycloalkyleneoxy, (C6-C12)aryleneoxy, (C2-C12)heteroaryleneoxy or a combination thereof.

[0063] For example, in the above chemical formula 1, R1 to R3 may be the same or different and are (C6-12)aryl or (C6-C12)aryloxy, specifically phenyl or phenyloxy; R4 is (C1-C4)alkylene, or (C2-C4)alkenylene, or propylene, or butylene, or propenylene; Y - is *-SO3 - or *-OSO3 - , M+ is an alkali metal ion, and X - may be a halide ion.

[0064] The compound represented by the above chemical formula 1 may be represented by the following chemical formula 2, and more specifically, may be represented by the following chemical formula 3.

[0065] [Chemical Formula 2]

[0066]

[0067] [Chemical Formula 3]

[0068]

[0069] In the above chemical formulas 2 and 3, R1 to R4, M + and X - is the same as the definition in the above chemical formula 1.

[0070] In one embodiment, the additive may be included in an amount of 0.001 wt% or more, or 0.01 wt% or more, or 0.1 wt% or more, or 0.5 wt% or more, or 0.7 wt% or more, based on the total weight of the non-aqueous electrolyte, and may be 10 wt% or less, or 7 wt% or less, or 5 wt% or less, or 3 wt% or less, or a value intermediate therebetween. More specifically, the additive may be included in an amount of 0.001 to 10 wt%, or 0.01 to 10 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.5 to 5 wt%, or 0.7 to 5 wt%. When the above range is satisfied, the effect of simultaneously improving the output characteristics and stability of a lithium secondary battery can be further improved.

[0071] The non-aqueous electrolyte according to one embodiment may further include an auxiliary additive, and the auxiliary additive may be one or two or more selected from a fluorine-containing cyclic carbonate compound, a vinyl-containing cyclic carbonate compound, a vinylene carbonate compound, a cyclic sulfate compound, a sultone compound, a fluorine-containing lithium phosphate compound, a lithium borate compound, a lactone compound, and a sulfonyl imide compound.

[0072] The above fluorine-containing cyclic carbonate compound may have a 5- to 7-membered cyclic structure, and may have a fluorine atom directly bonded to a carbon atom, or a fluorine-substituted alkyl group bonded to it. For example, it may include fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), and trifluoroethylene carbonate (TFPC).

[0073] The above vinyl group-containing cyclic carbonate compound may include, for example, vinyl ethylene carbonate (VES), and the above vinylidene carbonate compound may include, for example, vinylene carbonate (VC).

[0074] The cyclic sulfate compound may have a 5- to 7-membered cyclic structure, and may include, for example, ethylene sulfate (ESA), trimethylene sulfate (TMS), methyltrimethylene sulfate (MTMS), and 1,3-propanediol cyclic sulfate. In addition, the cyclic sulfate compound may be the bicyclic sulfate compound, and for example, the bicyclic sulfate compound may include 2,4,8,10-tetraoxa-3,9-dithiaspiro[5.5]undecane,3,3,9,9-tetraoxide, 4,4'-bi(1,3,2-dioxathiolane)]2,2,2',2'-tetraoxide, etc.

[0075] The above sultone compound may have a 5- to 7-membered cyclic structure and may include ethane sultone, 1,3-propane sultone, butane sultone, and propene sultone (prop-1-ene-1,3-sultone).

[0076] When the above auxiliary additive is further included, the auxiliary additive may be included in an amount of 0.01 to 10 wt%, or 0.01 to 5 wt%, 0.01 to 3 wt%, or 0.01 to 1 wt% based on the total weight of the non-aqueous electrolyte. In addition, the content weight ratio (A:B) of the additive (A) represented by the above chemical formula 1 and the auxiliary additive (B) may be 1:0.1 to 10, or 1:0.1 to 7, or 1:0.5 to 5.

[0077] The above non-aqueous organic solvent may be one or more selected from carbonate solvents, ester solvents (carboxylate solvents), ether solvents, ketone solvents, alcohol solvents, and aprotic solvents.

[0078] The carbonate solvent may include a linear carbonate solvent and a cyclic carbonate solvent. The linear carbonate solvent may include, for example, dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate, ethyl propyl carbonate, dipropyl carbonate, etc., and the cyclic carbonate solvent may include, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, etc.

[0079] The ester solvent may include a linear ester solvent and a cyclic ester solvent. The linear ester solvent may include, for example, methyl propionate, ethyl propionate, propyl acetate, butyl acetate, ethyl acetate, etc., and the cyclic ester solvent may include, for example, butyrolactone (g-butyrolactone), caprolactone, g-valerolactone, etc.

[0080] The above ether solvent may include dibutyl ether, tetraethylene glycol dimethyl ether (TEGDME), diethylene glycol dimethyl ether (DEGDME), dimethoxyethane, tetrahydrofuran (THF), and 2-methyltetrahydrofuran.

[0081] The ketone solvent may include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, diethyl ketone, cyclohexanone, methyl cyclohexanone, acetylacetone, etc., and the alcohol solvent may include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, etc.

[0082] The aprotic solvent may include at least one of nitrile solvents such as acetonitrile, succinonitrile, adiponitrile, and sebaconitrile; amide solvents such as dimethylformamide, dimethylacetamide, and 1-methyl-2-pyrrolidone (NMP); dioxolane solvents such as 1,3-dioxolane; and sulfolane solvents.

[0083] Specifically, the non-aqueous organic solvent may be a combination of a linear carbonate solvent and a cyclic carbonate solvent, and more specifically, may be a combination of one or more selected from ethylene carbonate (EC); and ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).

[0084] The above electrolyte salt may be a lithium salt, and the above lithium salt (Li + X - ) may be used, and a conventional lithium salt used in the relevant technical field may be used, and as a non-limiting example, the anion (X) of the lithium salt - ) is F - , Cl - , Br - , I - , NO3 - , N(CN)2 - , BF4 - , ClO4 - , PF6 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , CF3SO3 - , CF3CF2SO3 - , (CF3SO2)2N - , (FSO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3(CF2)7SO3 - , CF3CO2 - , CH3CO2 - , SCN - and (CF3CF2SO2)2N - It could be the back.

[0085] Specifically, the lithium salt may be, but is not limited to, LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(C2F5SO2)2, LiN(CF3SO2)2, CF3SO3Li, LiC(CF3SO2)3.

[0086] The lithium salt may be included in the organic solvent at a concentration of 0.01 to 5 M, preferably 0.01 to 2 M, and is preferably included within the concentration range because smooth movement of lithium ions and / or electrons can be expected during charging and discharging of the battery, but is not necessarily limited thereto.

[0087] In addition, one aspect of the present invention provides a storage device including the non-aqueous electrolyte.

[0088] Hereinafter, a storage device according to one aspect will be specifically described, but it is obvious that it can be manufactured with a structure known in the art using a manufacturing method and materials common in the art, except that it includes the non-aqueous electrolyte according to one aspect.

[0089] The above storage device may be a general term for a device that is composed of a positive electrode, a negative electrode, and a separator and includes a non-aqueous electrolyte and can store and release electricity through a reversible or irreversible action, and specifically may be a lithium battery, and the lithium battery may be a lithium primary battery, a lithium secondary battery, a lithium metal battery, a lithium-sulfur battery, a lithium-air battery, and more specifically may be a lithium secondary battery or a lithium metal battery.

[0090] The above positive electrode may include a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector.

[0091] Non-limiting examples of the positive electrode current collector may include a foil made of aluminum, nickel, or a combination thereof, and the positive electrode active material layer may further include a positive electrode active material, a binder, and a conductive material as needed.

[0092] The above cathode active material may be a conventional cathode active material used in this technical field, and non-limiting examples thereof include lithium cobalt oxide composite oxide (LiCoO2), spinel crystal type lithium manganate composite oxide (LiMn2O4), lithium manganate composite oxide (LiMnO2), lithium nickelate composite oxide (LiNiO2), lithium manganese phosphate (LiMnPO4), lithium cobalt phosphate (LiCoPO4), lithium nickel phosphate (LiNiPO4), lithium iron phosphate (LiFePO4), LiFeMnPO4, lithium iron pyrophosphate (Li2FeP2O7), lithium niobate composite oxide (LiNbO2), lithium ironate composite oxide (LiFeO2), lithium magnesiumate composite oxide (LiMgO2), lithium cuprate composite oxide (LiCuO2), lithium zincate composite oxide (LiZnO2), Lithium molybdate composite oxide (LiMoO2), lithium tantalate composite oxide (LiTaO2), lithium tungstate composite oxide (LiWO2), lithium permanganate nickel cobalt composite oxide (xLi2MnO3(1-x)LiMn1-y-zNiyCozO2), lithium nickel cobalt aluminum composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O2) and preferably a composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel; or a lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel, and manganese.

[0093] Specifically, the positive electrode active material may be a composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel, and may be LiNiO2, LiCoO2, LiMnO2, LiMn2O4, or a nickel-cobalt-manganese-based positive electrode active material represented by the following chemical formula 11.

[0094] [Chemical Formula 11]

[0095] LiNi aCo b Mn c O2

[0096] In the above chemical formula 11, a+b+c=1, and 0.5 <a<1.0, 0<b<0.5, 0<c<0.5이다.

[0097] For example, a+b+c=1, 0.6≤a≤0.9, and 0 <b≤0.2, 0<c≤0.2일 수 있다.

[0098] Specifically, the cathode active materials according to the aspect are LiCoO2, LiMn2O4, LiNiO2, LiCo 1-x Ni x O2(0.01 <x<1), LiCo1 / 3Ni1 / 3Mn1 / 3O2, LiCo 0.98 Mg 0.02 O2, LiNi1 / 2Mn3 / 2O4, LiNi 0.6 Co 0.2 Mn 0.2 O 2, LiNi 0.8 Co 0.1 Mn 0.1 O2, , LiNi 0.88 Co 0.06 Mn 0.06 O2, LiNi 0.9 Co 0.05 Mn 0.05 O2, or a mixture thereof, but is not limited thereto. In particular, the non-aqueous electrolyte according to one embodiment is LCM811 (LiNi 0.88 Co 0.06 Mn 0.06 It can also provide excellent stability to high-capacity cathode materials with low stability, such as O2.

[0099] In addition, the cathode active material according to one aspect may be a lithium-containing olivine-type phosphate such as lithium manganese phosphate (LiMnPO4), lithium cobalt phosphate (LiCoPO4), lithium nickel phosphate (LiNiPO4), lithium iron phosphate (LiFePO4), LiFeMnPO4, etc., but is not necessarily limited thereto.

[0100] The conductive material may include, but is not limited to, carbon black such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, etc.; conductive fibers such as carbon fibers and metal fibers; metal powders such as fluorinated carbon, aluminum, and nickel powders; conductive whiskeys such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives, but is not particularly limited as long as it has conductivity and does not cause chemical changes in the battery.

[0101] The above binder polymer may include one or more selected from the group consisting of nitrile butadiene rubber, polyethylene glycol, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, polypropylene oxide, polydimethylsiloxane, polyvinylidene fluoride, polyvinylidene carbonate, and polyvinylpyrrolidinone, and preferably one or more selected from the group consisting of polyvinylidene fluoride, polyvinylidene carbonate, and polyethylene glycol, but is not limited thereto.

[0102] The above negative electrode may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.

[0103] Non-limiting examples of the negative electrode current collector include a foil made of copper, gold, nickel, or a copper alloy or a combination thereof, and the negative electrode active material layer may further include a negative electrode active material, a binder, and a conductive material as needed.

[0104] The negative electrode active material may be a conventional negative electrode active material used in this technical field, and non-limiting examples thereof include any one carbon material selected from among soft carbon, hard carbon, artificial graphite, natural graphite, expanded graphite, carbon fiber, non-graphitizable carbon, carbon black, carbon nanotubes, acetylene black, Ketjen black, graphene, fullerene, activated carbon, and meso carbon microbeads; any one metal selected from among silicon, tin, lithium, aluminum, silver, bismuth, indium, germanium, lead, platinum, titanium, zinc, manganese, cadmium, cerium, copper, cobalt, nickel, and iron; an alloy including two or more of the above metals; and an oxide of one or more of the above metals; or lithium metal or a lithium alloy.

[0105] In particular, the non-aqueous electrolyte according to one embodiment can impart excellent stability to the lithium metal negative electrode. Specifically, the non-aqueous electrolyte according to one embodiment can suppress the decomposition of organic solvents occurring at a specific voltage by forming a solid electrolyte interface (SEI) film on the negative electrode surface and suppress the formation of dendrites on the lithium metal surface.

[0106] In addition, one aspect of the present invention provides a compound represented by the following chemical formula 1.

[0107] [Chemical Formula 1]

[0108]

[0109] (In the above chemical formula 1,

[0110] R1 to R3 are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C12)alkynyl, (C3-C12)cycloalkyl, (C2-C12)heterocycloalkyl, (C6-C12)aryl, (C2-C12)heteroaryl, (C1-C10)alkoxy, (C2-C10)alkenyloxy, (C2-C10)alkynyloxy or (C1-C10)alkylcarbonate;

[0111] The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkenyloxy, alkynyloxy and alkylcarbonate of the above R1 to R3 may contain one or more halogen elements;

[0112] R4 can be (C1-C10)alkylene, (C2-C10)alkenylene, (C2-C10)alkynylene, (C3-C12)cycloalkylene, (C2-C12)heterocycloalkylene, (C6-C12)arylene, (C2-C12)heteroarylene, (C1-C10)alkyleneoxy, (C2-C10)alkenyleneoxy, (C2-C10)alkynyleneoxy, (C3-C12)cycloalkyleneoxy, (C6-C12)aryleneoxy, (C2-C12)heteroaryleneoxy, or a combination thereof;

[0113] Y - is *-SO3 - , *-OSO3 - , *-OPO3H - , *-CO2 - or *-OCO2 - and;

[0114] M + is an alkali metal ion, ammonium (NH4 + ), Nitrosil (NO + ), triethylamine (Et3N + ), diazanium (N2H5 + ), hydronium (H3O + ), phosphonium (PH4 + ), diphosphonium (P2H5 + ), silyllium (SiH3 + ), or pyridinium;

[0115] X - is a halide ion, cyanide (CN - ), thiocyanate (SCN - ), cyanate (OCN - ), acetate (CH3COO - ), nitrate (NO3 - ), nitrite (NO2) - ), azide (N3- ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6) - ), trifluoromethanesulfonate (CF3SO3 - ), tetrafluorozirconate (ZrF4 - ), tetrafluoroaluminate (AlF4 - ), bisfluorosulfonylimide (FSI) - ) or bistrifluoromethanesulfonylimide (TFSI) - )am.

[0116] The compound represented by the above chemical formula 1 according to one aspect can be used as an additive for a non-aqueous electrolyte solution because it has the structural characteristics described above.

[0117] Specifically, the compound represented by the above chemical formula 1 can realize excellent ionic conductivity and solubility by being a compound having both a cation part and an anion part and by introducing ionic functional groups to the cation part and anion part of the compound. In addition, by forming a SEI (solid electrolyte interface) film on both the negative and positive electrode surfaces, it can suppress the decomposition of organic solvents occurring at a specific voltage, thereby significantly improving the battery life and stability. In addition, it can play a role in independently removing hydrofluoric acid and moisture within the electrolyte, and can effectively suppress side reactions between the battery and the electrolyte.

[0118] Hereinafter, the above-described implementation examples will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0119] <Physical property evaluation method>

[0120] 1. Initial discharge capacity

[0121] The lithium secondary batteries manufactured in the examples and comparative examples were charged for 3 hours in a constant temperature bath at 25°C at a constant current and constant voltage of 1C to a final voltage of 4.2V, and then discharged to a final voltage of 3.0V under a constant current of 1C, and the initial discharge capacity (C1) was measured.

[0122] 2. Capacity retention rate

[0123] For the lithium secondary batteries manufactured in the examples and comparative examples, the charging and discharging process was repeated 500 times according to the initial discharge capacity measurement method described above, and the 500th discharge capacity (C2) was measured and the capacity retention rate was calculated.

[0124] Capacity retention rate (%) = C2 / C1 X 100

[0125] 3. Output characteristics

[0126] The lithium secondary batteries manufactured in the examples and comparative examples were charged at 1C CC / CV (4.2 V CUT-OFF) and then discharged at 2C CC up to 150 mA. Thereafter, the C-rate was varied at 0.5C, 1C, 2C, and 4C, and the discharge and recharge were performed for 10 seconds each, and the DCIR was measured. The output (pulse power) value was calculated from the measured DCIR value.

[0127] <Additive Manufacturing>

[0128] [Example 1]

[0129] [Chemical Formula 5]

[0130]

[0131] Into a reactor equipped with a cooler on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 46.6 g of 1,3-Propanesultone, and 9.9 g of lithium fluoride (LiF) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained white powder was further dried under vacuum at 60°C for 24 hours to obtain an additive having the chemical formula 5 as a white solid (yield 70%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 2.

[0132] [Example 2]

[0133] [Chemical Formula 6]

[0134]

[0135] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 46.6 g of 1,3-Propanesultone, and 46.4 g of lithium difluorophosphate (LiPO2F2) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 164.6 g of an additive having the chemical formula 6 as a colorless transparent liquid (yield 88%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 3.

[0136] [Example 3]

[0137] [Chemical Formula 7]

[0138]

[0139] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 46.6 g of 1,3-Propanesultone, and 26.3 g of lithium nitrate (LiNO3) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and then filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 158.5 g of an additive having the chemical formula 7 as a colorless transparent liquid (yield 92%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 4.

[0140] [Example 4]

[0141] [Chemical Formula 8]

[0142]

[0143] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 46.6 g of 1,3-Propanesultone, and 35.8 g of lithium tetrafluoroborate (LiBF4) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through reduced pressure distillation, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 165.4 g of an additive having the chemical formula 8 as a colorless transparent liquid (yield 91%). The structure was confirmed using an infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 5.

[0144] [Example 5]

[0145] [Chemical Formula 9]

[0146]

[0147] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 46.6 g of 1,3-Propanesultone, and 59.5 g of lithium trifluoromethylsulfonate (CF3SO3Li) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 193.0 g of an additive having the chemical formula 9 as a colorless transparent liquid (yield 94%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 6.

[0148] [Example 6]

[0149] [Chemical Formula 10]

[0150]

[0151] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 46.6 g of 1,3-Propanesultone, and 41.9 g of lithium tetrafluoroaluminate (LiAlF4) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 157.8 g of an additive having the chemical formula 10 as a colorless transparent liquid (yield 82%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 7.

[0152] [Example 7]

[0153] [Chemical Formula 11]

[0154]

[0155] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 45.8 g of propene 1,3-sulfone, and 41.2 g of lithium difluorophosphate (LiPO2F2) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 145.3 g of an additive having the chemical formula 11 structure as a colorless transparent liquid (yield 78%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 8.

[0156] [Example 8]

[0157] [Chemical Formula 12]

[0158]

[0159] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 45.8 g of propene 1,3-sulfone, and 26.3 g of lithium nitrate (LiNO3) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 157.8 g of an additive having the chemical formula 12 as a colorless transparent liquid (yield 92%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 9.

[0160] [Example 9]

[0161] [Chemical Formula 13]

[0162]

[0163] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 45.8 g of propene 1,3-sulfone, and 35.8 g of lithium tetrafluoroborate (LiBF4) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 166.5 g of an additive having the chemical formula 13 as a colorless transparent liquid (yield 92%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 10.

[0164] [Example 10]

[0165] [Chemical Formula 14]

[0166]

[0167] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 45.8 g of propene 1,3-sulfonate, and 59.5 g of lithium trifluoromethylsulfonate (CF3SO3Li) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 169.8 g of an additive having the chemical formula 14 as a colorless transparent liquid (yield 83%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 11.

[0168] [Example 11]

[0169] [Chemical Formula 15]

[0170]

[0171] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphine, 45.8 g of propene 1,3-sulfone, and 42.0 g of lithium tetrafluoroaluminate (LiAlF4) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 144.0 g of an additive having the chemical formula 15 as a colorless transparent liquid (yield 77%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 12.

[0172] [Example 12]

[0173] [Chemical Formula 16]

[0174]

[0175] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphite ((C6H5-O)3-P), 39.4 g of propane sultone (1,3-Propanesultone), and 34.8 g of lithium difluorophosphate (LiPO2F2) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 135.8.0 g of an additive having the chemical formula 16 as a colorless transparent liquid (yield 78%). The structure was confirmed using an infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 13.

[0176] [Example 13]

[0177] [Chemical Formula 17]

[0178]

[0179] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphite ((C6H5-O)3-P), 39.4 g of propane sultone, and 22.2 g of lithium nitrate (LiNO3) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and then filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 130.9 g of an additive having the chemical formula 17 as a colorless transparent liquid (yield 81%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 14.

[0180] [Example 14]

[0181] [Chemical Formula 18]

[0182]

[0183] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenyl phosphite ((C6H5-O)3-P), 39.4 g of propane sultone (1,3-Propanesultone), and 30.2 g of lithium tetraborate (LiBF4) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 156.0 g of an additive having the chemical formula 18 structure as a colorless transparent liquid (yield 92%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 15.

[0184] [Example 15]

[0185] [Chemical Formula 19]

[0186]

[0187] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenyl phosphite ((C6H5-O)3-P), 39.4 g of propane sultone (1,3-Propanesultone), and 50.3 g of lithium trifluoromethyl sulfonate (CF3SO3Li) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 146.3 g of an additive having the chemical formula 19 structure as a colorless transparent liquid (yield 77%). The structure was confirmed using infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 16.

[0188] [Example 16]

[0189] [Chemical Formula 20]

[0190]

[0191] Into a reactor equipped with a condenser on top, 1,000 g of toluene solvent, 100 g of triphenylphosphite ((C6H5-O)3-P), 39.4 g of propane sultone (1,3-Propanesultone), and 35.4 g of lithium tetrafluoroaluminate (LiAlF4) were charged, heated to a temperature at which the solvent evaporated, stirred for 24 hours, and after the reaction was completed, allowed to stand, naturally cooled to room temperature, and filtered to remove the solid content. The solvent was removed from the remaining solution through distillation under reduced pressure, and the obtained colorless transparent liquid was further dried under vacuum at 60°C for 24 hours to obtain 127.6 g of an additive having the chemical formula 20 structure as a colorless transparent liquid (yield 73%). The structure was confirmed using an infrared absorption spectroscopy (FT-IR spectrometer), and the results are shown in Fig. 17.

[0192] <Manufacturing of non-aqueous electrolytes and lithium secondary batteries>

[0193] [Example 17]

[0194] Manufacturing of non-aqueous electrolyte

[0195] A 1.0 M LiPF6 solution was prepared using a mixed solvent of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) in a ratio of 3:7 (v / v). The additive (chemical formula 5) obtained in Example 1 was added to the LiPF6 solution in an amount of 0.5 wt% based on the total weight of the electrolyte (100 wt%), thereby preparing a non-aqueous electrolyte.

[0196] Lithium secondary battery manufacturing

[0197] NCM811(Li(Ni 0.8 Co 0.1 Mn 0.1 )O2), acetylene black and polyvinylidene fluoride (PVDF) were dissolved and mixed in N-methyl-2-pyrrolidone (NMP) at a weight ratio of 94:3:2 to prepare a positive electrode mixture paste. This positive electrode mixture paste was applied to one side of an aluminum foil (current collector, 20 ㎛ thick), dried, pressurized, and stamped into a predetermined size to produce a positive electrode sheet. The density of the part of the positive electrode excluding the current collector was 3.58 g / cm 3 It was.

[0198] Also, crystalline artificial graphite (d 002 =0.335 nm), acetylene black, and polyvinylidene fluoride were dissolved and mixed in N-methyl-2-pyrrolidone at a ratio of 92:1:7 to prepare a negative electrode mixture paste. This negative electrode mixture paste was applied to one side of a copper foil (current collector, thickness: 15 ㎛), dried, and pressurized to produce a negative electrode sheet by stamping it into a predetermined size. The density of the part of the negative electrode excluding the current collector was 1.5 g / cm. 3 It was.

[0199] The positive electrode sheet, separator (microporous polyethylene film), and negative electrode sheet obtained above were sequentially laminated, and the non-aqueous electrolyte obtained above was injected and sealed to manufacture a coin 3048 type lithium secondary battery (Fig. 1). The electrochemical properties of the manufactured lithium secondary battery were evaluated using the method described in the above physical property measurement method, and the results are shown in Table 2 below.

[0200] [Examples 18 to 37 and Comparative Examples 1 to 9]

[0201] When manufacturing a non-aqueous electrolyte, the same procedure as Example 17 was followed, except that the types and contents of additives were changed as shown in Table 1 below. The electrochemical properties of the manufactured lithium secondary battery were evaluated using the method described in the above property measurement method, and the results are shown in Table 2 below.

[0202] Additive Auxiliary Additive Type Content Type Content Example 17 Chemical Formula 50.5 wt%--Example 18 Chemical Formula 51.0 wt%--Example 19 Chemical Formula 52.0 wt%--Example 20 Chemical Formula 51.0 wt% B-11.0 wt% Example 21 Chemical Formula 51.0 wt% B-21.0 wt% Example 22 Chemical Formula 51.0 wt% B-31.0 wt% Example 23 Chemical Formula 61.0 wt%--Example 24 Chemical Formula 71.0 wt%--Example 25 Chemical Formula 81.0 wt%--Example 26 Chemical Formula 91.0 wt%--Example 27 Chemical Formula 101.0 wt%--Example 28 Chemical Formula 111.0 wt%--Example 29 Chemical Formula 121.0 wt%--Example 30 Chemical Formula 131.0 wt%--Example 31 Chemical Formula 141.0 wt%--Example 32 Chemical Formula 151.0 wt%--Example 33 Chemical Formula 161.0 wt%--Example 34 Chemical Formula 171.0 wt%--Example 35 Chemical Formula 181.0 wt%--Example 36 Chemical Formula 191.0 wt%--Example 37 Chemical Formula 201.0 wt%--Comparative Example 1A-10.5 wt%--Comparative Example 2A-11.0 wt%--Comparative Example 3A-21.0 wt%--Comparative Example 4A-31.0 wt%--Comparative Example 5A-41.0 wt%--Comparative Example 6A-11.0 Weight % B-11.0 Weight % Comparative Example 7A-21.0 Weight % B-11.0 Weight % Comparative Example 8A-31.0 Weight % B-11.0 Weight % Comparative Example 9A-41.0 Weight % B-11.0 Weight % A-1: ​​Lithium difluorophosphate A-2: Lithium tetrafluorophosphate A-3: Lithium difluoro(bisoxalato)phosphate (LIDFBOP) A-4: Lithium bis(oxalato)borate B-1: Vinylene carbonate B-2: Vinyl ethylene carbonate B-3: Fluoroethylene carbonate

[0203] 25°C room temperature life characteristics 25°C output characteristics Initial capacity (C1, mAh) 500 cycles capacity (C2, mAh) Capacity retention rate (%) Output (W) Example 17 297.3 280.194.262.3 Example 18 298.3 284.695.465.7 Example 19 298.7 284.795.364.8 Example 20 299.1 286.295.765.4 Example 21 299.2 286.095.665.1 Example 22 298.9 285.495.565.6 Example 23 297.6 280.194.266.3 Example 24 298.7 284.695.465.7 Example 25 298.5 284.795.363.8 Example 26 299.4 286.295.766.4 Example 27 299.7 286.0 95.664.1 Example 28 298.5 285.4 95.567.6 Example 29 298.6 287.796.365.7 Example 30 298.7 286.5 95.966.3 Example 31 298.8 284.395.167.2 Example 32 298.4 282.794.766.3 Example 33 298.3 284.395.366.4 Example 34 298.2 283.795.166.7 Example 35298.6285.695.665.5 Example 36298.7286.796.065.4 Example 37298.8287.596.264.7 Comparative Example 1298.3254.485.354.7 Comparative Example 2297.5242.881.662.3 Comparative Example 3297.3242.878.952.6 Comparative Example 4297.6252.184.760.9 Comparative Example 5297.7253.685.256.2 Comparative Example 6298.2273.491.760.2 Comparative Example 7298.4256.085.855.4 Comparative Example 8298.1270.490.758.8Comparison example 9298.1267.789.859.7

[0204] Referring to Table 2 above, it can be seen that the lithium secondary battery according to the present invention includes compounds of chemical formulae 5 to 20 as electrolyte additives, and thus the initial discharge capacity, life characteristics, and output characteristics are all improved compared to the lithium secondary battery of the comparative examples using the existing commercialized electrolyte additives. In particular, it can be seen that the examples using the additives of chemical formulae 5 to 20 alone achieve significantly improved life characteristics and output characteristics compared to the comparative examples 1 to 9 in which the auxiliary additive is added to the existing electrolyte additive.

[0205] 1: Positive can

[0206] 2: Negative can

[0207] 3: Bipolar

[0208] 4: Membrane

[0209] 5: Cathode

[0210] 6: Gasket

[0211] 7: Spacer disc

[0212] 8: Spring

Claims

1. Non-aqueous organic solvent; electrolyte salt; and A non-aqueous electrolyte comprising one or more additives selected from compounds represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1 to R3 are each independently hydrogen, halogen, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C3-C12)cycloalkyl, (C2-C12)heterocycloalkyl, (C6-C12)aryl, (C2-C12)heteroaryl, (C1-C10)alkoxy, (C6-C12)aryloxy, (C2-C10)alkenyloxy, (C2-C10)alkynyloxy or (C1-C10)alkylcarbonate; The alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl, alkoxy, aryloxy, alkenyloxy, alkynyloxy and alkylcarbonate of the above R1 to R3 may contain one or more halogen elements; R4 can be (C1-C10)alkylene, (C2-C10)alkenylene, (C2-C10)alkynylene, (C3-C12)cycloalkylene, (C2-C12)heterocycloalkylene, (C6-C12)arylene, (C2-C12)heteroarylene, (C1-C10)alkyleneoxy, (C2-C10)alkenyleneoxy, (C2-C10)alkynyleneoxy, (C3-C12)cycloalkyleneoxy, (C6-C12)aryleneoxy, (C2-C12)heteroaryleneoxy or a combination thereof; Y - is *-SO3 - , *-OSO3 - , *-OPO3H - , *-CO2 - or *-OCO2 - and; M + is an alkali metal ion, ammonium (NH4 + ), Nitrosil (NO + ), triethylamine (Et3N + ), diazanium (N2H5 + ), hydronium (H3O + ), phosphonium (PH4 + ), diphosphonium (P2H5 + ), silyllium (SiH3 + ), or pyridinium; X - is a halide ion, cyanide (CN - ), thiocyanate (SCN - ), cyanate (OCN - ), acetate (CH3COO - ), nitrate (NO3 - ), nitrite (NO2) - ), azide (N3 - ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6) - ), trifluoromethanesulfonate (CF3SO3 - ), tetrafluorozirconate (ZrF4 - ), tetrafluoroaluminate (AlF4 - ), difluorophosphate (PO2F2 - ), bisfluorosulfonylimide (FSI) - ) or bistrifluoromethanesulfonylimide (TFSI) - )am.

2. In paragraph 1, The compound represented by the above chemical formula 1 is a non-aqueous electrolyte represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R1 to R4, M + and X - is the same as the definition in paragraph 1 above.

3. In paragraph 1, A non-aqueous electrolyte, wherein the compound represented by the above chemical formula 1 is represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, R1 to R4 and X - is the same as the definition in paragraph 1 above.

4. In paragraph 1, R1 to R3 are each independently (C6-C12)aryl, (C6-C12)aryloxy, or (C2-C12)heteroaryl, and R4 is (C1-C4)alkylene, or (C2-C4)alkenylene; X - is F - , nitrate (NO3) - ), tetrafluoroborate (BF4 - ), hexafluorophosphate (PF6) - ), trifluoromethanesulfonate (CF3SO3 - ) tetrafluorozirconate (ZrF4 - ), tetrafluoroaluminate (AlF4 - ), difluorophosphate (PO2F2 - ), bisfluorosulfonylimide (FSI) - ) or bistrifluoromethanesulfonylimide (TFSI) - ) non-aqueous electrolyte.

5. In paragraph 1, A non-aqueous electrolyte, wherein the above additive is contained in an amount of 0.001 to 10 mass% based on the total weight of the non-aqueous electrolyte.

6. In paragraph 1, A non-aqueous electrolyte, wherein the non-aqueous organic solvent is one or more selected from linear carbonate solvents, cyclic carbonate solvents, linear ester solvents, cyclic ester solvents, ether solvents, ketone solvents, alcohol solvents, and aprotic solvents.

7. In paragraph 6, A non-aqueous electrolyte in which the above non-aqueous organic solvent is a combination of a linear carbonate solvent and a cyclic carbonate solvent.

8. In paragraph 1, The above electrolyte salt is a non-aqueous electrolyte that is a lithium salt.

9. In paragraph 1, A non-aqueous electrolyte further comprising one or more auxiliary additives selected from a fluorine-containing cyclic carbonate compound, a vinyl-containing cyclic carbonate compound, a vinylene carbonate compound, a cyclic sulfate compound, a sultone compound, a fluorine-containing lithium phosphate compound, a lithium borate compound, a lactone compound, and a sulfonyl imide compound.

10. In paragraph 9, A non-aqueous electrolyte, wherein the above auxiliary additive is contained in an amount of 0.01 to 10 wt% based on the total weight of the non-aqueous electrolyte.

11. A storage device comprising: a positive electrode; a negative electrode; and a non-aqueous electrolyte selected from any one of claims 1 to 10.

12. In paragraph 11, A storage device, wherein the active material of the positive electrode comprises a composite metal oxide with lithium containing one or more selected from cobalt, manganese, and nickel; or a lithium-containing olivine-type phosphate containing one or more selected from iron, cobalt, nickel, and manganese.

13. In paragraph 11, A storage device, wherein the active material of the negative electrode includes one or more selected from carbon materials, tin, tin compounds, silicon, silicon compounds, and lithium titanate.

14. In paragraph 11, A storage device in which the active material of the above negative electrode is lithium metal.

15. In paragraph 11, The above storage device is a storage device that is a lithium secondary battery.

16. A compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, R1 to R4, Y - , M + and X - is the same as the definition in paragraph 1 above.

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