WO2020111633A1 - Electrolyte solution composition and secondary battery using same - Google Patents

Electrolyte solution composition and secondary battery using same Download PDF

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Publication number
WO2020111633A1
WO2020111633A1 PCT/KR2019/015857 KR2019015857W WO2020111633A1 WO 2020111633 A1 WO2020111633 A1 WO 2020111633A1 KR 2019015857 W KR2019015857 W KR 2019015857W WO 2020111633 A1 WO2020111633 A1 WO 2020111633A1
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Prior art keywords
electrolyte composition
formula
secondary battery
compound represented
carbonate
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PCT/KR2019/015857
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French (fr)
Korean (ko)
Inventor
송관욱
금중한
이성철
최한영
Original Assignee
동우 화인켐 주식회사
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Priority claimed from KR1020190090420A external-priority patent/KR102138128B1/en
Application filed by 동우 화인켐 주식회사 filed Critical 동우 화인켐 주식회사
Priority to EP19891029.1A priority Critical patent/EP3890092A4/en
Priority to JP2021529842A priority patent/JP7194281B2/en
Priority to US17/296,461 priority patent/US20210399343A1/en
Priority to CN201980077640.3A priority patent/CN113169376A/en
Publication of WO2020111633A1 publication Critical patent/WO2020111633A1/en

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte composition and a secondary battery using the same, and more particularly, to an electrolyte composition having an excellent SEI film forming ability and HF removal ability and having improved lifespan characteristics and high temperature stability, and a secondary battery using the same.
  • lithium ions from the positive electrode active material such as lithium metal oxide move to the negative electrode active material and are inserted between the layers of the negative electrode active material.
  • the electrolyte composition and the materials constituting the negative electrode active material react on the surface of the negative electrode active material to form a kind of protective electrode, a Solid Electrolyte Interface (SEI) film, on the surface of the negative electrode active material.
  • SEI Solid Electrolyte Interface
  • an organic solvent molecule having a large molecular weight moving with lithium ions in the electrolyte composition is inserted between the layers of the negative electrode active material to prevent the negative electrode structure from being destroyed. Therefore, by preventing contact between the electrolyte composition and the negative electrode active material, decomposition of the electrolyte composition does not occur, and the amount of lithium ions in the electrolyte composition is reversibly maintained to maintain stable charge and discharge.
  • a cyclic fluorocarbonate-based compound such as fluoroethylene carbonate (FEC) is a compound that is widely used as a co-solvent while being used as a negative electrode film forming agent for lithium ion batteries due to its excellent ability to form a SEI film on the negative electrode surface [Korea] See Patent Registration No. 10-0977973].
  • FEC fluoroethylene carbonate
  • FEC can decompose in the electrolyte to produce hydrofluoric acid (HF).
  • HF can be decomposed during charge and discharge to release hydrogen gas. Especially at high temperatures, these phenomena may intensify and cause swelling or, if severe, an explosion.
  • HF is acidic and may cause corrosion of the electrode.
  • One object of the present invention is to provide an electrolyte composition having excellent SEI film formation ability and HF removal ability, and improved lifespan characteristics and high temperature stability.
  • Another object of the present invention is to provide a secondary battery using the electrolyte composition.
  • the present invention provides an electrolyte composition
  • a compound represented by the following formula (1) a compound represented by the following formula (1), a cyclic fluoro carbonate-based compound and a non-aqueous solvent.
  • R is a hydrogen atom or Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y ,
  • x, y and z are each independently an integer from 0 to 3.
  • R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y
  • x, y and z can each independently be an integer from 0 to 3 have.
  • the compound represented by Chemical Formula 1 may be included in an amount of 0.05 to 5% by weight based on 100% by weight of the total electrolyte composition.
  • the cyclic fluoro carbonate-based compound may include fluoroethylene carbonate.
  • the cyclic fluoro carbonate-based compound may be included in an amount of 0.5 to 30% by weight based on 100% by weight of the total electrolyte composition.
  • the mixing ratio of the compound represented by Chemical Formula 1 and the cyclic fluoro carbonate compound may be 1:1 to 1:20.
  • the electrolyte composition may further include a lithium salt.
  • the present invention provides a secondary battery comprising the electrolyte composition.
  • the secondary battery may be a lithium secondary battery.
  • the electrolyte composition according to the present invention has an excellent SEI film forming ability by including a cyclic fluorocarbonate-based compound and a propane sulfone compound substituted with a specific substituent, and has excellent room temperature life characteristics when applied to a battery, and output can be improved.
  • the electrolyte composition according to the present invention has excellent HF removal ability, and thus has excellent life characteristics even at high temperatures, and can improve durability by improving high temperature stability.
  • One embodiment of the present invention relates to an electrolyte composition
  • an electrolyte composition comprising a compound represented by the following formula (1), a cyclic fluoro carbonate-based compound and a non-aqueous solvent.
  • R is a hydrogen atom or Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y ,
  • x, y and z are each independently an integer from 0 to 3.
  • R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y
  • x, y and z can each independently be an integer from 0 to 3 have.
  • the compound represented by Formula 1 may be a compound represented by any one of the following Formulas 2 to 9.
  • the compound represented by Chemical Formula 1 is excellent in reactivity with HF, thereby removing HF present in the electrolyte composition, thereby improving stability, particularly high temperature stability.
  • R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y
  • x, y and z are each independently a compound represented by Formula 1, which is an integer of 0 to 3 It is preferred in terms of HF removal ability.
  • the compound represented by Chemical Formula 1 may be obtained by using a commercially available product or prepared by a method known in the art.
  • the compound represented by Formula 1 may be included in an amount of 0.05 to 5% by weight, preferably 0.05 to 3% by weight relative to 100% by weight of the total electrolyte composition.
  • the compound represented by Chemical Formula 1 is included in an amount of less than 0.05% by weight, the ability to form a SEI film decreases and a synergistic effect of high-temperature stability cannot be expected. Can be shortened.
  • the cyclic fluoro carbonate-based compound forms a stable SEI film on the surface of the negative electrode active material and serves as a co-solvent.
  • cyclic fluoro carbonate-based compound examples include fluoroethylene carbonate (FEC), 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,4,5-trifluoro Ethylene carbonate, 4,4,5,5-tetrafluoroethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methyl Ethylene carbonate, 4,4,5-trifluoro-5-methylethylene carbonate or a combination thereof, and fluoroethylene carbonate (FEC) is particularly preferred in terms of the ability to form an SEI film.
  • FEC fluoroethylene carbonate
  • the cyclic fluoro carbonate-based compound may be included in an amount of 0.5 to 30% by weight, preferably 0.5 to 20% by weight relative to 100% by weight of the total electrolyte composition.
  • the cyclic fluoro carbonate-based compound is included in an amount of less than 0.5% by weight, the ability to form an SEI film may be reduced, and when it is included in an amount of more than 30% by weight, HF may be excessively generated inside the electrolyte during operation.
  • the weight ratio of the compound represented by Formula 1 and the cyclic fluoro carbonate-based compound is 1:1 to 1:20, preferably 1:1 to 1:10, and more preferably 1: 1 to 1:5.
  • the weight ratio of the compound represented by Chemical Formula 1 and the cyclic fluorocarbonate-based compound is within the above range, it is particularly advantageous to simultaneously improve room temperature life characteristics, high temperature life characteristics, and high temperature stability.
  • the non-aqueous solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • non-aqueous solvent one generally used in the art may be used without particular limitation.
  • a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, or other aprotic solvent may be used as the non-aqueous solvent. These may be used alone or in combination of two or more.
  • carbonate-based solvent a chain carbonate-based solvent, a cyclic carbonate-based solvent, or a combination thereof can be used.
  • the chain carbonate-based solvent may be, for example, diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), Ethylpropyl carbonate (EPC), ethylmethyl carbonate (EMC), or a combination thereof
  • the cyclic carbonate-based solvent is, for example, ethylene carbonate (ethylene carbonate, EC), propylene carbonate (propylene) carbonate, PC), butylene carbonate (BC), vinylethylene carbonate (VEC), or combinations thereof.
  • the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, pentyl acetate, methyl propionate, ethyl propionate, butyl propionate, ⁇ -butyrolactone, decanolide, valero Lactone, mevalonolactone, caprolactone, methyl formate, ethyl formate, propyl formate, and the like can be used.
  • the ether-based solvents include dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. Can be used.
  • Cyclohexanone or the like may be used as the ketone-based solvent.
  • Ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol-based solvent.
  • Examples of the other aprotic solvent include dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidinone, Formamide, dimethylformamide, acetonitrile, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and the like can be used.
  • the electrolyte composition according to an embodiment of the present invention may further include a lithium salt.
  • the lithium salt serves as a source of lithium ions in the battery, and serves to promote the movement of lithium ions between the positive electrode and the negative electrode.
  • lithium salt examples include LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiN(SO 3 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiCl, LiBr, LiI, LiB(C 2 O 4 ) 2 (lithium bis(oxalato) borate), LiBOB, Li (CH 3 CO 2 ), Li(CF 3 SO 3 ), Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, and the like. These may be used alone or in combination of two or more.
  • the concentration of the lithium salt may be 0.1 to 2.0M. If the concentration of the lithium salt is within the above range, the electrolyte composition may have appropriate conductivity and viscosity.
  • One embodiment of the present invention relates to a secondary battery comprising the above-described electrolyte composition.
  • the secondary battery according to the present invention includes the electrolyte composition of the present invention comprising a cyclic fluorocarbonate-based compound and a compound represented by Formula 1, a stable SEI film can be formed on the negative electrode surface during initial charging (chemical conversion step). Not only is it excellent in life-span characteristics, but HF generated during battery operation can be removed, so stability, especially high-temperature stability, is excellent.
  • the secondary battery may be a lithium secondary battery, for example, a lithium ion secondary battery.
  • the lithium secondary battery includes a positive electrode, a negative electrode, and the electrolyte composition described above.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • the positive electrode current collector may be used without being particularly limited as long as it has conductivity without causing a chemical change in the battery.
  • the positive electrode current collector includes aluminum, copper, stainless steel, nickel, titanium, calcined carbon, surface treated with carbon, nickel, titanium, or silver on the surface of copper or stainless steel, aluminum-cadmium alloy, or the like. Can be used, in particular aluminum can be used.
  • the positive electrode current collector may have various shapes such as a foil, a net, and a porous body, and may form fine irregularities on the surface to enhance the bonding force of the positive electrode active material.
  • the thickness of the positive electrode current collector may be 3 to 500 ⁇ m.
  • the positive electrode active material layer includes a positive electrode active material, a binder, and optionally a conductive material.
  • the positive electrode active material a compound capable of reversible intercalation and deintercalation of lithium may be used.
  • the positive electrode active material at least one of cobalt, manganese, nickel, aluminum, iron, or a combination of metal and lithium oxide or composite phosphorus oxide may be used. More specifically, as the positive electrode active material, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, and the like can be used.
  • the binder serves to attach the positive electrode active material particles to each other and to attach the positive electrode active material to the positive electrode current collector.
  • the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl Pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylate styrene-butadiene rubber, epoxy resin, nylon, and the like can be used.
  • the conductive material is used to impart conductivity to the electrode, and can be used without limitation as long as it has electronic conductivity without causing chemical changes.
  • the conductive material includes carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fibers; Metal-based materials such as copper, nickel, aluminum, and silver; And conductive polymers such as polyphenylene derivatives.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
  • the negative electrode current collector may be used without particular limitation as long as it has conductivity without causing a chemical change in the battery.
  • the negative electrode current collector includes copper, aluminum, stainless steel, nickel, titanium, calcined carbon, surface treated with carbon, nickel, titanium, or silver on the surface of copper or stainless steel, aluminum-cadmium alloy, or the like. Can be used, in particular copper can be used.
  • the negative electrode current collector may have various forms such as a foil, a net, and a porous body, and may form fine irregularities on the surface to enhance the bonding force of the negative electrode active material.
  • the thickness of the negative electrode current collector may be 3 to 500 ⁇ m.
  • the negative active material layer includes a negative active material, a binder, and optionally a conductive material.
  • the negative electrode active material a material capable of reversible intercalation and deintercalation of lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, and a transition metal oxide may be used.
  • the material capable of reversible intercalation and deintercalation of the lithium ions is a carbon-based material, and crystalline carbon, amorphous carbon, or a combination thereof.
  • the crystalline carbon include amorphous, plate-like, flake-like, spherical or fibrous graphite, and may be natural graphite or artificial graphite.
  • the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, and calcined coke.
  • the lithium metal alloy is lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.
  • the alloy of the metal of choice can be used.
  • Materials capable of doping and dedoping lithium include Si, Si-C composites, SiO x (0 ⁇ x ⁇ 2), and Si-Q alloys (where Q is an alkali metal, alkaline earth metal, group 13 element, group 14 element, Element selected from the group consisting of group 15 elements, group 16 elements, transition metals, rare earth elements, and combinations thereof, and not Si), Sn, SnO 2 , Sn-R alloys (wherein R is an alkali metal, alkaline earth metal, An element selected from the group consisting of a group 13 element, a group 14 element, a group 15 element, a group 16 element, a transition metal, a rare earth element, and combinations thereof, but not Sn), and also at least one of them SiO 2 may also be used by mixing.
  • the elements Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, 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, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof can be used.
  • transition metal oxide examples include vanadium oxide, lithium vanadium oxide, lithium titanium oxide, and the like.
  • the binder serves to attach the negative electrode active material particles to each other and to attach the negative electrode active material to the negative electrode current collector.
  • the binder may be the same as that used for the positive electrode active material layer.
  • the conductive material is used to impart conductivity to the electrode, and can be used without limitation as long as it has electronic conductivity without causing chemical changes. Specifically, the conductive material may be the same as that used for the positive electrode active material layer.
  • the positive electrode and the negative electrode can be produced by a manufacturing method commonly known in the art.
  • the positive electrode and the negative electrode are prepared by mixing each active material, binder, and optionally conductive material in a solvent to prepare an active material composition, and applying the active material composition to a current collector.
  • NMP N-methylpyrrolidone
  • the positive electrode and the negative electrode may be separated by a separator.
  • the separator may be used without particular limitation, as long as it is commonly used in the art. In particular, it is suitable to have low resistance to ion migration in the electrolyte composition and to have excellent moisture-moisture ability of the electrolyte composition.
  • the separator may be a material selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof, and may be in the form of nonwoven or woven fabric.
  • the separator may have a pore diameter of 0.01 to 10 ⁇ m, and a thickness of 3 to 100 ⁇ m.
  • the separator may be a single film or a multilayer film.
  • the lithium secondary battery may be manufactured by a manufacturing method commonly known in the art.
  • the lithium secondary battery obtains a laminate through a separator between an anode and a cathode, and then winds or folds the laminate to accommodate it in a battery container, injects an electrolyte composition into the battery container, and seals it with a sealing member. Can be produced.
  • the battery container may be cylindrical, prismatic, thin film, or the like.
  • the secondary battery may be used in a mobile phone, a portable computer, an electric vehicle, and the like.
  • the secondary battery may be used in a hybrid vehicle or the like in combination with an internal combustion engine, a fuel cell, a supercapacitor, and the like, and may also be used in electric bicycles, power tools, etc. that require high power, high voltage and high temperature driving.
  • An electrolyte composition was prepared by adding in an amount of 1% by weight and adding fluoroethylene carbonate in an amount of 3% by weight.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2 was added in an amount of 0.05% by weight.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2 was added in an amount of 3% by weight.
  • the electrolyte composition was prepared in the same manner as in Example 1, except that fluoroethylene carbonate was added in an amount of 0.5% by weight.
  • the electrolyte composition was prepared in the same manner as in Example 1, except that fluoroethylene carbonate was added in an amount of 20% by weight.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 4 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 5 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 6 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 7 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 8 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 9 was used instead of the compound represented by Chemical Formula 2.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2 was not added.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that fluoroethylene carbonate was not added.
  • An electrolyte composition was prepared in the same manner as in Example 2, except that fluoroethylene carbonate was not added.
  • An electrolyte composition was prepared in the same manner as in Example 7, except that fluoroethylene carbonate was not added.
  • An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by the following formula (a) was used instead of the compound represented by the formula (2).
  • a secondary battery was prepared as follows using the electrolyte composition prepared in the above Examples and Comparative Examples, and the room temperature life characteristics, high temperature stability and high temperature life characteristics were measured in the following manner, and the discoloration characteristics after storage of the electrolyte composition It was observed, and the results are shown in Table 1 below.
  • a positive electrode active material a mixture of LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder, carbon conductive material (Super-P; Timcal Ltd.) and PVDF (polyvinylidene fluoride) binder in a weight ratio of 90:5:5
  • NMP N-methylpyrrolidone
  • the positive electrode slurry was coated to a thickness of about 40 ⁇ m on a 15 ⁇ m thick aluminum foil. It was dried at room temperature, dried again at 120° C., and rolled to prepare an anode.
  • a negative electrode slurry was prepared by adding N-methylpyrrolidone to a content of 60% by weight of N-methylpyrrolidone as a mixture of artificial graphite, styrene-butadiene rubber, and carboxymethylcellulose in a weight ratio of 90:5:5 as the negative electrode active material. .
  • the negative electrode slurry was coated to a thickness of about 40 ⁇ m on a 10 ⁇ m thick copper foil. It was dried at room temperature, dried again at 120° C., and rolled to prepare a negative electrode.
  • a secondary battery was manufactured using the positive electrode, the negative electrode, and the electrolyte composition and a separator made of polyethylene.
  • the prepared secondary battery was charged with a constant current until the voltage reached 4.2V at a current of 0.2C at 25°C, and then discharged with a constant current of 0.2C until the voltage reached 2.5V. Subsequently, the constant current was charged until the voltage reached 4.2V with a current of 0.5C, and the constant voltage was charged until the current became 0.05C while maintaining 4.2V. Subsequently, the discharge was discharged at a constant current of 0.5 C until the voltage reached 2.5 V (chemical conversion step).
  • the secondary battery that had undergone the chemical conversion step was charged with a constant current until the voltage reached 4.2V at a current of 1.0C at 25°C, and was charged with a constant voltage until the current reached 0.05C while maintaining 4.2V. Subsequently, the cycle of discharging with a constant current of 1.0C was repeated 300 times until the voltage reached 2.5V during discharge.
  • the capacity retention ratio (%) in the 300th cycle of each secondary battery was calculated by Equation 1 below.
  • the secondary battery that had undergone the chemical conversion step was charged with a constant current until the voltage reached 4.2V at a current of 1.0C at 25°C, and was charged with a constant voltage until the current reached 0.05C while maintaining 4.2V. Subsequently, while storing the charged secondary battery at 60°C, the voltage was measured using a multi-meter every 24 hours to measure the residual voltage at a high temperature of the charged state cell to measure the stability of high temperature voltage storage.
  • Voltage retention rate [%] [Opening voltage on the 15th day/Initial opening voltage] ⁇ 100
  • the electrolyte compositions prepared in Examples and Comparative Examples were evaluated under the following evaluation criteria by observing the color change after storage for 15 days at 60°C.
  • the secondary battery that had undergone the chemical conversion step was charged with a constant current until the voltage reached 4.2V at a current of 1.0C at 45°C, and was charged with a constant voltage until the current reached 0.05C while maintaining 4.2V. Subsequently, the cycle of discharging with a constant current of 1.0C was repeated 300 times until the voltage reached 2.5V during discharge.
  • the capacity retention ratio (%) in the 300th cycle of each secondary battery was calculated by Equation 1 above.
  • Example 1 94.0% 96.2% ⁇ 92.3%
  • Example 2 91.4% 95.5% ⁇ 89.3%
  • Example 3 87.1% 96.0% ⁇ 86.7%
  • Example 4 93.8% 96.2% ⁇ 90.4%
  • Example 5 87.8% 95.2% ⁇ 89.5%
  • Example 6 96.7% 95.7% ⁇ 88.2%
  • Example 7 94.2% 96.3% ⁇ 92.5%
  • Example 8 93.8% 96.1% ⁇ 90.8%
  • Example 9 93.3% 95.9% ⁇ 91.2%
  • Example 10 94.0% 96.2% ⁇ 91.1%
  • Example 11 93.9% 96.1% ⁇ 90.5%
  • Example 12 93.6% 96.3% ⁇ 90.8% Comparative Example 1 86.3% 94.3% ⁇ 79.3% Comparative Example 2 81.7% 96.0% ⁇ 75.4% Comparative Example 3 76.3% 95.5% ⁇
  • the secondary battery prepared by using the electrolyte composition of Examples 1 to 12 including the propane sulfone compound represented by Chemical Formula 1 according to the present invention and the cyclic fluoro carbonate compound is Comparative Examples 1 to Compared to the secondary battery prepared using the electrolyte composition of 5, it was confirmed that it not only has better life characteristics at room temperature, but also excellent stability and life characteristics at high temperatures.
  • the electrolyte composition of Comparative Example 5 was found to change color after storage for a period of time.

Abstract

The present invention provides: an electrolyte solution composition comprising a propane sulton compound substituted with a specific substituent group, a cyclic fluorocarbonate-based compound, and a nonaqueous solvent; and a secondary battery comprising the electrolyte solution composition. By including the cyclic fluorocarbonate-based compound together with the propane sulton compound substituted with a specific substituent group, the electrolyte solution composition according to the present invention exhibits excellent SEI film-forming ability and HF scavenging capacity, and thus can be improved in its lifespan characteristics and thermostability.

Description

전해액 조성물 및 이를 이용한 이차전지Electrolyte composition and secondary battery using the same
본 발명은 전해액 조성물 및 이를 이용한 이차전지에 관한 것으로, 보다 상세하게는 우수한 SEI 피막 형성 능력과 HF 제거능을 가져 수명특성과 고온안정성이 향상된 전해액 조성물 및 이를 이용한 이차전지에 관한 것이다.The present invention relates to an electrolyte composition and a secondary battery using the same, and more particularly, to an electrolyte composition having an excellent SEI film forming ability and HF removal ability and having improved lifespan characteristics and high temperature stability, and a secondary battery using the same.
최근 전기자동차 및 휴대용 전자기기 보급량이 늘면서 높은 에너지 밀도와 작동 전위를 나타내고, 자기방전율이 낮은 리튬 이차전지에 대한 수요가 급증하고 있다.2. Description of the Related Art In recent years, as the amount of electric vehicles and portable electronic devices has increased, demand for lithium secondary batteries having high energy density and operating potential and low self-discharge rate is rapidly increasing.
리튬 이차전지의 초기 충전시 리튬 금속 산화물 등의 양극 활물질로부터 나온 리튬 이온은 음극 활물질로 이동하여, 음극 활물질의 층간에 삽입된다. 이때, 리튬 이온은 반응성이 강하므로 음극 활물질 표면에서 전해액 조성물과 음극 활물질을 구성하는 물질이 반응하여 음극 활물질의 표면에 일종의 보호막인 SEI(Solid Electrolyte Interface) 피막을 형성하게 된다.During the initial charging of the lithium secondary battery, lithium ions from the positive electrode active material such as lithium metal oxide move to the negative electrode active material and are inserted between the layers of the negative electrode active material. At this time, since lithium ions are highly reactive, the electrolyte composition and the materials constituting the negative electrode active material react on the surface of the negative electrode active material to form a kind of protective electrode, a Solid Electrolyte Interface (SEI) film, on the surface of the negative electrode active material.
SEI 피막은 전해액 조성물 중에서 리튬 이온과 함께 이동하는 분자량이 큰 유기 용매 분자가 음극 활물질의 층간에 삽입되어 음극 구조가 파괴되는 것을 막아준다. 따라서, 전해액 조성물과 음극 활물질의 접촉을 방지함으로써 전해액 조성물의 분해가 발생하지 않고, 전해액 조성물 중의 리튬 이온의 양이 가역적으로 유지되어 안정적인 충방전이 유지된다.In the SEI coating, an organic solvent molecule having a large molecular weight moving with lithium ions in the electrolyte composition is inserted between the layers of the negative electrode active material to prevent the negative electrode structure from being destroyed. Therefore, by preventing contact between the electrolyte composition and the negative electrode active material, decomposition of the electrolyte composition does not occur, and the amount of lithium ions in the electrolyte composition is reversibly maintained to maintain stable charge and discharge.
이에, 음극의 표면에 안정적인 SEI 피막을 형성하여 수명특성을 개선하기 위한 첨가제에 대한 관심이 증가하고 있다. 특히, 플루오로에틸렌 카보네이트(FEC)와 같은 환상 플루오로 카보네이트계 화합물은 음극 표면에 SEI 피막을 형성하는 능력이 우수하여 리튬 이온전지의 음극 피막형성제로 사용되면서 공용매로서도 널리 사용되는 화합물이다[대한민국 등록특허 제10-0977973호 참조].Accordingly, interest in additives for improving the life characteristics by forming a stable SEI film on the surface of the cathode is increasing. In particular, a cyclic fluorocarbonate-based compound such as fluoroethylene carbonate (FEC) is a compound that is widely used as a co-solvent while being used as a negative electrode film forming agent for lithium ion batteries due to its excellent ability to form a SEI film on the negative electrode surface [Korea] See Patent Registration No. 10-0977973].
그러나, FEC는 전해액 중에서 분해되어 불산(HF)을 생성할 수 있다. 이러한 HF는 충방전 과정에서 분해되어 수소 가스를 방출할 수 있다. 특히 고온에서는 이러한 현상이 심화되어 스웰링 현상을 야기하거나, 심할 경우 폭발을 야기할 수도 있다. 또한, HF는 산성으로, 전극의 부식 등을 초래할 수도 있다.However, FEC can decompose in the electrolyte to produce hydrofluoric acid (HF). The HF can be decomposed during charge and discharge to release hydrogen gas. Especially at high temperatures, these phenomena may intensify and cause swelling or, if severe, an explosion. In addition, HF is acidic and may cause corrosion of the electrode.
따라서, SEI 피막을 형성하는 능력을 가지면서도 HF 제거능이 우수하여 수명특성과 고온안정성이 향상된 전해액 조성물에 대한 개발이 요구되고 있다.Accordingly, there is a need to develop an electrolyte composition having an ability to form an SEI film, and having an excellent HF removal ability, thereby improving lifespan characteristics and high temperature stability.
본 발명의 한 목적은 우수한 SEI 피막 형성 능력과 HF 제거능을 가져 수명특성과 고온안정성이 향상된 전해액 조성물을 제공하는 것이다.One object of the present invention is to provide an electrolyte composition having excellent SEI film formation ability and HF removal ability, and improved lifespan characteristics and high temperature stability.
본 발명의 다른 목적은 상기 전해액 조성물을 이용한 이차전지를 제공하는 것이다.Another object of the present invention is to provide a secondary battery using the electrolyte composition.
한편으로, 본 발명은 하기 화학식 1로 표시되는 화합물, 환상 플루오로 카보네이트계 화합물 및 비수용매를 포함하는 전해액 조성물을 제공한다.On the other hand, the present invention provides an electrolyte composition comprising a compound represented by the following formula (1), a cyclic fluoro carbonate-based compound and a non-aqueous solvent.
[화학식 1][Formula 1]
Figure PCTKR2019015857-appb-I000001
Figure PCTKR2019015857-appb-I000001
상기 식에서,In the above formula,
R은 수소 원자 또는 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, R is a hydrogen atom or Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y ,
x, y 및 z는 각각 독립적으로 0 내지 3의 정수이다.x, y and z are each independently an integer from 0 to 3.
본 발명의 일 실시형태에서, R은 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, x, y 및 z는 각각 독립적으로 0 내지 3의 정수일 수 있다.In one embodiment of the invention, R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y , and x, y and z can each independently be an integer from 0 to 3 have.
본 발명의 일 실시형태에서, 상기 화학식 1로 표시되는 화합물은 전해액 조성물 전체 100 중량%에 대하여 0.05 내지 5 중량%의 양으로 포함될 수 있다.In one embodiment of the present invention, the compound represented by Chemical Formula 1 may be included in an amount of 0.05 to 5% by weight based on 100% by weight of the total electrolyte composition.
본 발명의 일 실시형태에서, 상기 환상 플루오로 카보네이트계 화합물은 플루오로에틸렌카보네이트를 포함할 수 있다.In one embodiment of the present invention, the cyclic fluoro carbonate-based compound may include fluoroethylene carbonate.
본 발명의 일 실시형태에서, 상기 환상 플루오로 카보네이트계 화합물은 전해액 조성물 전체 100 중량%에 대하여 0.5 내지 30 중량%의 양으로 포함될 수 있다.In one embodiment of the present invention, the cyclic fluoro carbonate-based compound may be included in an amount of 0.5 to 30% by weight based on 100% by weight of the total electrolyte composition.
본 발명의 일 실시형태에서, 상기 화학식 1로 표시되는 화합물과 환상 플루오로 카보네이트계 화합물의 혼합비는 1:1 내지 1:20일 수 있다.In one embodiment of the present invention, the mixing ratio of the compound represented by Chemical Formula 1 and the cyclic fluoro carbonate compound may be 1:1 to 1:20.
본 발명의 일 실시형태에서, 상기 전해액 조성물은 리튬염을 추가로 포함할 수 있다.In one embodiment of the present invention, the electrolyte composition may further include a lithium salt.
다른 한편으로, 본 발명은 상기 전해액 조성물을 포함하는 이차전지를 제공한다.On the other hand, the present invention provides a secondary battery comprising the electrolyte composition.
본 발명의 일 실시형태에서, 상기 이차전지는 리튬 이차전지일 수 있다.In one embodiment of the present invention, the secondary battery may be a lithium secondary battery.
본 발명에 따른 전해액 조성물은 환상 플루오로 카보네이트계 화합물과 특정 치환기로 치환된 프로판 설톤 화합물을 함께 포함함으로써 우수한 SEI 피막 형성 능력을 가져 전지에 적용시 상온수명특성이 우수하고, 출력이 향상될 수 있다. 또한, 본 발명에 따른 전해액 조성물은 뛰어난 HF 제거능을 가져 고온에서도 수명특성이 우수하고, 고온안정성이 향상되어 내구성을 증진시킬 수 있다.The electrolyte composition according to the present invention has an excellent SEI film forming ability by including a cyclic fluorocarbonate-based compound and a propane sulfone compound substituted with a specific substituent, and has excellent room temperature life characteristics when applied to a battery, and output can be improved. . In addition, the electrolyte composition according to the present invention has excellent HF removal ability, and thus has excellent life characteristics even at high temperatures, and can improve durability by improving high temperature stability.
이하, 본 발명을 보다 상세히 설명한다. Hereinafter, the present invention will be described in more detail.
본 발명의 일 실시형태는 하기 화학식 1로 표시되는 화합물, 환상 플루오로 카보네이트계 화합물 및 비수용매를 포함하는 전해액 조성물에 관한 것이다.One embodiment of the present invention relates to an electrolyte composition comprising a compound represented by the following formula (1), a cyclic fluoro carbonate-based compound and a non-aqueous solvent.
[화학식 1][Formula 1]
Figure PCTKR2019015857-appb-I000002
Figure PCTKR2019015857-appb-I000002
상기 식에서,In the above formula,
R은 수소 원자 또는 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, R is a hydrogen atom or Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y ,
x, y 및 z는 각각 독립적으로 0 내지 3의 정수이다.x, y and z are each independently an integer from 0 to 3.
본 발명의 일 실시형태에서, R은 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, x, y 및 z는 각각 독립적으로 0 내지 3의 정수일 수 있다.In one embodiment of the invention, R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y , and x, y and z can each independently be an integer from 0 to 3 have.
본 발명의 일 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 내지 9 중 어느 하나로 표시되는 화합물일 수 있다.In one embodiment of the present invention, the compound represented by Formula 1 may be a compound represented by any one of the following Formulas 2 to 9.
[화학식 2][Formula 2]
Figure PCTKR2019015857-appb-I000003
Figure PCTKR2019015857-appb-I000003
[화학식 3][Formula 3]
Figure PCTKR2019015857-appb-I000004
Figure PCTKR2019015857-appb-I000004
[화학식 4][Formula 4]
Figure PCTKR2019015857-appb-I000005
Figure PCTKR2019015857-appb-I000005
[화학식 5][Formula 5]
Figure PCTKR2019015857-appb-I000006
Figure PCTKR2019015857-appb-I000006
[화학식 6][Formula 6]
Figure PCTKR2019015857-appb-I000007
Figure PCTKR2019015857-appb-I000007
[화학식 7][Formula 7]
Figure PCTKR2019015857-appb-I000008
Figure PCTKR2019015857-appb-I000008
[화학식 8][Formula 8]
Figure PCTKR2019015857-appb-I000009
Figure PCTKR2019015857-appb-I000009
[화학식 9][Formula 9]
Figure PCTKR2019015857-appb-I000010
Figure PCTKR2019015857-appb-I000010
본 발명의 일 실시형태에 있어서, 상기 화학식 1로 표시되는 화합물은 HF와의 반응성이 우수하여 전해액 조성물 내에 존재하는 HF를 제거함으로써 안정성, 특히 고온안정성을 향상시키는 역할을 수행할 수 있다. 특히, R이 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, x, y 및 z는 각각 독립적으로 0 내지 3의 정수인 화학식 1로 표시되는 화합물이 HF 제거 능력면에서 바람직하다.In one embodiment of the present invention, the compound represented by Chemical Formula 1 is excellent in reactivity with HF, thereby removing HF present in the electrolyte composition, thereby improving stability, particularly high temperature stability. In particular, R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y , and x, y and z are each independently a compound represented by Formula 1, which is an integer of 0 to 3 It is preferred in terms of HF removal ability.
상기 화학식 1로 표시되는 화합물은 시판되는 것을 입수하여 사용하거나 당해 분야에 알려진 방법으로 제조하여 사용할 수 있다.The compound represented by Chemical Formula 1 may be obtained by using a commercially available product or prepared by a method known in the art.
본 발명의 일 실시형태에서, 상기 화학식 1로 표시되는 화합물은 전해액 조성물 전체 100 중량%에 대하여 0.05 내지 5 중량%, 바람직하게는 0.05 내지 3 중량%의 양으로 포함될 수 있다. 상기 화학식 1로 표시되는 화합물이 0.05 중량% 미만의 양으로 포함되면 SEI 피막 형성 능력이 감소하고 고온안정성의 상승 효과를 기대할 수 없으며, 5 중량% 초과의 양으로 포함되면 저항을 증가시켜 전지의 수명을 단축시킬 수 있다.In one embodiment of the present invention, the compound represented by Formula 1 may be included in an amount of 0.05 to 5% by weight, preferably 0.05 to 3% by weight relative to 100% by weight of the total electrolyte composition. When the compound represented by Chemical Formula 1 is included in an amount of less than 0.05% by weight, the ability to form a SEI film decreases and a synergistic effect of high-temperature stability cannot be expected. Can be shortened.
본 발명의 일 실시형태에서, 상기 환상 플루오로 카보네이트계 화합물은 음극 활물질의 표면에 안정한 SEI 피막을 형성하고 공용매로서의 역할을 한다.In one embodiment of the present invention, the cyclic fluoro carbonate-based compound forms a stable SEI film on the surface of the negative electrode active material and serves as a co-solvent.
상기 환상 플루오로 카보네이트계 화합물로는 예를 들어, 플루오로에틸렌카보네이트(FEC), 4,5-디플루오로에틸렌카보네이트, 4,4-디플루오로에틸렌카보네이트, 4,4,5-트리플루오로에틸렌카보네이트, 4,4,5,5-테트라플루오로에틸렌카보네이트, 4-플루오로-5-메틸에틸렌카보네이트, 4-플루오로-4-메틸에틸렌카보네이트, 4,5-디플루오로-4-메틸에틸렌카보네이트, 4,4,5-트리플루오로-5-메틸에틸렌카보네이트 또는 이들의 조합을 들 수 있으며, 특히 플루오로에틸렌카보네이트(FEC)가 SEI 피막 형성 능력면에서 바람직하다.Examples of the cyclic fluoro carbonate-based compound include fluoroethylene carbonate (FEC), 4,5-difluoroethylene carbonate, 4,4-difluoroethylene carbonate, and 4,4,5-trifluoro Ethylene carbonate, 4,4,5,5-tetrafluoroethylene carbonate, 4-fluoro-5-methylethylene carbonate, 4-fluoro-4-methylethylene carbonate, 4,5-difluoro-4-methyl Ethylene carbonate, 4,4,5-trifluoro-5-methylethylene carbonate or a combination thereof, and fluoroethylene carbonate (FEC) is particularly preferred in terms of the ability to form an SEI film.
본 발명의 일 실시형태에서, 상기 환상 플루오로 카보네이트계 화합물은 전해액 조성물 전체 100 중량%에 대하여 0.5 내지 30 중량%, 바람직하게는 0.5 내지 20 중량%의 양으로 포함될 수 있다. 상기 환상 플루오로 카보네이트계 화합물이 0.5 중량% 미만의 양으로 포함되면 SEI 피막 형성 능력이 감소할 수 있고, 30 중량% 초과의 양으로 포함되면 구동 중 전해액 내부에 HF가 과량으로 발생할 수 있다.In one embodiment of the present invention, the cyclic fluoro carbonate-based compound may be included in an amount of 0.5 to 30% by weight, preferably 0.5 to 20% by weight relative to 100% by weight of the total electrolyte composition. When the cyclic fluoro carbonate-based compound is included in an amount of less than 0.5% by weight, the ability to form an SEI film may be reduced, and when it is included in an amount of more than 30% by weight, HF may be excessively generated inside the electrolyte during operation.
본 발명의 일 실시형태에서, 상기 화학식 1로 표시되는 화합물과 환상 플루오로 카보네이트계 화합물의 중량비는 1:1 내지 1:20, 바람직하게는 1:1 내지 1:10, 더욱 바람직하게는 1:1 내지 1:5일 수 있다. 상기 화학식 1로 표시되는 화합물과 환상 플루오로 카보네이트계 화합물의 중량비가 상기 범위일 때 상온수명특성, 고온수명특성 및 고온안정성을 동시에 향상시키는데 특히 유리하다.In one embodiment of the present invention, the weight ratio of the compound represented by Formula 1 and the cyclic fluoro carbonate-based compound is 1:1 to 1:20, preferably 1:1 to 1:10, and more preferably 1: 1 to 1:5. When the weight ratio of the compound represented by Chemical Formula 1 and the cyclic fluorocarbonate-based compound is within the above range, it is particularly advantageous to simultaneously improve room temperature life characteristics, high temperature life characteristics, and high temperature stability.
본 발명의 일 실시형태에서, 상기 비수용매는 전지의 전기화학적 반응에 관여하는 이온들이 이동할 수 있는 매질 역할을 한다.In one embodiment of the present invention, the non-aqueous solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
상기 비수용매로는 특별한 제한 없이 당해 분야에서 통상적으로 사용되는 것을 사용할 수 있다. 예를 들어, 상기 비수용매로는 카보네이트계 용매, 에스테르계 용매, 에테르계 용매, 케톤계 용매, 알코올계 용매, 또는 그 밖의 비양성자성 용매 등을 사용할 수 있다. 이들은 단독으로 또는 둘 이상을 조합하여 사용할 수 있다.As the non-aqueous solvent, one generally used in the art may be used without particular limitation. For example, a carbonate-based solvent, an ester-based solvent, an ether-based solvent, a ketone-based solvent, an alcohol-based solvent, or other aprotic solvent may be used as the non-aqueous solvent. These may be used alone or in combination of two or more.
상기 카보네이트계 용매로는 사슬형 카보네이트계 용매, 환상 카보네이트계 용매, 또는 이들의 조합을 사용할 수 있다.As the carbonate-based solvent, a chain carbonate-based solvent, a cyclic carbonate-based solvent, or a combination thereof can be used.
상기 사슬형 카보네이트계 용매는 예를 들어, 디에틸 카보네이트(diethyl carbonate, DEC), 디메틸 카보네이트(dimethyl carbonate, DMC), 디프로필 카보네이트(dipropyl carbonate, DPC), 메틸프로필 카보네이트(methylpropyl carbonate, MPC), 에틸프로필 카보네이트(ethylpropyl carbonate, EPC), 에틸메틸 카보네이트(ethylmethyl carbonate, EMC) 또는 이들의 조합을 들 수 있고, 상기 환상 카보네이트계 용매는 예를 들어 에틸렌 카보네이트(ethylene carbonate, EC), 프로필렌 카보네이트(propylene carbonate, PC), 부틸렌 카보네이트(butylene carbonate, BC), 비닐에틸렌 카보네이트(vinylethylene carbonate, VEC) 또는 이들의 조합을 들 수 있다.The chain carbonate-based solvent may be, for example, diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), Ethylpropyl carbonate (EPC), ethylmethyl carbonate (EMC), or a combination thereof, and the cyclic carbonate-based solvent is, for example, ethylene carbonate (ethylene carbonate, EC), propylene carbonate (propylene) carbonate, PC), butylene carbonate (BC), vinylethylene carbonate (VEC), or combinations thereof.
상기 에스테르계 용매로는 메틸아세테이트, 에틸아세테이트, n-프로필아세테이트, 펜틸아세테이트, 메틸프로피오네이트, 에틸프로피오네이트, 부틸프로피오네이트, γ-부티로락톤, 데카놀라이드(decanolide), 발레로락톤, 메발로노락톤(mevalonolactone), 카프로락톤(caprolactone), 메틸 포메이트(methyl formate), 에틸 포메이트(ethyl formate), 프로필 포메이트(propyl formate) 등이 사용될 수 있다.The ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, pentyl acetate, methyl propionate, ethyl propionate, butyl propionate, γ-butyrolactone, decanolide, valero Lactone, mevalonolactone, caprolactone, methyl formate, ethyl formate, propyl formate, and the like can be used.
상기 에테르계 용매로는 디부틸 에테르, 테트라글라임, 디글라임, 1,2-디메톡시에탄, 1,2-디에톡시에탄, 에톡시메톡시에탄, 2-메틸테트라히드로퓨란, 테트라히드로퓨란 등이 사용될 수 있다.The ether-based solvents include dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. Can be used.
상기 케톤계 용매로는 시클로헥사논 등이 사용될 수 있다.Cyclohexanone or the like may be used as the ketone-based solvent.
상기 알코올계 용매로는 에틸알코올, 이소프로필 알코올 등이 사용될 수 있다.Ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol-based solvent.
상기 그 밖의 비양성자성 용매로는 디메틸술폭시드, 1,2-디옥솔란, 설포란, 메틸설포란, 1,3-디메틸-2-이미다졸리디논, N-메틸-2-피롤리디논, 포름아미드, 디메틸포름아미드, 아세토니트릴, 니트로메탄, 인산트리메틸, 인산트리에틸, 인산트리옥틸 등이 사용될 수 있다.Examples of the other aprotic solvent include dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidinone, Formamide, dimethylformamide, acetonitrile, nitromethane, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and the like can be used.
본 발명의 일 실시형태에 따른 전해액 조성물은 리튬염을 추가로 포함할 수 있다.The electrolyte composition according to an embodiment of the present invention may further include a lithium salt.
상기 리튬염은 전지 내에서 리튬 이온의 공급원으로 작용하고, 양극과 음극 사이의 리튬 이온의 이동을 촉진하는 역할을 한다.The lithium salt serves as a source of lithium ions in the battery, and serves to promote the movement of lithium ions between the positive electrode and the negative electrode.
상기 리튬염의 예로는 LiPF6, LiBF4, LiSbF6, LiAsF6, LiN(SO2C2F5)2, Li(CF3SO2)2N, LiN(SO3C2F5)2, LiC4F9SO3, LiClO4, LiAlO2, LiAlCl4, LiCl, LiBr, LiI, LiB(C2O4)2(리튬 비스(옥살레이토) 보레이트(lithium bis(oxalato) borate), LiBOB), Li(CH3CO2), Li(CF3SO3), Li(FSO2)2N, Li(CF3SO2)3C 등을 들 수 있다. 이들은 단독으로 또는 둘 이상을 조합하여 사용할 수 있다.Examples of the lithium salt are LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiN(SO 3 C 2 F 5 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiCl, LiBr, LiI, LiB(C 2 O 4 ) 2 (lithium bis(oxalato) borate), LiBOB, Li (CH 3 CO 2 ), Li(CF 3 SO 3 ), Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 3 C, and the like. These may be used alone or in combination of two or more.
상기 리튬염의 농도는 0.1 내지 2.0M일 수 있다. 리튬염의 농도가 상기 범위 이내이면 전해액 조성물이 적절한 전도도 및 점도를 가질 수 있다.The concentration of the lithium salt may be 0.1 to 2.0M. If the concentration of the lithium salt is within the above range, the electrolyte composition may have appropriate conductivity and viscosity.
본 발명의 일 실시형태는 상술한 전해액 조성물을 포함하는 이차전지에 관한 것이다.One embodiment of the present invention relates to a secondary battery comprising the above-described electrolyte composition.
본 발명에 따른 이차전지는 환상 플루오로 카보네이트계 화합물과 화학식 1로 표시되는 화합물을 함께 포함하는 본 발명의 전해액 조성물을 포함하기 때문에 최초 충전시(화성 단계) 음극 표면에 안정한 SEI 피막이 형성될 수 있어 수명특성이 우수할 뿐만 아니라 전지 구동 중에 발생하는 HF가 제거될 수 있어 안정성, 특히 고온안정성이 탁월하다.Since the secondary battery according to the present invention includes the electrolyte composition of the present invention comprising a cyclic fluorocarbonate-based compound and a compound represented by Formula 1, a stable SEI film can be formed on the negative electrode surface during initial charging (chemical conversion step). Not only is it excellent in life-span characteristics, but HF generated during battery operation can be removed, so stability, especially high-temperature stability, is excellent.
본 발명의 일 실시형태에서, 상기 이차전지는 리튬 이차전지일 수 있으며, 예를 들어 리튬 이온 이차전지일 수 있다.In one embodiment of the present invention, the secondary battery may be a lithium secondary battery, for example, a lithium ion secondary battery.
상기 리튬 이차전지는 양극, 음극 및 상술한 전해액 조성물을 포함한다.The lithium secondary battery includes a positive electrode, a negative electrode, and the electrolyte composition described above.
상기 양극은 양극 집전체 및 상기 양극 집전체 상에 형성되는 양극 활물질층을 포함한다.The positive electrode includes a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
상기 양극 집전체로는 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되지 않고 사용될 수 있다. 구체적으로, 상기 양극 집전체로는 알루미늄, 구리, 스테인레스 스틸, 니켈, 티탄, 소성 탄소, 구리나 스테인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면 처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있으며, 특히 알루미늄이 사용될 수 있다. 상기 양극 집전체는 호일, 네트, 다공질체 등의 다양한 형태를 가질 수 있으며, 표면에 미세한 요철을 형성하여 양극 활물질의 결합력을 강화시킬 수도 있다.The positive electrode current collector may be used without being particularly limited as long as it has conductivity without causing a chemical change in the battery. Specifically, the positive electrode current collector includes aluminum, copper, stainless steel, nickel, titanium, calcined carbon, surface treated with carbon, nickel, titanium, or silver on the surface of copper or stainless steel, aluminum-cadmium alloy, or the like. Can be used, in particular aluminum can be used. The positive electrode current collector may have various shapes such as a foil, a net, and a porous body, and may form fine irregularities on the surface to enhance the bonding force of the positive electrode active material.
상기 양극 집전체의 두께는 3 내지 500 ㎛일 수 있다.The thickness of the positive electrode current collector may be 3 to 500 μm.
상기 양극 활물질층은 양극 활물질, 바인더 및 선택적으로 도전재를 포함한다.The positive electrode active material layer includes a positive electrode active material, a binder, and optionally a conductive material.
상기 양극 활물질로는 리튬의 가역적인 인터칼레이션 및 디인터칼레이션이 가능한 화합물을 사용할 수 있다. 구체적으로, 상기 양극 활물질로는 코발트, 망간, 니켈, 알루미늄, 철 또는 이들의 조합의 금속과 리튬과의 복합 산화물 또는 복합 인산화물 중에서 하나 이상을 사용할 수 있다. 더욱 구체적으로, 상기 양극 활물질로는 리튬 코발트 산화물, 리튬 니켈 산화물, 리튬 망간 산화물, 리튬 니켈 코발트 망간 산화물, 리튬 니켈 코발트 알루미늄 산화물, 리튬 철 인산화물 등을 사용할 수 있다.As the positive electrode active material, a compound capable of reversible intercalation and deintercalation of lithium may be used. Specifically, as the positive electrode active material, at least one of cobalt, manganese, nickel, aluminum, iron, or a combination of metal and lithium oxide or composite phosphorus oxide may be used. More specifically, as the positive electrode active material, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, and the like can be used.
상기 바인더는 양극 활물질 입자들을 서로 부착시키고, 양극 활물질을 양극 집전체에 부착시키는 역할을 한다. 구체적으로, 상기 바인더로는 폴리비닐알콜, 카르복시메틸셀룰로오스, 히드록시프로필셀룰로오스, 디아세틸셀룰로오스, 폴리비닐클로라이드, 카르복실화된 폴리비닐클로라이드, 폴리비닐플루오라이드, 에틸렌 옥사이드를 포함하는 폴리머, 폴리비닐피롤리돈, 폴리우레탄, 폴리테트라플루오로에틸렌, 폴리비닐리덴 플루오라이드, 폴리에틸렌, 폴리프로필렌, 스티렌-부타디엔 러버, 아크릴레이티드 스티렌-부타디엔 러버, 에폭시 수지, 나일론 등을 사용할 수 있다.The binder serves to attach the positive electrode active material particles to each other and to attach the positive electrode active material to the positive electrode current collector. Specifically, the binder includes polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl Pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylate styrene-butadiene rubber, epoxy resin, nylon, and the like can be used.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로, 화학변화를 야기하지 않고 전자 전도성을 갖는 것이면 제한 없이 사용가능하다. 구체적으로, 상기 도전재로는 천연 흑연, 인조 흑연, 카본 블랙, 아세틸렌 블랙, 케첸 블랙, 탄소 섬유 등의 탄소계 물질; 구리, 니켈, 알루미늄, 은 등의 금속계 물질; 폴리페닐렌 유도체 등의 도전성 폴리머 등을 사용할 수 있다.The conductive material is used to impart conductivity to the electrode, and can be used without limitation as long as it has electronic conductivity without causing chemical changes. Specifically, the conductive material includes carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, ketjen black, and carbon fibers; Metal-based materials such as copper, nickel, aluminum, and silver; And conductive polymers such as polyphenylene derivatives.
상기 음극은 음극 집전체 및 상기 음극 집전체 상에 형성되는 음극 활물질층을 포함한다.The negative electrode includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
상기 음극 집전체로는 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되지 않고 사용될 수 있다. 구체적으로, 상기 음극 집전체로는 구리, 알루미늄, 스테인레스 스틸, 니켈, 티탄, 소성 탄소, 구리나 스테인레스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면 처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있으며, 특히 구리가 사용될 수 있다. 상기 음극 집전체는 호일, 네트, 다공질체 등의 다양한 형태를 가질 수 있으며, 표면에 미세한 요철을 형성하여 음극 활물질의 결합력을 강화시킬 수도 있다.The negative electrode current collector may be used without particular limitation as long as it has conductivity without causing a chemical change in the battery. Specifically, the negative electrode current collector includes copper, aluminum, stainless steel, nickel, titanium, calcined carbon, surface treated with carbon, nickel, titanium, or silver on the surface of copper or stainless steel, aluminum-cadmium alloy, or the like. Can be used, in particular copper can be used. The negative electrode current collector may have various forms such as a foil, a net, and a porous body, and may form fine irregularities on the surface to enhance the bonding force of the negative electrode active material.
상기 음극 집전체의 두께는 3 내지 500 ㎛일 수 있다.The thickness of the negative electrode current collector may be 3 to 500 μm.
상기 음극 활물질층은 음극 활물질, 바인더 및 선택적으로 도전재를 포함한다.The negative active material layer includes a negative active material, a binder, and optionally a conductive material.
상기 음극 활물질로는 리튬 이온의 가역적인 인터칼레이션 및 디인터칼레이션이 가능한 물질, 리튬 금속, 리튬 금속의 합금, 리튬에 도프 및 탈도프 가능한 물질, 전이 금속 산화물 등을 사용할 수 있다.As the negative electrode active material, a material capable of reversible intercalation and deintercalation of lithium ions, a lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, and a transition metal oxide may be used.
상기 리튬 이온의 가역적인 인터칼레이션 및 디인터칼레이션이 가능한 물질은 탄소계 물질로, 결정질 탄소, 비정질 탄소 또는 이들을 함께 사용할 수 있다. 상기 결정질 탄소의 예로는 무정형, 판상, 플레이크상(flake), 구형 또는 섬유형의 흑연을 들 수 있고, 천연 흑연 또는 인조 흑연일 수 있다. 상기 비정질 탄소의 예로는 소프트 카본 또는 하드 카본, 메조페이스 피치 탄화물, 소성된 코크스 등을 들 수 있다.The material capable of reversible intercalation and deintercalation of the lithium ions is a carbon-based material, and crystalline carbon, amorphous carbon, or a combination thereof. Examples of the crystalline carbon include amorphous, plate-like, flake-like, spherical or fibrous graphite, and may be natural graphite or artificial graphite. Examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, and calcined coke.
상기 리튬 금속의 합금으로는 리튬과 Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al 및 Sn으로 이루어진 군에서 선택되는 금속의 합금이 사용될 수 있다.The lithium metal alloy is lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn. The alloy of the metal of choice can be used.
상기 리튬에 도프 및 탈도프 가능한 물질로는 Si, Si-C 복합체, SiOx(0 < x < 2), Si-Q 합금(상기 Q는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 15족 원소, 16족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si는 아님), Sn, SnO2, Sn-R 합금(상기 R은 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 15족 원소, 16족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 등을 들 수 있고, 또한 이들 중 적어도 하나와 SiO2를 혼합하여 사용할 수도 있다. 상기 원소 Q 및 R로는 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, 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, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po 및 이들의 조합으로 이루어진 군에서 선택되는 것을 사용할 수 있다.Materials capable of doping and dedoping lithium include Si, Si-C composites, SiO x (0 <x <2), and Si-Q alloys (where Q is an alkali metal, alkaline earth metal, group 13 element, group 14 element, Element selected from the group consisting of group 15 elements, group 16 elements, transition metals, rare earth elements, and combinations thereof, and not Si), Sn, SnO 2 , Sn-R alloys (wherein R is an alkali metal, alkaline earth metal, An element selected from the group consisting of a group 13 element, a group 14 element, a group 15 element, a group 16 element, a transition metal, a rare earth element, and combinations thereof, but not Sn), and also at least one of them SiO 2 may also be used by mixing. The elements Q and R include Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, 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, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof can be used.
상기 전이 금속 산화물로는 바나듐 산화물, 리튬 바나듐 산화물 또는 리튬 티타늄 산화물 등을 들 수 있다.Examples of the transition metal oxide include vanadium oxide, lithium vanadium oxide, lithium titanium oxide, and the like.
상기 바인더는 음극 활물질 입자들을 서로 부착시키고, 음극 활물질을 음극 집전체에 부착시키는 역할을 한다. 구체적으로, 상기 바인더로는 상기 양극 활물질층에 사용된 것과 동일한 것을 사용할 수 있다.The binder serves to attach the negative electrode active material particles to each other and to attach the negative electrode active material to the negative electrode current collector. Specifically, the binder may be the same as that used for the positive electrode active material layer.
상기 도전재는 전극에 도전성을 부여하기 위해 사용되는 것으로, 화학변화를 야기하지 않고 전자 전도성을 갖는 것이면 제한 없이 사용가능하다. 구체적으로, 상기 도전재로는 상기 양극 활물질층에 사용된 것과 동일한 것을 사용할 수 있다.The conductive material is used to impart conductivity to the electrode, and can be used without limitation as long as it has electronic conductivity without causing chemical changes. Specifically, the conductive material may be the same as that used for the positive electrode active material layer.
상기 양극 및 음극은 당해 분야에서 통상적으로 알려져 있는 제조방법에 의하여 제조할 수 있다.The positive electrode and the negative electrode can be produced by a manufacturing method commonly known in the art.
구체적으로, 상기 양극 및 음극은 각각의 활물질, 바인더 및 선택적으로 도전재를 용매 중에서 혼합하여 활물질 조성물을 제조하고, 상기 활물질 조성물을 집전체에 도포하여 제조한다.Specifically, the positive electrode and the negative electrode are prepared by mixing each active material, binder, and optionally conductive material in a solvent to prepare an active material composition, and applying the active material composition to a current collector.
상기 용매로는 N-메틸피롤리돈(NMP), 아세톤, 물 등이 사용될 수 있다.As the solvent, N-methylpyrrolidone (NMP), acetone, water, or the like can be used.
상기 양극과 음극은 세퍼레이터에 의해 분리될 수 있다. 상기 세퍼레이터로는 당해 분야에서 통상적으로 사용되는 것이라면 특별히 제한 없이 사용될 수 있다. 특히 전해액 조성물 내 이온 이동에 대하여 저저항이면서 전해액 조성물의 함습 능력이 우수한 것이 적합하다. 상기 세퍼레이터는 유리 섬유, 폴리에스테르, 테프론, 폴리에틸렌, 폴리프로필렌, 폴리테트라플루오로에틸렌(PTFE) 및 이들의 조합 중에서 선택되는 재질일 수 있으며, 부직포 또는 직포 형태일 수 있다. 상기 세퍼레이터는 기공 직경이 0.01 내지 10㎛이고, 두께가 3 내지 100㎛일 수 있다. 상기 세퍼레이터는 단일막 또는 다층막일 수 있다.The positive electrode and the negative electrode may be separated by a separator. The separator may be used without particular limitation, as long as it is commonly used in the art. In particular, it is suitable to have low resistance to ion migration in the electrolyte composition and to have excellent moisture-moisture ability of the electrolyte composition. The separator may be a material selected from glass fiber, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), and combinations thereof, and may be in the form of nonwoven or woven fabric. The separator may have a pore diameter of 0.01 to 10㎛, and a thickness of 3 to 100㎛. The separator may be a single film or a multilayer film.
상기 리튬 이차전지는 당해 분야에서 통상적으로 알려져 있는 제조방법에 의하여 제조할 수 있다.The lithium secondary battery may be manufactured by a manufacturing method commonly known in the art.
구체적으로, 상기 리튬 이차전지는 양극과 음극 사이에 세퍼레이터를 개재하여 적층체를 얻은 다음, 상기 적층체를 와인딩하거나 접어서 전지 용기에 수용시키고, 상기 전지 용기 내에 전해액 조성물을 주입하고 봉입 부재로 밀봉하여 제조할 수 있다.Specifically, the lithium secondary battery obtains a laminate through a separator between an anode and a cathode, and then winds or folds the laminate to accommodate it in a battery container, injects an electrolyte composition into the battery container, and seals it with a sealing member. Can be produced.
상기 전지 용기는 원통형, 각형, 박막형 등일 수 있다.The battery container may be cylindrical, prismatic, thin film, or the like.
상기 이차전지는 휴대폰, 휴대용 컴퓨터, 전기차량(Electric Vehicle) 등에 사용될 수 있다. 또한, 상기 이차전지는 내연기관, 연료전지, 수퍼커패시터 등과 결합하여 하이브리드차량(Hybrid Vehicle) 등에도 사용될 수 있으며, 고출력, 고전압 및 고온 구동이 요구되는 전기 자전거, 전동 공구 등에도 사용이 가능하다.The secondary battery may be used in a mobile phone, a portable computer, an electric vehicle, and the like. In addition, the secondary battery may be used in a hybrid vehicle or the like in combination with an internal combustion engine, a fuel cell, a supercapacitor, and the like, and may also be used in electric bicycles, power tools, etc. that require high power, high voltage and high temperature driving.
이하, 실시예, 비교예 및 실험예에 의해 본 발명을 보다 구체적으로 설명하고자 한다. 이들 실시예, 비교예 및 실험예는 오직 본 발명을 설명하기 위한 것으로, 본 발명의 범위가 이들에 국한되지 않는다는 것은 당업자에게 있어서 자명하다.Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. It is apparent to those skilled in the art that these examples, comparative examples and experimental examples are only for describing the present invention, and the scope of the present invention is not limited to them.
합성예 1: 화학식 4로 표시되는 화합물의 합성Synthesis Example 1: Synthesis of Compound Represented by Formula 4
반응 용매로서 아세토니트릴 중에서 화학식 3의 화합물 1.4g과 1,3-비스(3,3,3-트리플루오로프로필)-1,1,3,3-테트라메틸디실라잔 3.6g을 25℃ 온도에서 1 시간 동안 반응시킨 후 진공증류로 정제하여 화학식 4로 표시되는 화합물 2.8g(수율: 98%)을 수득하였다.As a reaction solvent, 1.4 g of the compound of Formula 3 and 3.6 g of 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane in acetonitrile at a temperature of 25° C. After reacting for 1 hour, the mixture was purified by vacuum distillation to obtain 2.8 g of a compound represented by Chemical Formula 4 (yield: 98%).
[화학식 4][Formula 4]
Figure PCTKR2019015857-appb-I000011
Figure PCTKR2019015857-appb-I000011
1H NMR (299.87 MHz, CDCl3): δ = 0.16-0.28(t, 6H), 0.82-0.87(dt, 2H), 2.01-2.14(m, 2H), 3.14-3.18(dd, 1H), 3.50-3.55(dd, 1H), 4.20-4.24(dd, 1H), 4.51-4.55(dd, 1H), 4.83-4.89(qui, 1H)ppm 1 H NMR (299.87 MHz, CDCl 3 ): δ = 0.16-0.28 (t, 6H), 0.82-0.87 (dt, 2H), 2.01-2.14 (m, 2H), 3.14-3.18 (dd, 1H), 3.50 -3.55(dd, 1H), 4.20-4.24(dd, 1H), 4.51-4.55(dd, 1H), 4.83-4.89(qui, 1H)ppm
실시예 1: 전해액 조성물의 제조Example 1: Preparation of electrolyte composition
에틸렌 카보네이트(EC)와 에틸메틸 카보네이트(EMC)를 3:7 부피비로 혼합한 혼합 용매에 LiPF6를 1.0M이 되도록 첨가한 다음, 전해액 조성물 전체 100 중량%에 대하여 하기 화학식 2로 표시되는 화합물을 1 중량%의 양으로 첨가하고, 플루오로에틸렌카보네이트를 3 중량%의 양으로 첨가하여 전해액 조성물을 제조하였다.After adding LiPF 6 to 1.0 M in a mixed solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a 3:7 volume ratio, the compound represented by the following formula (2) with respect to 100% by weight of the total electrolyte composition: An electrolyte composition was prepared by adding in an amount of 1% by weight and adding fluoroethylene carbonate in an amount of 3% by weight.
[화학식 2][Formula 2]
Figure PCTKR2019015857-appb-I000012
Figure PCTKR2019015857-appb-I000012
실시예 2: 전해액 조성물의 제조Example 2: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 3으로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 3 was used instead of the compound represented by Chemical Formula 2.
[화학식 3][Formula 3]
Figure PCTKR2019015857-appb-I000013
Figure PCTKR2019015857-appb-I000013
실시예 3: 전해액 조성물의 제조Example 3: Preparation of electrolyte composition
화학식 2로 표시되는 화합물을 0.05 중량%의 양으로 첨가하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2 was added in an amount of 0.05% by weight.
실시예 4: 전해액 조성물의 제조Example 4: Preparation of electrolyte composition
화학식 2로 표시되는 화합물을 3 중량%의 양으로 첨가하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2 was added in an amount of 3% by weight.
실시예 5: 전해액 조성물의 제조Example 5: Preparation of electrolyte composition
플루오로에틸렌카보네이트를 0.5 중량%의 양으로 첨가하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.The electrolyte composition was prepared in the same manner as in Example 1, except that fluoroethylene carbonate was added in an amount of 0.5% by weight.
실시예 6: 전해액 조성물의 제조Example 6: Preparation of electrolyte composition
플루오로에틸렌카보네이트를 20 중량%의 양으로 첨가하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.The electrolyte composition was prepared in the same manner as in Example 1, except that fluoroethylene carbonate was added in an amount of 20% by weight.
실시예 7: 전해액 조성물의 제조Example 7: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 4로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 4 was used instead of the compound represented by Chemical Formula 2.
[화학식 4][Formula 4]
Figure PCTKR2019015857-appb-I000014
Figure PCTKR2019015857-appb-I000014
실시예 8: 전해액 조성물의 제조Example 8: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 5로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 5 was used instead of the compound represented by Chemical Formula 2.
[화학식 5][Formula 5]
Figure PCTKR2019015857-appb-I000015
Figure PCTKR2019015857-appb-I000015
실시예 9: 전해액 조성물의 제조Example 9: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 6으로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 6 was used instead of the compound represented by Chemical Formula 2.
[화학식 6][Formula 6]
Figure PCTKR2019015857-appb-I000016
Figure PCTKR2019015857-appb-I000016
실시예 10: 전해액 조성물의 제조Example 10: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 7로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 7 was used instead of the compound represented by Chemical Formula 2.
[화학식 7][Formula 7]
Figure PCTKR2019015857-appb-I000017
Figure PCTKR2019015857-appb-I000017
실시예 11: 전해액 조성물의 제조Example 11: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 8로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 8 was used instead of the compound represented by Chemical Formula 2.
[화학식 8][Formula 8]
Figure PCTKR2019015857-appb-I000018
Figure PCTKR2019015857-appb-I000018
실시예 12: 전해액 조성물의 제조Example 12: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 9로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 9 was used instead of the compound represented by Chemical Formula 2.
[화학식 9][Formula 9]
Figure PCTKR2019015857-appb-I000019
Figure PCTKR2019015857-appb-I000019
비교예 1: 전해액 조성물의 제조Comparative Example 1: Preparation of electrolyte composition
화학식 2로 표시되는 화합물을 첨가하지 않는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 2 was not added.
비교예 2: 전해액 조성물의 제조Comparative Example 2: Preparation of electrolyte composition
플루오로에틸렌카보네이트를 첨가하지 않는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that fluoroethylene carbonate was not added.
비교예 3: 전해액 조성물의 제조Comparative Example 3: Preparation of electrolyte composition
플루오로에틸렌카보네이트를 첨가하지 않는 것을 제외하고, 실시예 2와 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 2, except that fluoroethylene carbonate was not added.
비교예 4: 전해액 조성물의 제조Comparative Example 4: Preparation of electrolyte composition
플루오로에틸렌카보네이트를 첨가하지 않는 것을 제외하고, 실시예 7과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 7, except that fluoroethylene carbonate was not added.
비교예 5: 전해액 조성물의 제조Comparative Example 5: Preparation of electrolyte composition
화학식 2로 표시되는 화합물 대신 하기 화학식 a로 표시되는 화합물을 사용하는 것을 제외하고, 실시예 1과 동일하게 수행하여 전해액 조성물을 제조하였다.An electrolyte composition was prepared in the same manner as in Example 1, except that the compound represented by the following formula (a) was used instead of the compound represented by the formula (2).
[화학식 a][Formula a]
Figure PCTKR2019015857-appb-I000020
Figure PCTKR2019015857-appb-I000020
실험예 1: Experimental Example 1:
상기 실시예 및 비교예에서 제조된 전해액 조성물을 이용하여 아래와 같이 이차전지를 제조하였으며, 이때의 상온수명특성, 고온안정성 및 고온수명특성을 하기와 같은 방법으로 측정하고, 전해액 조성물의 저장 후 변색 특성을 관찰하여, 그 결과를 하기 표 1에 나타내었다.A secondary battery was prepared as follows using the electrolyte composition prepared in the above Examples and Comparative Examples, and the room temperature life characteristics, high temperature stability and high temperature life characteristics were measured in the following manner, and the discoloration characteristics after storage of the electrolyte composition It was observed, and the results are shown in Table 1 below.
<이차전지의 제조><Production of secondary battery>
양극 활물질로서 LiNi1/3Co1/3Mn1/3O2 분말, 탄소 도전재(Super-P; Timcal Ltd.) 및 PVDF(polyvinylidene fluoride) 바인더를 90:5:5의 중량비로 혼합한 혼합물에 용매로서 N-메틸피롤리돈(NMP)을 고형분의 함량이 60 중량%가 되도록 첨가하여 양극 슬러리를 제조하였다. 15㎛ 두께의 알루미늄 호일 위에 약 40 ㎛의 두께로 상기 양극 슬러리를 코팅하였다. 이를 상온에서 건조하고, 120℃에서 다시 건조한 후 압연하여 양극을 제조하였다.As a positive electrode active material, a mixture of LiNi 1/3 Co 1/3 Mn 1/3 O 2 powder, carbon conductive material (Super-P; Timcal Ltd.) and PVDF (polyvinylidene fluoride) binder in a weight ratio of 90:5:5 As a solvent, N-methylpyrrolidone (NMP) was added so that the content of solid content was 60% by weight to prepare a positive electrode slurry. The positive electrode slurry was coated to a thickness of about 40 μm on a 15 μm thick aluminum foil. It was dried at room temperature, dried again at 120° C., and rolled to prepare an anode.
음극 활물질로서 인조 흑연, 스티렌-부타디엔 러버, 카르복시메틸셀룰로오즈를 90:5:5의 중량비로 혼합한 혼합물에 N-메틸피롤리돈을 고형분의 함량이 60 중량%가 되도록 첨가하여 음극 슬러리를 제조하였다. 10㎛ 두께의 구리 호일 위에 약 40 ㎛의 두께로 상기 음극 슬러리를 코팅하였다. 이를 상온에서 건조하고, 120℃에서 다시 건조한 후 압연하여 음극을 제조하였다.A negative electrode slurry was prepared by adding N-methylpyrrolidone to a content of 60% by weight of N-methylpyrrolidone as a mixture of artificial graphite, styrene-butadiene rubber, and carboxymethylcellulose in a weight ratio of 90:5:5 as the negative electrode active material. . The negative electrode slurry was coated to a thickness of about 40 μm on a 10 μm thick copper foil. It was dried at room temperature, dried again at 120° C., and rolled to prepare a negative electrode.
상기 양극, 음극 및 전해액 조성물과 폴리에틸렌 재질의 세퍼레이터를 사용하여 이차 전지를 제조하였다.A secondary battery was manufactured using the positive electrode, the negative electrode, and the electrolyte composition and a separator made of polyethylene.
상기 제조된 이차전지를 25℃에서 0.2C의 전류로 전압이 4.2V에 이를 때까지 정전류로 충전하고, 이어서 전압이 2.5V에 이를 때까지 0.2C의 정전류로 방전하였다. 이어서, 0.5C의 전류로 전압이 4.2V에 이를 때까지 정전류 충전하고, 4.2V를 유지하면서 전류가 0.05C가 될 때까지 정전압 충전하였다. 이어서, 방전시에 전압이 2.5V에 이를 때까지 0.5C의 정전류로 방전하였다 (화성 단계).The prepared secondary battery was charged with a constant current until the voltage reached 4.2V at a current of 0.2C at 25°C, and then discharged with a constant current of 0.2C until the voltage reached 2.5V. Subsequently, the constant current was charged until the voltage reached 4.2V with a current of 0.5C, and the constant voltage was charged until the current became 0.05C while maintaining 4.2V. Subsequently, the discharge was discharged at a constant current of 0.5 C until the voltage reached 2.5 V (chemical conversion step).
(1) 상온수명특성(1) Room temperature life characteristics
상기 화성 단계를 거친 이차전지를 25℃에서 1.0C의 전류로 전압이 4.2V에 이를 때까지 정전류 충전하고, 4.2V를 유지하면서 전류가 0.05C가 될 때까지 정전압 충전하였다. 이어서, 방전시에 전압이 2.5V에 이를 때까지 1.0C의 정전류로 방전하는 사이클을 300회 반복하였다.The secondary battery that had undergone the chemical conversion step was charged with a constant current until the voltage reached 4.2V at a current of 1.0C at 25°C, and was charged with a constant voltage until the current reached 0.05C while maintaining 4.2V. Subsequently, the cycle of discharging with a constant current of 1.0C was repeated 300 times until the voltage reached 2.5V during discharge.
각각의 이차전지의 300번째 사이클에서의 용량 유지율(capacity retention ratio, %)을 하기 수학식 1로 계산하였다.The capacity retention ratio (%) in the 300th cycle of each secondary battery was calculated by Equation 1 below.
[수학식 1][Equation 1]
용량유지율[%]=[300번째 사이클에서의 방전용량/1번째 사이클에서의 방전용량]×100Capacity retention rate [%]=[Discharge capacity at 300th cycle/1 Discharge capacity at 1st cycle]×100
(2) 고온 전압 보존 안정성(2) High temperature voltage storage stability
상기 화성 단계를 거친 이차전지를 25℃에서 1.0C의 전류로 전압이 4.2V에 이를 때까지 정전류 충전하고, 4.2V를 유지하면서 전류가 0.05C가 될 때까지 정전압 충전하였다. 이어서, 충전된 이차전지를 60℃에서 보관하면서 24시간마다 multi-meter를 이용하여 전압을 측정하여 충전상태 셀의 고온에서 잔류 전압을 측정하여 고온 전압 보존 안정성을 측정하였다.The secondary battery that had undergone the chemical conversion step was charged with a constant current until the voltage reached 4.2V at a current of 1.0C at 25°C, and was charged with a constant voltage until the current reached 0.05C while maintaining 4.2V. Subsequently, while storing the charged secondary battery at 60°C, the voltage was measured using a multi-meter every 24 hours to measure the residual voltage at a high temperature of the charged state cell to measure the stability of high temperature voltage storage.
각각의 이차전지의 15일째 측정 시 전압 유지율(Voltage retention, %)을 하기 수학식 2로 계산하였다.When measuring the 15th day of each secondary battery, the voltage retention (%) was calculated by Equation 2 below.
[수학식 2][Equation 2]
전압 유지율[%]=[15일째 개방전압/초기 개방전압]×100Voltage retention rate [%]=[Opening voltage on the 15th day/Initial opening voltage]×100
(3) 변색 특성(3) Discoloration characteristics
실시예 및 비교예에서 제조된 전해액 조성물을 60℃ 하에서 15일 동안 저장 후 색변화를 관찰하여 하기 평가기준으로 평가하였다.The electrolyte compositions prepared in Examples and Comparative Examples were evaluated under the following evaluation criteria by observing the color change after storage for 15 days at 60°C.
<평가기준><Evaluation criteria>
○: 색변화 없음○: No color change
×: 색변화 있음×: There is color change
(4) 고온수명특성(4) High temperature life characteristics
상기 화성 단계를 거친 이차전지를 45℃에서 1.0C의 전류로 전압이 4.2V에 이를 때까지 정전류 충전하고, 4.2V를 유지하면서 전류가 0.05C가 될 때까지 정전압 충전하였다. 이어서, 방전시에 전압이 2.5V에 이를 때까지 1.0C의 정전류로 방전하는 사이클을 300회 반복하였다.The secondary battery that had undergone the chemical conversion step was charged with a constant current until the voltage reached 4.2V at a current of 1.0C at 45°C, and was charged with a constant voltage until the current reached 0.05C while maintaining 4.2V. Subsequently, the cycle of discharging with a constant current of 1.0C was repeated 300 times until the voltage reached 2.5V during discharge.
각각의 이차전지의 300번째 사이클에서의 용량 유지율(capacity retention ratio, %)을 상기 수학식 1로 계산하였다.The capacity retention ratio (%) in the 300th cycle of each secondary battery was calculated by Equation 1 above.
상온수명특성Room temperature life characteristics 고온안정성High temperature stability 변색 특성Discoloration characteristics 고온수명특성High temperature life characteristics
실시예 1Example 1 94.0%94.0% 96.2%96.2% ○○ 92.3%92.3%
실시예 2Example 2 91.4%91.4% 95.5%95.5% ○○ 89.3%89.3%
실시예 3Example 3 87.1%87.1% 96.0%96.0% ○○ 86.7%86.7%
실시예 4Example 4 93.8%93.8% 96.2%96.2% ○○ 90.4%90.4%
실시예 5Example 5 87.8%87.8% 95.2%95.2% ○○ 89.5%89.5%
실시예 6Example 6 96.7%96.7% 95.7%95.7% ○○ 88.2%88.2%
실시예 7Example 7 94.2%94.2% 96.3%96.3% ○○ 92.5%92.5%
실시예 8Example 8 93.8%93.8% 96.1%96.1% ○○ 90.8%90.8%
실시예 9Example 9 93.3%93.3% 95.9%95.9% ○○ 91.2%91.2%
실시예 10Example 10 94.0%94.0% 96.2%96.2% ○○ 91.1%91.1%
실시예 11Example 11 93.9%93.9% 96.1%96.1% ○○ 90.5%90.5%
실시예 12Example 12 93.6%93.6% 96.3%96.3% ○○ 90.8%90.8%
비교예 1Comparative Example 1 86.3%86.3% 94.3%94.3% ○○ 79.3%79.3%
비교예 2Comparative Example 2 81.7%81.7% 96.0%96.0% ○○ 75.4%75.4%
비교예 3Comparative Example 3 76.3%76.3% 95.5%95.5% ○○ 70.3%70.3%
비교예 4Comparative Example 4 82.1%82.1% 96.0%96.0% ○○ 78.4%78.4%
비교예 5Comparative Example 5 84.1%84.1% 93.8%93.8% ×× 79.3%79.3%
상기 표 1에 나타낸 바와 같이, 본 발명에 따른 화학식 1로 표시되는 프로판 설톤 화합물과 환상 플루오로 카보네이트계 화합물을 포함하는 실시예 1 내지 12의 전해액 조성물을 이용하여 제조된 이차전지는 비교예 1 내지 5의 전해액 조성물을 이용하여 제조된 이차전지에 비해 상온에서 더욱 우수한 수명특성을 가질 뿐만 아니라 고온에서도 우수한 안정성과 수명특성을 나타내는 것을 확인할 수 있었다.As shown in Table 1, the secondary battery prepared by using the electrolyte composition of Examples 1 to 12 including the propane sulfone compound represented by Chemical Formula 1 according to the present invention and the cyclic fluoro carbonate compound is Comparative Examples 1 to Compared to the secondary battery prepared using the electrolyte composition of 5, it was confirmed that it not only has better life characteristics at room temperature, but also excellent stability and life characteristics at high temperatures.
이는 본 발명에 따른 전해액 조성물 중의 환상 플루오로 카보네이트계 화합물이 SEI 피막을 형성하고, 화학식 1로 표시되는 프로판 설톤 화합물이 환상 플루오로 카보네이트계 화합물에 의해 생성될 수 있는 HF를 제거하면서 전기화학 반응에 의하여 개환되어 SEI 피막 형성에 기여하기 때문인 것으로 보인다.This is in the electrochemical reaction while the cyclic fluorocarbonate-based compound in the electrolyte composition according to the present invention forms an SEI film, and the propane sulfone compound represented by the formula (1) removes HF that can be produced by the cyclic fluorocarbonate-based compound. It seems to be because it is opened and contributes to SEI film formation.
비교예 5의 전해액 조성물은 일정 시간 저장 후 색변화가 일어나는 것으로 나타났다.The electrolyte composition of Comparative Example 5 was found to change color after storage for a period of time.
이상으로 본 발명의 특정한 부분을 상세히 기술하였는 바, 본 발명이 속한 기술분야에서 통상의 지식을 가진 자에게 있어서 이러한 구체적인 기술은 단지 바람직한 구현예일 뿐이며, 이에 본 발명의 범위가 제한되는 것이 아님은 명백하다. 본 발명이 속한 기술분야에서 통상의 지식을 가진 자라면 상기 내용을 바탕으로 본 발명의 범주 내에서 다양한 응용 및 변형을 행하는 것이 가능할 것이다. Since the specific parts of the present invention have been described in detail above, it is obvious that for those skilled in the art to which the present invention pertains, this specific technology is only a preferred embodiment, and the scope of the present invention is not limited thereto. Do. Those skilled in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above.
따라서, 본 발명의 실질적인 범위는 첨부된 특허청구범위와 그의 등가물에 의하여 정의된다고 할 것이다.Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (10)

  1. 하기 화학식 1로 표시되는 화합물, 환상 플루오로 카보네이트계 화합물 및 비수용매를 포함하는 전해액 조성물:Electrolyte composition comprising a compound represented by the formula (1), a cyclic fluoro carbonate-based compound and a non-aqueous solvent:
    [화학식 1][Formula 1]
    Figure PCTKR2019015857-appb-I000021
    Figure PCTKR2019015857-appb-I000021
    상기 식에서,In the above formula,
    R은 수소 원자 또는 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, R is a hydrogen atom or Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y ,
    x, y 및 z는 각각 독립적으로 0 내지 3의 정수이다.x, y and z are each independently an integer from 0 to 3.
  2. 제1항에 있어서, R은 Si[(CH2)xCH3]y[(CH2)zCF3]3-y이고, x, y 및 z는 각각 독립적으로 0 내지 3의 정수인 전해액 조성물.The electrolyte composition according to claim 1, wherein R is Si[(CH 2 ) x CH 3 ] y [(CH 2 ) z CF 3 ] 3-y , and x, y and z are each independently an integer of 0 to 3.
  3. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 하기 화학식 2 내지 9 중 어느 하나로 표시되는 화합물인 전해액 조성물.The composition of claim 1, wherein the compound represented by Formula 1 is a compound represented by any one of Formulas 2 to 9 below.
    [화학식 2][Formula 2]
    Figure PCTKR2019015857-appb-I000022
    Figure PCTKR2019015857-appb-I000022
    [화학식 3][Formula 3]
    Figure PCTKR2019015857-appb-I000023
    Figure PCTKR2019015857-appb-I000023
    [화학식 4][Formula 4]
    Figure PCTKR2019015857-appb-I000024
    Figure PCTKR2019015857-appb-I000024
    [화학식 5][Formula 5]
    Figure PCTKR2019015857-appb-I000025
    Figure PCTKR2019015857-appb-I000025
    [화학식 6][Formula 6]
    Figure PCTKR2019015857-appb-I000026
    Figure PCTKR2019015857-appb-I000026
    [화학식 7][Formula 7]
    Figure PCTKR2019015857-appb-I000027
    Figure PCTKR2019015857-appb-I000027
    [화학식 8][Formula 8]
    Figure PCTKR2019015857-appb-I000028
    Figure PCTKR2019015857-appb-I000028
    [화학식 9][Formula 9]
    Figure PCTKR2019015857-appb-I000029
    Figure PCTKR2019015857-appb-I000029
  4. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물은 전해액 조성물 전체 100 중량%에 대하여 0.05 내지 5 중량%의 양으로 포함되는 전해액 조성물.The method of claim 1, wherein the compound represented by Formula 1 is an electrolyte composition contained in an amount of 0.05 to 5% by weight relative to the total 100% by weight of the electrolyte composition.
  5. 제1항에 있어서, 상기 환상 플루오로 카보네이트계 화합물은 플루오로에틸렌카보네이트를 포함하는 전해액 조성물.The electrolyte composition of claim 1, wherein the cyclic fluorocarbonate-based compound comprises fluoroethylene carbonate.
  6. 제1항에 있어서, 상기 환상 플루오로 카보네이트계 화합물은 전해액 조성물 전체 100 중량%에 대하여 0.5 내지 30 중량%의 양으로 포함되는 전해액 조성물.The electrolyte composition of claim 1, wherein the cyclic fluorocarbonate-based compound is included in an amount of 0.5 to 30% by weight based on 100% by weight of the total electrolyte composition.
  7. 제1항에 있어서, 상기 화학식 1로 표시되는 화합물과 환상 플루오로 카보네이트계 화합물의 중량비는 1:1 내지 1:20인 전해액 조성물.The electrolyte composition according to claim 1, wherein the weight ratio of the compound represented by Chemical Formula 1 and the cyclic fluorocarbonate compound is 1:1 to 1:20.
  8. 제1항에 있어서, 리튬염을 추가로 포함하는 전해액 조성물.The electrolyte composition of claim 1, further comprising a lithium salt.
  9. 제1항 내지 제8항 중 어느 한 항에 따른 전해액 조성물을 포함하는 이차전지.A secondary battery comprising the electrolyte composition according to any one of claims 1 to 8.
  10. 제9항에 있어서, 상기 이차전지가 리튬 이차전지인 이차전지.The secondary battery according to claim 9, wherein the secondary battery is a lithium secondary battery.
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WO2007064076A1 (en) * 2005-09-15 2007-06-07 Lg Chem, Ltd. Nonaqueous electrolyte for improving performance and lithium secondary battery comprising the same
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KR100977973B1 (en) 2007-01-09 2010-08-24 주식회사 엘지화학 Non-aqueous electrolyte and secondary battery comprising the same
JP2013089390A (en) * 2011-10-14 2013-05-13 Ube Ind Ltd Nonaqueous electrolyte and power storage device using the same
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