WO2019107855A1 - Électrolyte polymère pour batterie secondaire et batterie secondaire le comprenant - Google Patents

Électrolyte polymère pour batterie secondaire et batterie secondaire le comprenant Download PDF

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WO2019107855A1
WO2019107855A1 PCT/KR2018/014638 KR2018014638W WO2019107855A1 WO 2019107855 A1 WO2019107855 A1 WO 2019107855A1 KR 2018014638 W KR2018014638 W KR 2018014638W WO 2019107855 A1 WO2019107855 A1 WO 2019107855A1
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polymer electrolyte
secondary battery
electrolyte
organic solvent
formula
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PCT/KR2018/014638
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English (en)
Korean (ko)
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박솔지
안경호
이철행
한준혁
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주식회사 엘지화학
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Priority claimed from KR1020180145929A external-priority patent/KR102255538B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18884399.9A priority Critical patent/EP3648229B1/fr
Priority to PL18884399.9T priority patent/PL3648229T3/pl
Priority to CN201880049382.3A priority patent/CN110998954A/zh
Priority to US16/633,237 priority patent/US11670800B2/en
Publication of WO2019107855A1 publication Critical patent/WO2019107855A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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 a polymer electrolyte for a secondary battery and a secondary battery comprising the same.
  • the lithium secondary battery can be divided into a lithium ion battery using a liquid electrolyte and a lithium polymer battery using a polymer electrolyte according to an applied electrolyte.
  • the gel polymer electrolyte containing the solid polymer electrolyte or the electrolyte is used as the electrolyte, the safety can be improved. In addition, it has flexibility and can be developed in various forms such as a small size or a thin film type.
  • the solid polymer electrolyte exhibits a significantly lower ion conductivity than the liquid electrolyte, which is not suitable for commercialization.
  • polyethylene oxide which is widely used as a polymer electrolyte, is excellent in the ability to dissociate an ion conductive metal salt in spite of its solid state. That is, since the cation of the alkali metal salt is stabilized by forming a complex with the oxygen atoms present in the polyethylene oxide to form a complex, it can exist in a stable ion state without a solvent.
  • the polyethylene oxide has a semi-crystalline structure at room temperature, and since such a crystal structure interferes with the movement of the dissociated metal salt, it has a disadvantage that it has a low ionic conductivity value of about 1.0 ⁇ 10 -8 S / cm at room temperature . Therefore, it is not suitable for commercialization.
  • the present invention provides a polymer electrolyte for a secondary battery having improved mechanical strength and ionic conductivity.
  • the present invention also provides a lithium secondary battery having improved capacity retention, output characteristics, and oxidation stability by including the polymer electrolyte for a secondary battery of the present invention.
  • polymer electrolyte for a secondary battery comprising a polymer comprising a repeating unit represented by the following formula (1).
  • R 0 is an alkylene group having 1 to 5 carbon atoms substituted with at least one halogen atom
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, a halogen atom, or an alkyl group having 1 to 5 carbon atoms in which at least one halogen atom is substituted or unsubstituted,
  • A is at least one cation selected from the group consisting of Li + , H + , Na + and K +
  • n and m each represent the number of repeating units
  • n is an integer of 1 to 100
  • n is an integer of 1 to 100;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, a halogen atom or an alkyl group having 1 to 3 carbon atoms, A is Li + . & Lt; / RTI > Specifically, the halogen element may be a fluorine element.
  • the repeating unit represented by the formula (1) may be at least one selected from the group consisting of repeating units represented by the following formulas (1a) to (1d).
  • n1: m1 is the number of repeating units
  • n1 is an integer of 1 to 100
  • n1 is an integer of 1 to 100;
  • n2: m2 is the number of repeating units
  • n2 is an integer of 1 to 100
  • m < 2 &gt is an integer of any one of 1 to 100.
  • n3 is an integer of 1 to 100
  • n3 is any integer from 1 to 100.
  • n4 is any integer from 1 to 100
  • n4 is any integer of 1 to 100.
  • the polymer electrolyte for the secondary battery may be a free-standing solid polymer electrolyte or a gel polymer electrolyte.
  • the polymer electrolyte for a secondary battery may be a gel polymer electrolyte further comprising a non-aqueous electrolyte including an electrolyte and a fluorine-based organic solvent.
  • the fluorinated organic solvent contained in the non-aqueous electrolyte may be at least one selected from the group consisting of fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), fluorodimethyl carbonate (F-DMC), fluoroethylmethyl carbonate (FEMC) (Trifluoromethyl) -1,3-dioxolane (TFDOL), methyl 2,2,2-trifluoroethyl carbonate (F3-EMC), trifluoroethyl phosphite (TFEPi) Trifluoroethyl phosphate (TFEPa), 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (1,1,2,2-Tetrafluoroethyl 2,2- 2-trifluoroethyl ether, monofluorobenzene (FB), difluorobenzene, trifluorobenzene, tetrafluorobenzene, pen
  • the non-aqueous electrolyte solution may further include a non-fluorine-based organic solvent.
  • the fluorine-based organic solvent and non-fluorine-based organic solvent may be contained in a volume ratio of 0.5: 95.5 to 100: 0.
  • non-aqueous electrolyte may further include an ionic liquid.
  • the ionic liquid may be at least one selected from the group consisting of diethylmethylammonium trifluoromethanesulfonate, dimethylpropylammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) Methyl-N-propylpiperidiumbis (trifluoromethanesulfonyl) imide, N-butyl-N-methylpyrrolidiumbis (trifluoromethanesulfonyl) imide, And methylpropylpiperidium trifluoromethanesulfonylimide.
  • an embodiment of the present invention provides a lithium secondary battery comprising the polymer electrolyte for a secondary battery of the present invention.
  • a polymer electrolyte for a secondary battery which can secure high ionic conductivity and mechanical strength by using a polymer containing at least one repeating unit containing the same cation and sulfonate group as the cation of the electrolyte salt in the structure . Also, by including it, a lithium secondary battery having improved capacity retention, output characteristics and oxidation stability can be manufactured.
  • FIG. 1 is a graph showing a capacity retention measurement result of a lithium secondary battery according to Experimental Example 4 of the present invention.
  • the polymer electrolyte for a secondary battery includes a polymer including a repeating unit represented by the following formula (1).
  • R 0 is an alkylene group having 1 to 5 carbon atoms substituted with at least one halogen atom
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, a halogen atom, or an alkyl group having 1 to 5 carbon atoms in which at least one halogen atom is substituted or unsubstituted,
  • A is at least one cation selected from the group consisting of Li + , H + , Na + and K +
  • n and m each represent the number of repeating units
  • n is an integer of 1 to 100
  • n is an integer of 1 to 100
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are each independently hydrogen, a halogen atom or an alkyl group having 1 to 3 carbon atoms, A is Li + . & Lt; / RTI > Specifically, the halogen element may be a fluorine element.
  • the repeating units n and m may be alternately arranged in a graft form or randomly arranged with or without a certain rule have.
  • the molar ratio of the repeating unit number n: m may be from 1: 1 to 1: 100, more specifically from 1: 1 to 1:10.
  • the ionic conductivity can be reduced by lowering the efficiency of dissociating or moving the Li salt and repeating
  • the molar ratio of the unit number m is less than 1, the mechanical properties may be deteriorated.
  • the weight average molecular weight (Mw) of the polymer containing the repeating unit represented by the formula (1) may independently be 5,000 g / mol to 2,000,000 g / mol, specifically 100,000 g / mol to 1,000,000 g / mol.
  • the weight average molecular weight (Mw) of the repeating unit represented by the formula (1) can be measured by Gel Permeation Chromatography (GPC). For example, after a sample of a certain concentration is prepared, the GPC measurement system alliance 4 apparatus is stabilized. Once the instrument is stabilized, the chromatogram can be obtained by injecting standard and sample samples into the instrument and then calculating the molecular weight according to the analytical method (system: Alliance 4, column: Ultrahydrogel linear X 2, eluent: 0.1M NaNO 3 pH 7.0 phosphate buffer, flow rate: 0.1 mL / min, temp: 40 ° C, injection: 100 ⁇ L).
  • the repeating unit represented by the formula (1) may be at least one selected from the group consisting of repeating units represented by the following formulas (1a) to (1d).
  • n1: m1 is the number of repeating units
  • n1 is an integer of 1 to 100
  • n1 is an integer of 1 to 100;
  • n2: m2 is the number of repeating units
  • n2 is an integer of 1 to 100
  • m < 2 &gt is an integer of any one of 1 to 100.
  • n3 is an integer of 1 to 100
  • n3 is any integer from 1 to 100.
  • n4 is any integer from 1 to 100
  • n4 is any integer of 1 to 100.
  • the polymer electrolyte for a secondary battery of the present invention may be a free-standing solid polymer electrolyte including a polymer containing a repeating unit represented by the general formula (1).
  • the electrolyte of the present invention is the self-supporting solid polymer electrolyte
  • the cationic source of the electrolyte salt is present in the polymer containing the repeating unit represented by the general formula (1)
  • the electrolyte The battery can also be driven in the form of an all solid-ion battery.
  • the self-supporting solid polymer electrolyte of the present invention can be formed according to a conventional solution casting method known in the art.
  • a coating solution is prepared by dissolving a polymer containing at least one of the repeating units represented by the above-described formula (1) in an organic solvent, casting it on a support substrate (casting film) and may be formed in a film form.
  • a glass substrate polyethylene terephthalate
  • Teflon polyethylene terephthalate
  • FEP film may be used as the supporting substrate, or an electrode such as a cathode or a cathode may be used.
  • a separation membrane may be used.
  • a coating solution is prepared by dissolving a polymer containing at least one of the repeating units represented by the formula (1) in an organic solvent, coating on the surface of the electrode (cathode) You may.
  • the thickness of the solid polymer electrolyte can be suitably controlled from several micrometers to several nanometers depending on the type of the supporting substrate. Specifically, the thickness of the free-standing solid polymer electrolyte is 10 m to 100 m, Specifically, it may be 10 [mu] m to 50 [mu] m.
  • the organic solvent used in the coating solution for preparing the self-supporting solid polymer electrolyte may be a low boiling point volatile organic solvent for easy removal during drying.
  • the organic solvent include N, N'-dimethylacetamide, N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF) and acetonitrile acetonitrile, AN).
  • NMP N-methylpyrrolidone
  • DMSO dimethylsulfoxide
  • DMF N-dimethylformamide
  • AN acetonitrile acetonitrile
  • the organic solvent is not particularly limited as long as the polymer containing the repeating unit represented by the formula (1) is dissolved in a uniform thickness and then easily removed.
  • the organic solvent may be used in an amount of about 100 parts by weight to 10,000 parts by weight, specifically 5,000 parts by weight to 10,000 parts by weight, based on 100 parts by weight of the polymer containing the repeating unit represented by the formula (1).
  • the amount of the organic solvent is more than 10,000 parts by weight, it is difficult to remove the organic solvent in a short period of time, and it is difficult to sufficiently secure the mechanical strength, thin film thickness and ionic conductivity of the polymer electrolyte due to the residual organic solvent .
  • the amount of the organic solvent used is less than 100 parts by weight, it is difficult to dissolve the polymer containing the repeating unit represented by the formula (1), and the uniformity of the film may be lowered during the molding of the polymer electrolyte.
  • solid polymer electrolyte has a disadvantage in that it has a low ion conductivity because its resistance in a cell is larger than that of a liquid electrolyte and thus the movement speed of lithium ions is slow.
  • the solid polymer including the repeating unit represented by the formula (1) of the present invention is a conjugated polymer in which the cation of the electrolyte salt, for example, A is Li + ion, by containing both + ions and sulfonate groups, as well as to suppress the decomposition of the side reaction, and the salt (salt) of the lithium ion (Li +) by anion stationary phase, by the liberalization of lithium ion (free Li +), The migration effect of lithium ions can be improved.
  • the lithium secondary battery including the lithium secondary battery can realize excellent capacity retention rate, cycle life characteristics, output characteristics, and thermal or chemical stability.
  • the solid gel polymer electrolyte of the present invention since the solid gel polymer electrolyte of the present invention has a cation source in the polymer containing the repeating unit represented by the formula (1), it has an ion-transfer characteristic without using a conventional electrolyte salt-containing liquid electrolyte, The ion transport characteristic may be lower than that of the liquid electrolyte due to the strong attraction of the liquid electrolyte.
  • a gel polymer electrolyte (for example, a solid-liquid hybrid electrolyte) formed by additionally injecting a non-aqueous electrolyte containing an electrolyte salt and an organic solvent into the solid polymer electrolyte may be provided to impart an ion- .
  • the gel polymer electrolyte of the present invention together with the solid polymer electrolyte and the nonaqueous electrolytic solution containing the electrolyte salt, it is possible to realize an electrolyte system that is more stable than the liquid electrolyte while improving the ion transfer characteristics.
  • the flux of Li can be made uniform, and even when applied to a lithium metal ion battery, dendrite generation can be reduced, .
  • a sulfonate group (SO 3 - ) into the repeating unit structure, thermal instability such as an exothermic reaction can be reduced by an anionic repulsion effect by Li + salt, thereby securing thermal stability.
  • the gel polymer electrolyte of the present invention is obtained by interposing a solid polymer electrolyte containing a polymer containing a repeating unit represented by the formula (1) of the present invention in an electrode assembly, storing the electrode assembly in a battery case, A non-aqueous electrolytic solution capable of swelling can be injected without dissolving it, and the solid polymer electrolyte may be swelled.
  • the non-aqueous electrolyte solution injected for preparing the gel polymer electrolyte may be a solution in which an electrolyte salt is dissolved in a fluorine-based organic solvent.
  • the electrolyte salt may be any of conventionally used electrolytes for a lithium secondary battery, and may include, for example, the same cation as the cation contained in the polymer containing the repeating unit represented by the formula (1), specifically Li + , H + , Na +, and K + , and the anion includes at least one selected from the group consisting of F - , Cl - , Br - , I - , NO 3 - , N (CN) 2 - , BF 4 - , ClO 4 -, AlO 4 - , AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, BC 4 O 8 -, PF 4 C 2 O 4 -, PF 2 C 4 O 8 -, (CF 3 ) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF
  • the electrolyte salt is preferably comprises the same cation and A in compounds of the formula 1, LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 Cl 10, which specifically include the Li + as the cation , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , LiAlO 4 and LiCH 3 SO 3 or a mixture of two or more thereof have.
  • the electrolytic salt may contain any one or more within a usable range and may be contained in the electrolytic solution at a concentration of 0.5 M to 4 M in order to obtain an effect of forming an anti-corrosive film on the optimum electrode surface. If the concentration of the electrolyte salt exceeds 4 M, the ion transfer characteristic may be significantly reduced due to the high viscosity.
  • the fluorine-based organic solvent is not particularly limited as long as it can minimize decomposition due to an oxidation reaction or the like during charging and discharging of the secondary battery and can exhibit desired properties together with additives.
  • Specific examples thereof include fluoroethylene carbonate (FEC), di (DFEC), fluorodimethyl carbonate (F-DMC), fluoroethyl methyl carbonate (FEMC), 2,2-bis (trifluoromethyl) -1,3-dioxolane (TFDOL) Methyl 2,2,2-trifluoroethyl carbonate (F3-EMC), Trifluoroethyl phosphite (TFEPi), Trifluoroethyl phosphate (TFEPa), 1,1,2,2 Trifluoromethyl ether, 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether, monofluorobenzene (FB), difluorobenzene, tetrafluoroethylene- Triflu
  • the fluorinated organic solvent may be at least one selected from the group consisting of fluoroethylene carbonate, difluoroethylene carbonate (DFEC), fluorodimethyl carbonate, fluoroethylmethyl carbonate (FEMC) and 2,2-bis (trifluoromethyl) , 3-dioxolane (TFDOL), and the like.
  • DFEC difluoroethylene carbonate
  • FEMC fluororodimethyl carbonate
  • FEMC fluoroethylmethyl carbonate
  • TFDOL 2,2-bis (trifluoromethyl) , 3-dioxolane
  • the gel polymer electrolyte of the present invention can further improve the impregnation property of the solid polymer electrolyte of the present invention as compared with a non-aqueous electrolyte using a non-fluorinated organic solvent by using a fluorinated organic solvent as the non-aqueous electrolyte organic solvent.
  • the fluorine-based solvent is uniformly distributed in the non-aqueous electrolyte by the fluorine element existing in the structure, the overall polarity of the non-aqueous electrolyte can be reduced.
  • the impregnation property of the non-aqueous electrolyte containing the fluorine- The gel polymer electrolyte uniformly impregnated with the nonaqueous electrolytic solution can be formed on the entire surface of the polymer electrolyte. Therefore, the flux uniformity of lithium ion (Li + ) is improved in the gel polymer electrolyte, thereby improving not only the cycle life characteristics and the output characteristics of the secondary battery, but also the safety improvement effect.
  • the organic solvent contained in the non-aqueous electrolyte may further include at least one non-fluorinated organic solvent selected from the group consisting of a carbonate-based organic solvent, an ester-based organic solvent, an ether-based organic solvent and an amide-based organic solvent in addition to the fluorinated organic solvent .
  • the carbonate-based organic solvent may be a cyclic carbonate-based organic solvent or a linear carbonate-based organic solvent.
  • the cyclic carbonate-based organic solvent is a high-viscosity organic solvent having high permittivity and high dissociation of electrolyte salts in the electrolyte, and examples thereof include ethylene carbonate (EC), propylene carbonate (PC), 1,2- And at least one selected from the group consisting of ethylene carbonate, ethylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and vinylene carbonate.
  • the linear carbonate-based organic solvent is an organic solvent having a low viscosity and a low dielectric constant, and examples thereof include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC) , Methyl propyl carbonate, and ethyl propyl carbonate.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethylmethyl carbonate
  • Methyl propyl carbonate Methyl propyl carbonate
  • ethyl propyl carbonate Methyl propyl carbonate
  • ester-based organic solvent may include a linear ester organic solvent or a cyclic ester organic solvent.
  • linear ester organic solvent examples include at least one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate and butyl propionate .
  • cyclic ester organic solvent examples include any one selected from the group consisting of? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone, or 2 Mixtures of two or more species may be used.
  • ether organic solvents include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether and 1,3-dioxolane (DOL) At least one < / RTI >
  • the nonaqueous electrolyte solution is mixed with a fluorochemical organic solvent such as fluoromethylmethyl carbonate (FMMC) or fluoroethylmethyl carbonate (FEMC), a cyclic carbonate organic solvent, a linear carbonate organic solvent and a linear ester organic solvent
  • a fluorochemical organic solvent such as fluoromethylmethyl carbonate (FMMC) or fluoroethylmethyl carbonate (FEMC)
  • FMMC fluoromethylmethyl carbonate
  • FEMC fluoroethylmethyl carbonate
  • the fluorinated organic solvent and non-fluorinated organic solvent have a volume ratio of 0.5: 95.5 to 100: 0 by volume, specifically 10:90 to 70:30 by volume, more specifically 30:70 to 60:40 Volume ratio.
  • the non-aqueous electrolyte is hardly uniformly impregnated on the entire surface of the solid polymer electrolyte including the polymer having the repeating unit represented by Formula 1,
  • the life characteristic and the output characteristic improvement effect may be insignificant.
  • the organic solvent constituting the non-aqueous electrolyte is prepared by mixing fluoroethylene carbonate (FEC), a fluorinated organic solvent, and ethylmethyl carbonate, which is a linear carbonate-based organic solvent, in a volume ratio of 3: 7 or fluoroethylmethyl carbonate (EC): Ethylmethyl carbonate (EMC) was mixed in a volume ratio of 3: 3: 4, or a mixture of ethylene carbonate (EC): ethyl methyl carbonate (EMC) 2.5: 7 by volume ratio, or FEC: F3-EMC: 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether in a volume ratio of 2: 6: 2 Ratio can be used.
  • FEC fluoroethylene carbonate
  • EC fluorinated organic solvent
  • ethylmethyl carbonate which is a linear carbonate-based organic solvent
  • the non-aqueous electrolyte may further include a nonvolatile organic solvent having a high boiling point such as tetraglyme to easily swell the polymer electrolyte to maintain the gel polymer electrolyte form.
  • a nonvolatile organic solvent having a high boiling point such as tetraglyme to easily swell the polymer electrolyte to maintain the gel polymer electrolyte form.
  • the amount of the main liquid of the nonaqueous electrolyte solution is not particularly limited, and the electrode assembly is sufficiently wetted according to a conventional method, and the uniformity of the membrane in forming the gel polymer electrolyte and the mechanical strength, thin film thickness and ion conductivity Can be used.
  • the gel polymer electrolyte may further include an ionic liquid if necessary.
  • an ionic liquid can be used by injecting a non-aqueous electrolytic solution containing an electrolytic salt, followed by further pouring.
  • the ionic liquid is a component having a high ionic conductivity.
  • the ionic liquid is impregnated with the electrolytic solution alone or with the electrolytic solution on the polymer electrolyte to improve the migration (Li + flux) of the lithium ion in the polymer electrolyte so that Li +
  • the phenomenon of stripping can be made uniform, the generation of lithium dendrite can be suppressed, and the flame retardant property can be obtained when applied inside the battery.
  • Examples of such an ionic liquid include diethylmethylammonium trifluoromethanesulfonate, dimethylpropylammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium Bis (trifluoromethanesulfonyl) imide, N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide, N-butyl-N-methylpyrrolidium bis (trifluoromethanesulfonyl) ) Imide, and methylpropylpiperidium trifluoromethanesulfonylimide. ≪ Desc / Clms Page number 7 >
  • the ionic liquid may be contained in an amount of 50 parts by weight or less, specifically 0.1 part by weight to 50 parts by weight, more specifically 1 part by weight to 30 parts by weight, based on 100 parts by weight of the nonaqueous electrolyte solution to be injected.
  • the content of the ionic liquid exceeds 50 parts by weight based on the total weight of the nonaqueous electrolyte solution, migration of lithium ions is difficult due to a high viscosity, so that a uniform lithium ion transfer effect can not be provided. Dendrites can be formed.
  • the lithium secondary battery of the present invention comprises
  • the polymer electrolyte may include a self-supporting solid polymer electrolyte or a gel polymer electrolyte.
  • the positive electrode, the negative electrode, and the separator forming the lithium secondary battery of the present invention can be used any of those conventionally manufactured and used in the production of the lithium secondary battery.
  • the positive electrode can be produced by forming a positive electrode mixture layer on the positive electrode collector.
  • the positive electrode material mixture layer may be prepared by coating a positive electrode slurry containing a positive electrode active material, a binder, a conductive material and a solvent, followed by drying and rolling.
  • the positive electrode collector is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the positive electrode collector may be formed of a metal such as carbon, stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode active material is a compound capable of reversibly intercalating and deintercalating lithium, and may specifically include a lithium composite metal oxide including lithium and at least one metal such as cobalt, manganese, nickel, or aluminum have. More specifically, the lithium composite metal oxide may be at least one selected from the group consisting of lithium-manganese-based oxides (for example, LiMnO 2 and LiMn 2 O 4 ), lithium-cobalt oxides (for example, LiCoO 2 ), lithium- (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.
  • LiMnO 2 and LiMn 2 O 4 lithium-cobalt oxides
  • LiCoO 2 lithium-
  • lithium-manganese-cobalt oxide e. g., (in which LiCo 1-Y2 Mn Y2 O 2 , 0 ⁇ Y2 ⁇ 1), LiMn 2-z1 Co z1 O 4 ( here, 0 ⁇ z1 ⁇ 2) and the like
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (for example, Li (Ni 1/3 Mn 1/3 Co 1 / 3 ) O 2 , Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2, Li (Ni 0.7 Mn 0.15 Co 0.15) O 2 and Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 ), or lithium nickel cobalt aluminum oxide (e.g., Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.) and the like.
  • lithium nickel cobalt aluminum oxide e.g., Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.
  • the positive electrode active material may include 80 wt% to 99.5 wt%, specifically 85 wt% to 95 wt%, based on the total weight of the solid content in the positive electrode slurry. At this time, when the cathode active material content is 80 wt% or less, the energy density is lowered and the capacity may be lowered.
  • the binder is a component that assists in bonding of the active material to the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the solid content in the positive electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene (Ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM tetrafluoroethylene
  • EPDM tetrafluoroethylene
  • EPDM sulfonated EPDM
  • the conductive material is usually added in an amount of 1 to 30% by weight based on the total weight of the solid content in the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery.
  • Conductive fibers such as carbon fiber and metal fiber;
  • Metal powders such as carbon fluoride, aluminum, and nickel powder;
  • Conductive whiskey such as zinc oxide and potassium titanate;
  • Conductive metal oxides such as titanium oxide;
  • Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that provides a preferable viscosity when the positive electrode active material and optionally a binder and a conductive material are included.
  • NMP N-methyl-2-pyrrolidone
  • the solid content in the slurry containing the cathode active material and optionally the binder and the conductive material may be 10 wt% to 60 wt%, preferably 20 wt% to 50 wt%.
  • the negative electrode may be manufactured by forming a negative electrode mixture layer on the negative electrode collector.
  • the negative electrode material mixture layer may be formed by coating an anode current collector with a negative electrode slurry including a negative electrode active material, a binder, a conductive material, and a solvent, followed by drying and rolling.
  • the anode current collector generally has a thickness of 3 to 500 mu m.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • Examples of the negative electrode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used.
  • fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
  • the negative electrode active material may be a lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, lithium capable of doping and dedoping lithium Materials and transition metal oxide transition metal oxides.
  • the carbonaceous material capable of reversibly intercalating / deintercalating lithium ions is not particularly limited as long as it is a carbonaceous anode active material generally used in a lithium ion secondary battery.
  • the carbonaceous material include crystalline carbon, Amorphous carbon or any combination thereof.
  • the crystalline carbon include graphite such as natural graphite or artificial graphite in the form of amorphous, plate-like, flake, spherical or fiber, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.
  • the metal or an alloy of these metals and lithium may be selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, And Sn, or an alloy of these metals and lithium may be used.
  • metal composite oxide is PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, GeO, GeO 2, Bi 2 O 3, Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0 x 1), Li x WO 2 (0 x 1) and Sn x Me 1-x Me y O z (Me: Mn, Fe, Pb, Ge; Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, Halogen; 0 ⁇ x? 1; 1? Y? 3; 1? Z? Can be used.
  • Si As the material capable of doping and dedoping lithium, Si, SiO x (0 ⁇ x? 2), Si-Y alloy (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element and an element selected from the group consisting of combinations thereof, and not Sn), and at least one of them may be mixed with SiO 2 .
  • Si-Y alloy Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si
  • Sn, SnO 2 Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element
  • the element Y may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Se, Te, Po, and combinations thereof.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be contained in an amount of 80% by weight to 99% by weight based on the total weight of the solid content in the negative electrode slurry.
  • the binder is a component that assists in bonding between the conductive material, the active material and the current collector, and is usually added in an amount of 1 to 30% by weight based on the total weight of the solid content in the negative electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers thereof.
  • the conductive material is a component for further improving the conductivity of the negative electrode active material and may be added in an amount of 1 to 20 wt% based on the total weight of the solid content in the negative electrode slurry.
  • a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, for example, graphite such as natural graphite or artificial graphite; Carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskey such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include water or an organic solvent such as NMP, alcohol, etc., and may be used in an amount in which the negative electrode active material and, optionally, a binder, a conductive material, and the like are contained in a desired viscosity.
  • the solid content in the slurry containing the negative electrode active material and optionally the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 65 wt%.
  • the lithium secondary battery of the present invention may further include a separator if necessary.
  • the separation membrane blocks the internal short circuit of both electrodes and impregnates the electrolyte.
  • the separation membrane composition is prepared by mixing a polymer resin, a filler, and a solvent, and then the separation membrane composition is directly coated on the electrode and dried, Or may be formed by casting and drying the separation membrane composition on a support, and then laminating the separation membrane film peeled off from the support on the electrode.
  • the separator may be a porous polymer film commonly used, such as a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer
  • the polymer film may be used alone or as a laminate thereof, or may be a nonwoven fabric made of a conventional porous nonwoven fabric, for example, glass fiber of high melting point, polyethylene terephthalate fiber or the like, but is not limited thereto.
  • the pore diameter of the porous separation membrane is generally 0.01 to 50 ⁇ m, and the porosity may be 5 to 95%. Also, the thickness of the porous separation membrane may be generally in the range of 5 to 300 mu m.
  • the secondary battery of the present invention places the polymer electrolyte of the present invention on one or both surfaces of at least one of the positive electrode and the negative electrode, or at least one surface or both surfaces of the positive electrode, the negative electrode and the separator.
  • the polymer electrolyte may be prepared in the form of a film using a polymer containing the repeating unit represented by the formula (1), and then, at least one of the prepared negative electrode, positive electrode, (2) dissolving a polymer containing a repeating unit represented by the above formula (1) in an organic solvent to prepare a coating solution, and then coating the coating solution with at least one of the prepared negative electrode, positive electrode and separator Or directly on both surfaces or both surfaces thereof, followed by drying and interposition.
  • a solid polymer electrolyte membrane is formed on one or both surfaces of at least one of a cathode, an anode and a separator, and then the liquid electrolyte is further injected to swell the solid polymer electrolyte to form a gel polymer electrolyte (solid-liquid mixed electrolyte) As shown in FIG.
  • the thickness of the membrane-shaped polymer electrolyte is preferably as thin as possible in consideration of ion conductivity, but it may be specifically from 0.1 mu m to 300 mu m.
  • the thickness of the electrolyte membrane is less than 0.1 ⁇ , the strength of the membrane is considerably decreased and it is difficult to apply it as an electrolyte membrane.
  • the thickness exceeds 300 ⁇ , a proton (Li + There is a disadvantage that it is difficult to produce a secondary battery having a high energy density.
  • the polymer electrolyte is a self-supporting solid polymer electrolyte, it may be 10 ⁇ to 100 ⁇ , more specifically 10 ⁇ to 50 ⁇ , in order to secure mechanical strength.
  • the polymer electrolyte is a gel polymer electrolyte formed by injecting a liquid electrolyte, consideration may be given to swelling, the polymer electrolyte may be 10 ⁇ or less, specifically 5 ⁇ .
  • a 4.2V LiCoO 2 compound as a cathode active material, carbon black as a conductive material, and PVDF as a binder component were added to N-methyl-2-pyrrolidone (NMP) as a solvent at a weight ratio of 92: 4: 2 to prepare a cathode active material slurry 60% by weight).
  • NMP N-methyl-2-pyrrolidone
  • the cathode active material slurry was coated on the surface of an aluminum (Al) thin film having a thickness of 20 ⁇ and dried to prepare a positive electrode having a positive electrode mixture layer having a thickness of 10 ⁇ .
  • lithium metal was coated on the Cu thin film, and then rolled to prepare a negative electrode having a thickness of 20 ⁇ .
  • a negative electrode having the positive electrode and the polymer electrolyte formed thereon was sequentially laminated to produce an electrode assembly, and the electrode assembly was housed in a pouch-shaped battery case to prepare a 4.2 V-class lithium secondary battery (full cell).
  • a 4.2V LiCoO 2 compound as a cathode active material, carbon black as a conductive material, and PVDF as a binder component were added to N-methyl-2-pyrrolidone (NMP) as a solvent at a weight ratio of 92: 4: 2 to prepare a cathode active material slurry 60% by weight).
  • NMP N-methyl-2-pyrrolidone
  • the cathode active material slurry was coated on the surface of an aluminum (Al) thin film having a thickness of 20 ⁇ and dried to prepare a positive electrode having a positive electrode mixture layer having a thickness of 10 ⁇ .
  • lithium metal was coated on the Cu thin film, and then rolled to prepare a negative electrode having a thickness of 20 ⁇ .
  • a negative electrode comprising the positive electrode and the polymer electrolyte, and a polyolefin-based separator (thickness: 20 ⁇ m) were sequentially laminated to produce an electrode assembly, and the electrode assembly was housed in a pouch-shaped battery case.
  • FEC fluoroethylene carbonate
  • EMC ethyl methyl carbonate
  • a secondary battery was produced in the same manner as in Example 5, except that 140 ⁇ l (20 parts by weight) of the ionic liquid (Pyr13-FSI) after the non-aqueous electrolyte was injected at the time of manufacturing the secondary battery.
  • 140 ⁇ l (20 parts by weight) of the ionic liquid (Pyr13-FSI) after the non-aqueous electrolyte was injected at the time of manufacturing the secondary battery.
  • a secondary battery was produced in the same manner as in Example 8, except that 140 ⁇ l (20 parts by weight) of an ionic liquid (Pyr13-FSI) was further injected into the nonaqueous electrolyte solution during the production of the secondary battery.
  • 140 ⁇ l (20 parts by weight) of an ionic liquid (Pyr13-FSI) was further injected into the nonaqueous electrolyte solution during the production of the secondary battery.
  • a nonaqueous electrolyte solution composed of an organic solvent (fluoroethylmethyl carbonate (FEMC): ethylene carbonate (EC): ethyl methyl carbonate (EMC) 3: 3: 4 by volume ratio) in which 1 M LiPF 6 was dissolved
  • FEMC fluoroethylmethyl carbonate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • FEC fluoro-ethylene carbonate
  • TFDOL 2,2- bis (trifluoromethyl) -1,3-dioxolane
  • EMC ethyl methyl carbonate
  • a nonaqueous electrolytic solution composed of an organic solvent (fluoroethylene carbonate (FEC): ethylene carbonate (EC): ethyl methyl carbonate (EMC) 0.5: 2.5: 7 by volume) in which 1 M LiPF 6 is dissolved is injected in the production of the secondary battery
  • FEC fluoroethylene carbonate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • a secondary battery was produced in the same manner as in Example 13, except that 140 ⁇ ⁇ (20 parts by weight) of an ionic liquid (Pyr13-FSI) was added after the non-aqueous electrolyte was injected in the production of the secondary battery.
  • 140 ⁇ ⁇ (20 parts by weight) of an ionic liquid (Pyr13-FSI) was added after the non-aqueous electrolyte was injected in the production of the secondary battery.
  • a secondary battery was produced in the same manner as in Example 14, except that 140 ⁇ ⁇ (20 parts by weight) of an ionic liquid (Pyr13-FSI) was added after the nonaqueous electrolyte solution was poured during the production of the secondary battery.
  • 140 ⁇ ⁇ (20 parts by weight) of an ionic liquid (Pyr13-FSI) was added after the nonaqueous electrolyte solution was poured during the production of the secondary battery.
  • Electrolyte specimens were prepared using the mixed solution for preparing solid polymer electrolyte prepared in Examples 1 to 4 and the mixed solution for preparing solid polymer electrolyte prepared in Comparative Examples 1 and 2, and the tensile strengths of these specimens were measured.
  • the electrolyte specimens were prepared collectively through ASTM standard D638 (Type V specimens) and tensile strength was measured using Lloyd LR-10K at a rate of 5 mm per minute at 25 ° C and 30% relative humidity. The results are shown in Table 1 below.
  • Example 1 8.9
  • Example 2 9.3
  • Example 3 7.8
  • Example 4 7.2 Comparative Example 1 5.2 Comparative Example 2 0.01
  • the tensile strength of the solid polymer electrolyte prepared using the mixed solution for preparing solid polymer electrolytes according to Examples 1 to 4 of the present invention was about 7.2 MPa or more, which is superior to the solid polymer electrolyte prepared by using the solution.
  • the lithium secondary batteries prepared in Examples 1 to 4 and the lithium secondary batteries prepared in Comparative Examples 1 and 2 were charged at 25 ° C at 0.2 ° C / 4.25V constant current / constant voltage (CC / CV) C / 3.0V constant current. The charge and discharge were performed as one cycle, and the charge and discharge were performed for 100 cycles.
  • the solid polymer electrolyte was pulsed in a coin cell form, the solid polymer electrolyte was laminated on a first steel use stainless steel film usable as a working electrode.
  • FEC fluoro ethylene carbonate
  • EMC ethyl methyl carbonate
  • Layer structure composed of the first SUS film / gel polymer electrolyte / second SUS film was formed on the gel polymer electrolyte by covering the second SUS film. Then, using a VMP3 measuring instrument and a precision impedance analyzer (4294A), a frequency band of 100 MHz The ion conductivity was measured at ⁇ 0.1 Hz, and the results are shown in Table 3 below.
  • the gel polymer electrolytes of Examples 6 to 16 and the gel polymer electrolytes of Comparative Example Layer structure composed of the first SUS membrane / gel polymer electrolyte / second SUS membrane was prepared in the same manner as described above, except that the gel polymer electrolyte of the same composition as the gel polymer electrolyte of Comparative Example 3 to Comparative Example 5 was applied Respectively.
  • Example 5 Ion conductivity (S / cm) Example 5 2.0 x 10 -4 Example 6 1.8 ⁇ 10 -4 Example 7 2.2 x 10 -4 Example 8 2.4 ⁇ 10 -4 Example 9 1.5 x 10 -4 Example 10 1.2 ⁇ 10 -4 Example 11 1.4 x 10 -4 Example 12 2.2 x 10 -4 Example 13 1.3 ⁇ 10 -4 Example 14 2.0 x 10 -4 Example 15 1.2 ⁇ 10 -4 Example 16 1.6 x 10 -4 Comparative Example 3 5.0 ⁇ 10 -5 Comparative Example 4 2.0 x 10 -6 Comparative Example 5 1.1 ⁇ 10 -4
  • the ionic conductivity of the gel polymer electrolyte prepared in Comparative Examples 3 to 5 was mostly 1.1 ⁇ 10 -4 S / cm or less, while the gel prepared in Examples 5 to 16
  • the ion conductivity of the polymer electrolyte is 1.2 x 10 -4 S / cm or more, which is higher than that of the gel polymer electrolyte prepared in Comparative Examples 3 to 5.
  • the lithium secondary batteries prepared in Examples 5 to 16 and the lithium secondary batteries prepared in Comparative Examples 3 to 5 were each subjected to a constant current / constant voltage (CC / CV) condition at 25 ° C. and 25 ° C. at 0.2 C / And discharged at a constant current of 0.5C / 3.0V.
  • CC / CV constant current / constant voltage
  • the charge and discharge were performed as one cycle, and the charge and discharge were performed for 100 cycles.
  • Example 5 93
  • Example 6 60
  • Example 7 78
  • Example 8 47
  • Example 9 88
  • Example 10 75
  • Example 12 102
  • Example 13 95
  • Example 14 99
  • Example 15 86
  • Example 16 93 Comparative Example 3 16 Comparative Example 4 4 Comparative Example 5 45
  • the capacity of the secondary battery of Comparative Example 3 is rapidly lowered after two cycles, and the capacity of the secondary battery of Comparative Example 4 is reduced from 25 cycles.
  • the secondary batteries produced in Examples 5 to 8 showed a slower capacity after 40 cycles, and thus the cycle life characteristics were improved as compared with the secondary batteries prepared in Comparative Example 4 and Comparative Example 5 have.
  • the lithium secondary batteries produced in Examples 1 to 16 showed an oxidation initiation voltage at a high voltage range of about 4.7 V or more, indicating excellent electrochemical (oxidation) stability.
  • the lithium secondary batteries prepared in Comparative Examples 1 to 5 exhibit an oxidation starting voltage in the region of 4.6 V or lower, which is lower than those of the secondary batteries of Examples 1 to 16.

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Abstract

La présente invention concerne un électrolyte polymère destiné à une batterie secondaire qui peut garantir une conductivité ionique et une résistance mécanique élevées, et une batterie secondaire au lithium le comprenant.
PCT/KR2018/014638 2017-11-28 2018-11-26 Électrolyte polymère pour batterie secondaire et batterie secondaire le comprenant WO2019107855A1 (fr)

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EP18884399.9A EP3648229B1 (fr) 2017-11-28 2018-11-26 Électrolyte polymère pour batterie secondaire et batterie secondaire le comprenant
PL18884399.9T PL3648229T3 (pl) 2017-11-28 2018-11-26 Elektrolit polimerowy dla akumulatora i zawierający go akumulator
CN201880049382.3A CN110998954A (zh) 2017-11-28 2018-11-26 用于二次电池的聚合物电解质和包括该聚合物电解质的二次电池
US16/633,237 US11670800B2 (en) 2017-11-28 2018-11-26 Polymer electrolyte for secondary battery and secondary battery including the same

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