WO2018106078A1 - Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant - Google Patents

Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant Download PDF

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WO2018106078A1
WO2018106078A1 PCT/KR2017/014432 KR2017014432W WO2018106078A1 WO 2018106078 A1 WO2018106078 A1 WO 2018106078A1 KR 2017014432 W KR2017014432 W KR 2017014432W WO 2018106078 A1 WO2018106078 A1 WO 2018106078A1
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secondary battery
lithium secondary
electrolyte
group
formula
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PCT/KR2017/014432
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English (en)
Korean (ko)
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오정우
안경호
이철행
이정훈
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주식회사 엘지화학
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Priority to CN201780015219.0A priority Critical patent/CN108886165B/zh
Priority to US16/078,151 priority patent/US10553903B2/en
Priority to JP2018565316A priority patent/JP6775843B2/ja
Priority to PL17878254T priority patent/PL3531491T3/pl
Priority to EP17878254.6A priority patent/EP3531491B1/fr
Priority claimed from KR1020170168433A external-priority patent/KR102102985B1/ko
Publication of WO2018106078A1 publication Critical patent/WO2018106078A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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 for a lithium secondary battery having improved high temperature durability and a lithium secondary battery including the same.
  • the lithium secondary battery generally includes a positive electrode and a negative electrode including an electrode active material capable of inserting / releasing lithium ions, and an electrolyte which is a transfer medium of lithium ions.
  • a liquid electrolyte containing a non-aqueous organic solvent in which an electrolyte salt is dissolved or a gel polymer electrolyte further comprising a matrix polymer in the liquid electrolyte is used.
  • the electrolyte is decomposed during charging and discharging of the lithium secondary battery, or gas may be generated inside the secondary battery by side reaction between the electrode and the electrolyte, and such gas generation is further increased during high temperature storage.
  • This continuously generated gas not only causes deformation of the battery, such as causing an increase in the internal pressure of the battery, thereby expanding the thickness of the battery, but also locally changing the adhesion on the electrode surface of the battery, so that the electrode reaction does not occur identically on the entire electrode surface. It can cause problems.
  • lithium secondary battery in order to improve the stability and high output characteristics of the lithium secondary battery, it is necessary to develop a lithium secondary battery having improved stability by suppressing gas generation and exothermic reaction during high temperature storage and overcharging.
  • the present invention has been made to solve such a problem
  • a second technical problem of the present invention is to provide a lithium secondary battery having improved stability at high temperature storage and overcharge by including the electrolyte for a lithium secondary battery.
  • R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • R 1 to R 3 are each independently an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with fluorine,
  • R 4 is an alkylene group having 1 to 4 carbon atoms
  • R ' is hydrogen or an alkyl group having 1 to 3 carbon atoms
  • a 1 to 3
  • n is the number of repeat units
  • n is an integer of any one of 1 to 75.
  • the aliphatic hydrocarbon group may be substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A substituted or unsubstituted cycloalkenylene group having 4 to 20 carbon atoms; And at least one alicyclic hydrocarbon group selected from the group consisting of a substituted or unsubstituted heterocycloalkylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; Substituted or unsubstituted C1-C20 alkylene group containing an isocyanate group (NCO); A substituted or unsubstituted alkoxylene group having 1 to 20 carbon atoms; A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; And a linear
  • the aromatic hydrocarbon group is substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.
  • the oligomer represented by Formula 1 may be an oligomer represented by Formula 1a.
  • R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • R 1 is an alkylene group having 1 to 5 carbon atoms substituted or unsubstituted with fluorine,
  • n1 is the number of repeat units
  • n1 is an integer of any one of 1-75.
  • the oligomer represented by Formula 1a may be an oligomer represented by Formula 1a-1.
  • n2 is the number of repeat units
  • n2 is an integer of any one of 20-75.
  • the oligomer represented by Chemical Formula 1 may be included in an amount of 0.5 wt% to 20 wt%, specifically 0.5 wt% to 15 wt%, based on the total weight of the lithium secondary battery electrolyte.
  • the lithium secondary battery electrolyte may be a liquid electrolyte.
  • the lithium secondary battery electrolyte may be a gel polymer electrolyte.
  • the polymer derived from the oligomer represented by Formula 1 may be a matrix polymer formed in a three-dimensional structure by polymerization of the oligomer represented by Formula 1 in the presence of a polymerization initiator.
  • the gel polymer electrolyte may further include inorganic particles.
  • Such inorganic particles include BaTiO 3 , BaTiO 3 , Pb (Zr x Ti 1-x ) O 3 (0 ⁇ x ⁇ 1) (PZT), Pb 1- b La b Zr 1-c Ti c O 3 (PLZT, where , 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1), Pb (Mg 1/3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT), Hafnia (HfO 2 ), SrTiO 3 , SnO 2 , It may include a single or a mixture of two or more selected from the group consisting of CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiC and mixtures thereof.
  • the inorganic particles may be included in 10% by weight to 25% by weight based on the total weight of the electrolyte for a lithium secondary battery.
  • a cathode interposed between the cathode, the anode, the cathode and the anode, and
  • the lithium secondary battery electrolyte may be a liquid electrolyte or a gel polymer electrolyte.
  • the present invention by including oligomers having hydrophilic and hydrophobic functional groups, the surface tension with the electrode surface can be lowered to improve wettability, and a stable ion conductive film is formed on the electrode surface during initial charging.
  • a lithium secondary battery electrolyte having improved high temperature durability by preventing electrolyte side reactions and oxidation reactions during high temperature storage and overcharge.
  • the present invention provides a lithium secondary battery having such a lithium secondary battery electrolyte, thereby suppressing an exothermic reaction during high temperature storage and overcharging, thereby improving a lithium secondary battery having improved overall performance such as stability.
  • Example 1 is a graph showing the gas content generated from the lithium secondary battery of Example 1 and Comparative Example 1 according to Experimental Example 2 of the present invention.
  • FIG. 2 is a graph showing the gas content generated from the lithium secondary battery of Examples 5 and 6 and Comparative Example 3 according to Experimental Example 3 of the present invention.
  • Example 3 is a graph showing the results of evaluation of the oxidation stability of the gel polymer electrolyte of Example 5 and the liquid electrolyte of Comparative Example 1 according to Experimental Example 4 of the present invention.
  • Example 4 is a graph showing the results of evaluating the reduction stability of the gel polymer electrolyte of Example 6 and the liquid electrolyte of Comparative Example 2 according to Experimental Example 4 of the present invention.
  • Example 5 is a graph showing the results of the performance evaluation at room temperature (25 °C) of the lithium secondary battery of Example 5 and Comparative Example 3 according to Experimental Example 5 of the present invention.
  • FIG. 6 is a graph illustrating performance evaluation results at low temperatures ( ⁇ 10 ° C.) of lithium secondary batteries of Example 5 and Comparative Example 3 according to Experimental Example 6 of the present invention.
  • FIG. 6 is a graph illustrating performance evaluation results at low temperatures ( ⁇ 10 ° C.) of lithium secondary batteries of Example 5 and Comparative Example 3 according to Experimental Example 6 of the present invention.
  • Example 7 is a graph illustrating thermal stability evaluation results of the lithium secondary battery of Example 5 and Comparative Example 3 according to Experimental Example 7 of the present invention.
  • R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • R 1 to R 3 are each independently an alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with fluorine,
  • R 4 is an alkylene group having 1 to 4 carbon atoms
  • R ' is hydrogen or an alkyl group having 1 to 3 carbon atoms
  • a 1 to 3
  • n is the number of repeat units
  • n is an integer of any one of 1 to 75.
  • the lithium salt may be used without limitation those conventionally used in the electrolyte for lithium secondary batteries, for example, includes Li + as the cation of the lithium salt anion include 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 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 -, (CF
  • the lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , 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
  • It may include a single or a mixture of two or more selected from the group consisting of, in addition to these LiBTI (lithium bisperfluoroethanesulfonimide, LiN (SO 2 C 2 F) commonly used in the electrolyte of the lithium secondary battery 5 ) without limitation lithium salts such as lithium imide salts represented by 2 ), LiFSI (lithium fluorosulfonyl imide, LiN (SO 2 F) 2 ), and LiTFSI (lithium (bis) trifluoromethanesulfonimide, LiN (SO 2 CF 3 ) 2 ) Can be used.
  • the lithium salt is a single or two selected from the group consisting of LiPF 6 , LiBF 4 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiCH 3 SO 3 , LiFSI, LiTFSI and LiN (C 2 F 5 SO 2 ) 2 It may contain a mixture of the above.
  • the lithium salt may be appropriately changed within a range generally available, and specifically, may be included in the electrolyte for lithium secondary batteries at 0.8 M to 3M, specifically 1.0M to 2.5M. If the concentration of the lithium salt is greater than 3M, the viscosity of the electrolyte may be increased to reduce the lithium ion migration effect.
  • the organic solvent in the electrolyte for a lithium secondary battery according to an embodiment of the present invention, if the organic solvent can minimize the decomposition by the oxidation reaction, etc. in the charge and discharge process of the secondary battery, and if it can exhibit the desired characteristics with additives no limits.
  • the organic solvent may be used alone or in combination of two or more of an ether solvent, an ester solvent, an amide solvent, and the like.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether and ethylpropyl ether, or a mixture of two or more thereof may be used. It is not limited to this.
  • the ester solvent may include at least one compound selected from the group consisting of a cyclic carbonate compound, a linear carbonate compound, a linear ester compound, and a cyclic ester compound.
  • cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, and 1,2-pentylene carbonate. , 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC), or any one or a mixture of two or more thereof.
  • linear carbonate compound examples include dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (diethyl carbonate, DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate Any one selected from, or a mixture of two or more thereof may be representatively used, but is not limited thereto.
  • the linear ester compound is any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
  • the above mixture and the like can be used representatively, but is not limited thereto.
  • the cyclic ester compound is any one selected from the group consisting of ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -caprolactone, or two or more thereof Mixtures may be used, but are not limited thereto.
  • the cyclic carbonate-based compound is a high viscosity organic solvent and has a high dielectric constant, and thus may be preferably used because it dissociates lithium salts in the electrolyte.
  • the cyclic carbonate-based compound has low viscosity and low viscosity such as dimethyl carbonate and diethyl carbonate
  • an electrolyte having a high electrical conductivity can be made, which can be used more preferably.
  • the lithium secondary battery electrolyte according to an embodiment of the present invention may include an oligomer represented by the formula (1).
  • the oligomer represented by the formula (1) exhibits a balanced affinity with the positive electrode or separator (SRS layer) and the negative electrode or separator fabric in the secondary battery is electrochemically stable, which is a great help in improving lithium secondary battery performance.
  • the oligomer represented by the formula (1) contains an acrylate-based functional group which is a hydrophilic part capable of forming crosslinking at both ends thereof, and also contains a fluorine-substituted ethylene group which is a hydrophobic part, and thus is an interface in a battery.
  • the interfacial resistance can be lowered by maintaining balanced affinity with the positive electrode, the negative electrode, and the separator (SRS layer), respectively. Therefore, the electrolyte for a lithium secondary battery including the oligomer represented by Chemical Formula 1 may further improve the wettability effect.
  • the oligomer represented by the formula (1) has the ability to dissociate lithium salts to improve the lithium ion mobility, in particular containing an alkyl group substituted with fluorine at the end, and at the same time repeating Since it contains a fluorine-substituted ethylene group which is very chemically stable and has low reactivity with Li ions, a stable ion conductive film is formed on the surface of the electrode during initial charging, so that the electrolyte and lithium ions (Li + ) and Side reactions, electrolyte oxidation reactions and decomposition reactions of lithium salts can be controlled.
  • a polymer having an alkylene oxide skeleton such as ethylene oxide, propylene oxide, or butylene oxide which has been commercialized at the time of preparing a gel polymer electrolyte, or a block copolymer having a dialkyl siloxane, a fluorosiloxane, or a unit thereof;
  • the secondary battery electrolyte of the present invention including the oligomer represented by Chemical Formula 1 in place of the graft polymer may reduce electrolyte side reactions and oxidation reactions, thereby realizing an interfacial stability effect between the electrode and the electrolyte, thereby improving high temperature durability.
  • the aliphatic hydrocarbon group may be substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A substituted or unsubstituted cycloalkenylene group having 4 to 20 carbon atoms; And at least one alicyclic hydrocarbon group selected from the group consisting of a substituted or unsubstituted heterocycloalkylene group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; Substituted or unsubstituted C1-C20 alkylene group containing an isocyanate group (NCO); A substituted or unsubstituted alkoxylene group having 1 to 20 carbon atoms; A substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms; And a linear
  • the aromatic hydrocarbon group is substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms.
  • the oligomer represented by Formula 1 may be an oligomer represented by Formula 1a.
  • R is an aliphatic hydrocarbon group or an aromatic hydrocarbon group
  • R 1 is an alkylene group having 1 to 5 carbon atoms substituted or unsubstituted with fluorine,
  • n1 is the number of repeat units
  • n1 is an integer of any one of 1-75.
  • the oligomer represented by Formula 1a may be an oligomer represented by Formula 1a-1.
  • n2 is the number of repeat units
  • n2 is an integer of any one of 20-75.
  • the oligomer represented by Chemical Formula 1 may be included in an amount of 0.5 wt% to 20 wt%, specifically 0.5 wt% to 15 wt%, and more specifically 0.5 wt% to 10 wt%, based on the total weight of the lithium secondary battery electrolyte.
  • a gel polymer electrolyte having a stable network structure may be prepared, and when the content of the oligomer is 20% by weight or less, an increase in resistance due to the addition of an excessive oligomer is prevented to ensure wettability. At the same time, it is possible to prevent the disadvantages such as lowering the ion conductivity by improving the movement restriction of lithium ions.
  • the weight average molecular weight (MW) of the oligomer represented by Formula 1 may be adjusted by the number of repeating units, about 1,000 g / mol 100,000 g / mol, specifically 1,000 g / mol to 50,000 g / mol, More specifically, it may be 2,000 g / mol to 7,000 g / mol.
  • the weight average molecular weight of the oligomer is in the above range, it is possible to effectively form a polymer matrix by the appropriate oligomer molecular weight.
  • various functional groups can be easily substituted as necessary, various various performance improvement effects can be obtained.
  • the weight average molecular weight of the oligomer is less than 1,000 g / mol, since it is difficult to form a stable polymer network, its own electrochemical stability and the role of a surfactant cannot be expected, and the weight average molecular weight exceeds 100,000 g / mol. In other words, the oligomer properties are rigid and the affinity with the electrolyte solvent is lowered due to the increase in viscosity, so that the solubility is lowered.
  • the weight average molecular weight may mean a conversion value for standard polystyrene measured by gel permeation chromatography (GPC), and unless otherwise specified, molecular weight may mean weight average molecular weight.
  • GPC gel permeation chromatography
  • the GPC conditions are measured using Agilent's 1200 series, and the column used may be an Agilent PL mixed B column, and the solvent may be THF.
  • the lithium secondary battery electrolyte according to one embodiment of the present invention includes the oligomer represented by Formula 1, the lithium secondary battery electrolyte of the present invention may be a liquid electrolyte.
  • the lithium secondary battery electrolyte according to an embodiment of the present invention includes a polymer derived from the oligomer represented by the formula (1)
  • the lithium secondary battery electrolyte may be a gel polymer electrolyte.
  • the polymer derived from the oligomer represented by Formula 1 may be a matrix polymer formed in a three-dimensional structure by polymerization of the oligomer represented by Formula 1 in the presence of a polymerization initiator.
  • a polymerization initiator used to form a gel may be a conventional polymerization initiator capable of generating radicals by heat and light used in preparing a conventional gel polymer electrolyte. Can be used without limitation.
  • the polymerization initiator may be decomposed by heat in the secondary battery, for example, but not limited to 30 ° C. to 100 ° C., specifically 60 ° C. to 80 ° C., or may be decomposed at room temperature (5 ° C. to 30 ° C.) to form radicals.
  • the polymerization initiator may be included in about 0.01 parts by weight to about 20 parts by weight, specifically 5 parts by weight based on 100 parts by weight of the total oligomer, and if included in the above range to facilitate the gelling reaction, the composition is injected into a battery It is possible to prevent the gelation occurs during the operation, or the unreacted polymerization initiator remains after the polymerization reaction to cause side reactions.
  • some polymerization initiators may generate nitrogen or oxygen gas in the process of generating radicals by heat or the like. This gas generation is often lead to gas trap or gas bubbling phenomenon in the gel polymer electrolyte formation process. This gas generation causes a defect in the gel polymer electrolyte, resulting in a decrease in electrolyte quality. Therefore, when the polymerization initiator is included in the above range, it is possible to more effectively prevent the disadvantages such as the generation of a large amount of gas.
  • some polymerization initiators may generate nitrogen or oxygen gas in the process of generating radicals by heat or the like. This gas generation is often lead to gas trap or gas bubbling phenomenon in the gel polymer electrolyte formation process. This gas generation causes a defect in the gel polymer electrolyte, resulting in electrolyte quality deterioration. Therefore, when the polymerization initiator is included in the above range, it is possible to more effectively prevent the disadvantages such as the generation of a large amount of gas.
  • the gel polymer electrolyte of the present invention may have a gel content of about 1% by weight or more, specifically about 20% by weight or more at 25 ° C.
  • the gel polymer electrolyte of the present invention may further include inorganic particles.
  • the inorganic particles may be impregnated in the polymer network to allow the high viscosity solvent to penetrate well through the pores formed by the void space between the inorganic particles. That is, by including the inorganic particles, it is possible to obtain an effect of further improving the wettability to a high viscosity solvent by affinity between the polar substances and capillary phenomenon.
  • inorganic particles having a high dielectric constant and which do not generate an oxidation and / or reduction reaction in an operating voltage range of the lithium secondary battery (for example, 0 to 5V based on Li / Li + ) may be used.
  • the inorganic particles are representative examples of BaTiO 3 , BaTiO 3 , Pb (Zr x Ti 1-x ) O 3 (0 ⁇ x ⁇ 1) (PZT), Pb 1 ⁇ b La b having a dielectric constant of 5 or more.
  • Zr 1 - c Ti c O 3 (PLZT, where 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 1), Pb (Mg 1/3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT), half Single substance selected from the group consisting of nia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiC and mixtures thereof Or a mixture of two or more thereof.
  • nia HfO 2
  • SrTiO 3 SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiC and mixtures thereof Or a mixture of two or more thereof.
  • inorganic particles having lithium ion transfer ability that is, lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li d Ti e (PO 4 ) 3 , 0 ⁇ d ⁇ 2, 0 ⁇ e ⁇ 3 ), Lithium aluminum titanium phosphate (Li a1 Al b1 Ti c1 (PO 4 ) 3 , 0 ⁇ a1 ⁇ 2, 0 ⁇ b1 ⁇ 1, 0 ⁇ c1 ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2- (LiAlTiP) a2 O b2 series glass such as 39P 2 O 5 (0 ⁇ a2 ⁇ 4, 0 ⁇ b2 ⁇ 13), lithium lanthanum titanate (Li a3 La b3 TiO 3 , 0 ⁇ a3 ⁇ 2, 0 ⁇ b3 ⁇ 3), Li 3 .
  • lithium phosphate Li 3 PO 4
  • lithium titanium phosphate Li d Ti e (PO
  • the inorganic particles may be included in 10% by weight to 25% by weight based on the total weight of the electrolyte for a lithium secondary battery.
  • the inorganic particle content is less than 10% by weight, it is difficult to expect an effect of improving wetting in a high viscosity solvent, and when it exceeds 25% by weight, it may cause a decrease in resistance performance of the battery.
  • the average particle diameter of the inorganic particles is preferably in the range of about 0.001 ⁇ m to 10 ⁇ m so as to have a proper porosity with a uniform thickness in the gel polymer electrolyte. If the average particle size is less than 0.001 ⁇ m dispersibility may be lowered, if the average particle diameter is more than 10 ⁇ m not only can increase the thickness of the porous coating layer, but also agglomeration of inorganic particles occurs gel gel electrolyte Exposure to the outside can lower the mechanical strength.
  • the gel polymer electrolyte may have a content of unreacted oligomers of 20% or less relative to the total amount of reactive oligomers at 25 ° C.
  • the content of the unreacted oligomer may be implemented by implementing a gel polymer electrolyte, extracting the gel polymer electrolyte with a solvent (acetone), and then checking the extracted solvent through nuclear magnetic resonance (NMR) measurement.
  • a solvent acetone
  • the electrolyte for a lithium secondary battery according to an embodiment of the present invention may further include an additive for forming an SEI film as needed.
  • SEI film-forming additives usable in the present invention are representative examples thereof, such as vinylene carbonate, vinylethylene carbonate, fluoroethylene carbonate, cyclic sulfite, saturated sultone, unsaturated sultone, acyclic sulfone, etc., alone or in combination of two or more thereof. Can be used.
  • the cyclic sulfites include ethylene sulfite, methyl ethylene sulfite, ethyl ethylene sulfite, 4,5-dimethyl ethylene sulfite, 4,5-diethyl ethylene sulfite, propylene sulfite, 4,5-dimethyl Propylene sulfite, 4,5-diethyl propylene sulfite, 4,6-dimethyl propylene sulfite, 4,6-diethyl propylene sulfite, 1,3-butylene glycol sulfite, and the like. Examples thereof include 1,3-propane sultone and 1,4-butane sultone.
  • unsaturated sultone examples include ethene sultone, 1,3-propene sultone, 1,4-butene sultone, 1-methyl-1,3 -Propene sulfone, and the like, and acyclic sulfones include divinyl sulfone, dimethyl sulfone, diethyl sulfone, methylethyl sulfone, and methyl vinyl sulfone.
  • the additive for forming the SEI film is preferably included 7 wt% or less, specifically 0.01 wt% to 5 wt% based on the total weight of the electrolyte for the lithium secondary battery in order to increase resistance and prevent side reactions due to the use of additives in excess. .
  • the gel polymer electrolyte of the present invention includes a matrix polymer formed by polymerizing the oligomer represented by Chemical Formula 1 in a three-dimensional structure, not only the mechanical properties and the ionic conductivity are improved, but also the oxidation reaction is inhibited during high temperature storage and overcharge. High temperature durability can be ensured.
  • a protective layer made of a polymer on the surface of the positive electrode and the negative electrode, or by using a polymer structure to suppress side reactions through anion stabilization and to increase the adhesion between the electrodes can suppress the generation of gas inside the battery at a high temperature. Therefore, a lithium secondary battery having improved stability at high temperature storage and overcharging may be manufactured.
  • a cathode interposed between the cathode, the anode, the cathode and the anode, and
  • the lithium secondary battery electrolyte may be a liquid electrolyte or a gel polymer electrolyte.
  • the lithium secondary battery of the present invention accommodates an electrode assembly formed by sequentially stacking a separator interposed between a positive electrode, a negative electrode, and a positive electrode and a negative electrode in a secondary battery case or an exterior material. It can be prepared by injecting the electrolyte for a lithium secondary battery of the present invention.
  • the lithium secondary battery electrolyte is a gel polymer electrolyte containing a polymer matrix formed by the polymerization of the oligomer represented by the formula (1)
  • the lithium secondary battery of the present invention selectively between the positive electrode, the negative electrode, and the positive electrode and the negative electrode
  • the electrode assembly formed by sequentially stacking the intervening separator may be accommodated in a secondary battery case or an exterior member, and then injected into the lithium secondary battery electrolyte, followed by curing reaction.
  • the thermal polymerization temperature may be 60 °C to 100 °C, specifically 60 °C to 80 °C.
  • the positive electrode, the negative electrode and the separator may be used all those prepared and used in a conventional manner when manufacturing a lithium secondary battery.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on a positive electrode current collector.
  • the cathode mixture layer may be formed by coating a cathode active material slurry including a cathode active material, a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (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.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like), lithium-manganese-cobal
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , or 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 the like, or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2 , and the like.
  • 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
  • the cathode active material may be included in an amount of 80 wt% to 99 wt%, specifically 85 wt% to 95 wt%, based on the total weight of solids in the cathode active material slurry.
  • the content of the positive electrode active material is 80% by weight or less, the energy density is lowered and thus the capacity may be lowered.
  • the binder is a component that assists in bonding the active material and the conductive material and bonding to the current collector, and is generally added in an amount of 1 wt% to 30 wt% based on the total weight of solids in the cathode active material slurry.
  • binders examples include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • carbon black acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black may be used.
  • Carbon powder Graphite powders such as natural graphite, artificial graphite, or graphite with very advanced crystal structure
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
  • Conductive whiskeys 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 conductive material is typically added in an amount of 1 wt% to 30 wt% based on the total weight of solids in the cathode active material slurry.
  • the conductive material is Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, etc., Ketjenblack, EC series (Armak Company) Armak Company), Vulcan XC-72 (Cabot Company), and Super P (manufactured by Timcal) can also be used.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the solids in the positive electrode active material and, optionally, the slurry including the binder and the conductive material may be 10 wt% to 70 wt%, preferably 20 wt% to 60 wt%.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a negative electrode active material slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material may be 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, and may dope and undo lithium. At least one selected from the group consisting of materials, and transition metal oxide transition metal oxides.
  • any carbon-based negative electrode active material generally used in a lithium ion secondary battery may be used without particular limitation.
  • Examples thereof include crystalline carbon, Amorphous carbons or these may be used together.
  • Examples of the crystalline carbon include graphite such as amorphous, plate, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, calcined coke, or the like.
  • the metals or alloys of these metals with lithium include Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al And a metal selected from the group consisting of Sn or an alloy of these metals with lithium may be used.
  • the metal complex oxide may include 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 x8 WO 2 (0 ⁇ x8 ⁇ 1), and Sn x Me 1- x Me ' y O z (Me: Mn, Fe 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 ⁇ 8 Any one selected from the group can be used.
  • Examples of materials capable of doping and undoping lithium include Si, SiO x7 (0 ⁇ x7 ⁇ 2), Si-Y alloys (wherein Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, Is an element selected from the group consisting of rare earth elements and combinations thereof, not Si), Sn, SnO 2 , Sn-Y (Y is an alkali metal, alkaline earth metal, group 13 element, group 14 element, transition metal, rare earth) An element selected from the group consisting of elements and combinations thereof, and not Sn; and at least one of these and SiO 2 may be mixed and used.
  • 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 included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the negative electrode active material slurry.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1% by weight to 30% by weight based on the total weight of solids in the negative electrode active material slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butad
  • 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 wt% to 20 wt% based on the total weight of solids in the negative electrode active material slurry.
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black may be used.
  • Carbon powder such as natural graphite, artificial graphite, or graphite with very advanced crystal structure
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
  • Conductive whiskeys 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 water or NMP, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including 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 separator serves to block internal short circuits of both electrodes and to impregnate the electrolyte, to prepare a separator composition by mixing a polymer resin, a filler, and a solvent, and then directly coating and drying the separator composition on the electrode.
  • the separator film separated from the support may be formed by lamination on the electrode.
  • the separator is a porous polymer film commonly used, for example, a porous polymer made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer
  • the polymer film may be used alone or in a stack thereof, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used, but is not limited thereto.
  • the pore diameter of the porous separator is generally 0.01 to 50 ⁇ m, porosity may be 5% to 95%.
  • the thickness of the porous separator may generally range from 5 to 300 ⁇ m.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • a cathode active material LiNi 1/3 Co 1/ 3 Mn 1/3 O 2; NCM
  • a conductive material of carbon black (carbon black) 3% by weight a solvent for polyvinylidene fluoride, 3 weight% of a binder Phosphorus N-methyl-2-pyrrolidone (NMP) was added to prepare a positive electrode active material slurry (50% by weight solid content).
  • the positive electrode active material slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of 20 ⁇ m, and dried to prepare a positive electrode, followed by a roll press to prepare a positive electrode.
  • Al aluminum
  • Negative active material slurry (65 wt% solids) by adding carbon powder as a negative electrode active material, PVDF as a binder and carbon black as a conductive material at 96 wt%, 3 wt% and 1 wt%, respectively, to NMP as a solvent.
  • the negative electrode active material slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, and dried to prepare a negative electrode, followed by roll press, to prepare a negative electrode.
  • Cu copper
  • the electrode assembly was prepared by sequentially stacking the separator consisting of the prepared positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and then storing the assembled electrode assembly in a battery case.
  • the lithium secondary battery was manufactured by pouring the liquid electrolyte.
  • Example 1 In preparing the liquid electrolyte of Example 1, except that the compound of Formula 1a-1 is not included, a liquid electrolyte and a secondary battery including the same were prepared in the same manner as in Example 1 (Table 1 below). Reference).
  • a cathode active material LiNi 1/3 Co 1/ 3 Mn 1/3 O 2; NCM
  • a conductive material of carbon black (carbon black) 3% by weight a solvent for polyvinylidene fluoride, 3 weight% of a binder Phosphorus N-methyl-2-pyrrolidone (NMP) was added to prepare a positive electrode active material slurry (50% by weight solid content).
  • the positive electrode active material slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of 20 ⁇ m, and dried to prepare a positive electrode, followed by a roll press to prepare a positive electrode.
  • Al aluminum
  • Negative active material slurry (65 wt% solids) by adding carbon powder as a negative electrode active material, PVDF as a binder and carbon black as a conductive material at 96 wt%, 3 wt% and 1 wt%, respectively, to NMP as a solvent.
  • the negative electrode W rutile slurry was applied to a thin copper (Cu) thin film which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
  • the electrode assembly was prepared by sequentially stacking the separator consisting of the prepared positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and then storing the assembled electrode assembly in a battery case.
  • the gel polymer electrolyte composition was infused and then aged for 2 days. Thereafter, this was cured at 70 ° C. for 5 hours to obtain a lithium secondary battery including a gel polymer electrolyte thermally polymerized.
  • Example 5 In preparing the gel polymer electrolyte composition of Example 5, the same procedure as in Example 5 was performed except that 0.3g of the oligomer represented by Chemical Formula 1a-1 and 0.03g of a polymerization initiator were used in 98.67g of the non-aqueous organic solvent. By the method, a gel polymer electrolyte composition and a lithium secondary battery using the same were prepared (see Table 1 below).
  • the amount of the organic solvent is 83.5 g
  • the gel polymer electrolyte is the same as in Example 5, except that 10 g of the inorganic particles (TiO 2 ) is further included.
  • the composition and a lithium secondary battery using the same were prepared (see Table 1 below).
  • Example 5 In the preparation of the gel polymer electrolyte composition of Example 5, the composition for gel polymer electrolyte in the same manner as in Example 5, except that the compound of the formula (2) instead of the oligomer of Formula 1a-1 as an oligomer And a lithium secondary battery using the same (see Table 1 below).
  • the lithium secondary battery comprising the liquid electrolytes prepared in Examples 1 to 4 and the lithium secondary battery comprising the liquid electrolytes prepared in Comparative Examples 1 and 2 were fully charged at 0.33C / 4.15V constant current-constant voltage, respectively, and the SOC 50 Initial charge and discharge were performed by discharging at 5C for 10 seconds. After initial charging and discharging, each was charged to 4.15V, and stored at 80 ° C. for 10 weeks (SOC; 100 of state), and then the thickness increase rate (%) and the resistance increase rate (%) were measured.
  • the thickness increase rate (%) and the resistance increase rate (%) are shown in Table 2 below.
  • the thickness increase rate (%) and the resistance increase rate (%) of the battery were calculated using the following Equations 1 and 2.
  • Battery thickness increase rate (%) [(final thickness-initial thickness) / initial thickness] ⁇ 100 (%)
  • the thickness increase rate at 80 ° C. for the lithium secondary battery including the gel polymer electrolytes prepared in Examples 5 to 10 and the lithium secondary battery including the gel polymer electrolytes prepared in Comparative Example 3 ( %) And resistance increase rate (%) were measured.
  • the thickness increase rate (%) and the resistance increase rate (%) are shown in Table 2 below.
  • Comparative Example 1 provided with a liquid electrolyte not containing oligomer And it can be seen that the thickness increase rate (%) after 10 weeks at 80 °C compared to the lithium secondary battery of 2 is significantly lower.
  • the lithium secondary batteries of Examples 1 to 4 having the liquid electrolyte containing the oligomer represented by the formula (1a-1) of the present invention the lithium of Comparative Examples 1 and 2 provided with the liquid electrolyte containing no oligomer It can be seen that the resistance increase rate (%) was significantly reduced after 10 weeks at 80 ° C. compared with the secondary battery.
  • the gel polymer electrolyte including the polymer derived from the compound of the formula (2) is provided.
  • the resistance increase rate (%) was significantly reduced after 10 weeks at 80 ° C.
  • the amount of CO gas generated in the lithium secondary battery of Example 1 having the liquid electrolyte including the oligomer of the present invention was about 100 ⁇ l, and the amount of CO 2 gas was about 200 ⁇ l or less. have.
  • the generated CO gas content is about 700 ⁇ l
  • the CO 2 gas content is about 500 ⁇ l
  • the secondary battery of Example 1 In contrast, it can be seen that about 6 times more gas is generated.
  • liquid electrolyte including the oligomer according to the embodiment of the present invention showed excellent oxidative stability and significantly reduced the amount of gas generated inside the secondary battery.
  • the CO gas content generated in the lithium secondary batteries of Examples 5 and 6 including the gel polymer electrolyte including the oligomer-derived polymer according to the embodiment of the present invention is about 500 ⁇ l, and CO 2 It can be seen that the gas content is about 300 ⁇ l or less.
  • the generated CO gas content is about 1000 ⁇ l
  • CO 2 gas content is about 2000 ⁇ l
  • the CO gas was reduced by 50% or more, and the CO 2 gas was reduced by about 70% to 80% or more compared with the secondary battery of Comparative Example 3.
  • the gel electrolyte including the oligomer according to the embodiment of the present invention shows excellent oxidative stability, and the amount of gas generated in the secondary battery is significantly reduced.
  • the gel polymer electrolyte of Example 5 including the polymer derived from the oligomer represented by Chemical Formula 1 has excellent stability against oxidation even in a high voltage region of 4.4 V or higher.
  • Working electrode Graphite (brand name: AGM1 100) Counter electrode Li metal Reference electrode Li metal Voltage range OV ⁇ 3V Scan rate 1 mV / S
  • the lithium secondary battery with the gel polymer electrolyte prepared in Example 5 and the lithium secondary battery with the gel polymer electrolyte prepared in Comparative Example 3 were charged to 25V at 0.5C constant current at 25 ° C., respectively. Charging was terminated when the battery was charged at a constant voltage of 4.2V and the charging current reached 0.275 mA. Thereafter, the battery was discharged for 10 minutes and then discharged until it became 3.0V at 0.5C constant current. After 700 cycles of charging and discharging, the battery capacity was measured and shown in FIG. 5.
  • the lithium secondary battery of Example 5 had almost no change in capacity retention even after 700 cycles, and showed a capacity retention of 93% or more even at the 700th cycle.
  • the lithium secondary battery of Comparative Example 3 exhibited a capacity retention rate similar to that of the secondary battery of Example 5 of the present invention until the initial 200 cycles, but decreased significantly from about 250 cycles, to about 88% in 700 cycles. It showed a sharp decrease.
  • the lithium secondary battery of Example 5 of the present invention has improved cycle life characteristics at room temperature compared to the lithium secondary battery of Comparative Example 3.
  • the lithium secondary battery of Example 5 having the gel polymer electrolyte containing the oligomer of the present invention has a relatively low voltage drop compared to the lithium secondary battery of Comparative Example 3.
  • the lithium secondary battery of Example 5 having the gel polymer electrolyte including the oligomer of the present invention has improved low temperature characteristics compared to the secondary battery of Comparative Example 3.
  • the negative electrode was subjected to differential scanning calorimetry (DSC). : differential scanning calorimeter). Measurement conditions were measured at intervals of 10 ° C / min from 25 ° C to 400 ° C. The results are shown in FIG.
  • a solid polymer electrolyte (SEI) film is formed on the surface of the negative electrode during initial charging. If the membrane is not decomposed at high temperature, side reaction between the negative electrode and the electrolyte is prevented, thereby improving battery stability.
  • SEI solid polymer electrolyte
  • the secondary battery of Example 5 using the gel polymer electrolyte containing the oligomer according to the embodiment of the present invention it can be seen that the decomposition temperature of the SEI film on the surface of the negative electrode is about 60 °C higher than in Comparative Example 1. Therefore, it can be seen that the lithium secondary battery of Example 5 of the present invention is more excellent in passion stability than the lithium secondary battery of Comparative Example 3.

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Abstract

La présente invention concerne un électrolyte pour une batterie secondaire au lithium et une batterie secondaire au lithium le comprenant et, plus particulièrement, un électrolyte pour une batterie secondaire au lithium comprenant un sel de lithium, un solvant organique, et un oligomère représenté par la formule 1 décrite dans la présente invention, et une batterie secondaire au lithium le comprenant, l'électrolyte supprimant la réactivité avec le lithium-métal pour améliorer les performances globales.
PCT/KR2017/014432 2016-12-08 2017-12-08 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium le comprenant WO2018106078A1 (fr)

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US16/078,151 US10553903B2 (en) 2016-12-08 2017-12-08 Electrolyte for lithium secondary battery and lithium secondary battery including the same
JP2018565316A JP6775843B2 (ja) 2016-12-08 2017-12-08 リチウム二次電池用電解質およびそれを含むリチウム二次電池
PL17878254T PL3531491T3 (pl) 2016-12-08 2017-12-08 Elektrolit dla akumulatora litowego i zawierający go akumulator litowy
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CN112074982A (zh) * 2018-09-10 2020-12-11 株式会社Lg化学 用于锂二次电池的热固性电解质组合物、由该热固性电解质组合物制备的凝胶聚合物电解质和包括该电解质的锂二次电池
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US11973190B2 (en) 2019-08-30 2024-04-30 Lg Energy Solution, Ltd. Electrolyte for lithium secondary battery and lithium secondary battery including the same
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