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WO2019054622A1 - Secondary battery solid electrolyte composition and solid electrolyte prepared therefrom - Google Patents

Secondary battery solid electrolyte composition and solid electrolyte prepared therefrom Download PDF

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Publication number
WO2019054622A1
WO2019054622A1 PCT/KR2018/008244 KR2018008244W WO2019054622A1 WO 2019054622 A1 WO2019054622 A1 WO 2019054622A1 KR 2018008244 W KR2018008244 W KR 2018008244W WO 2019054622 A1 WO2019054622 A1 WO 2019054622A1
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WIPO (PCT)
Prior art keywords
polymer
solid electrolyte
crosslinking agent
electrolyte
secondary battery
Prior art date
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Ceased
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PCT/KR2018/008244
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French (fr)
Korean (ko)
Inventor
권수지
윤정애
윤성수
김경오
채종현
이연주
김대일
김루시아
곽종헌
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LG Chem Ltd
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LG Chem Ltd
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Filing date
Publication date
Priority claimed from KR1020180080139A external-priority patent/KR102183663B1/en
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2020514998A priority Critical patent/JP6976422B2/en
Priority to ES18856085T priority patent/ES2976141T3/en
Priority to CN201880057969.9A priority patent/CN111095654B/en
Priority to US16/646,982 priority patent/US11417909B2/en
Priority to EP18856085.8A priority patent/EP3664210B1/en
Publication of WO2019054622A1 publication Critical patent/WO2019054622A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • 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
    • 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 solid electrolyte composition for a secondary battery and a solid electrolyte prepared therefrom.
  • Lithium secondary batteries which are mainly used in notebook computers and smart phones, are composed of a cathode made of lithium oxide, a carbon-based cathode, a separator, and a liquid or solid electrolyte.
  • a lithium secondary battery composed of a liquid electrolyte has a problem of stability such as leakage and explosion, and has a disadvantage in that the battery design becomes complicated in order to prevent it.
  • the gel-type polymer electrolyte is an electrolyte exhibiting conductivity by impregnating a liquid electrolyte having a high boiling point in a polymer film and fixing it with a lithium salt, and thus has a similar ionic conductivity to that of a pure liquid electrolyte because it contains a large amount of liquid electrolyte. Is left.
  • the solid polymer electrolyte contains no liquid electrolyte, which improves the stability problem related to leakage, and has a high chemical and electrochemical stability.
  • the ion conductivity at room temperature is about 100 times lower than that of the liquid electrolyte, so that much research has been conducted to improve the ion conductivity.
  • the most widely used solid polymer electrolyte is polyethylene oxide (PEO), which has the ability to conduct lithium ions despite being solid.
  • PEO polyethylene oxide
  • the linear PEO polymer electrolyte has a limited fluidity of the chain due to its high crystallinity and has a low dielectric constant (5.0), which makes it difficult to dissolve a large amount of lithium ions and thus has a very low conductivity at room temperature.
  • Patent Document 1 Korean Patent No. 10-0796989 (Jan. 16, 2008), " Hydrogen-ion conductive crosslinked fluoropolymer electrolyte membrane "
  • Patent Document 2 Korean Patent No. 10-0796990 (Jan. 16, 2008), " Organic fluorine-based copolymer electrolyte membrane into which hydrophilic and sulfonation group is introduced "
  • the present inventors have conducted various studies to solve the above problems. As a result, they have found that an alkylene oxide having ionic conductivity and a monomer containing a crosslinkable functional group are graft copolymerized on a fluoride polymer having a high dielectric constant to form a solid electrolyte for a lithium secondary battery It was confirmed that the ionic conductivity and the electrochemical stability of the electrolyte were improved, thereby completing the present invention.
  • an object of the present invention is to provide a solid electrolyte composition for a secondary battery, which comprises a polymer on which an alkylene oxide and a monomer containing a crosslinkable functional group are grafted, on a fluorinated polymer.
  • a solid electrolyte composition for a secondary battery which comprises a polymer obtained by grafting an alkylene oxide and a monomer containing a crosslinkable functional group onto a fluorine polymer.
  • the fluorine-based polymer may include a structure represented by the following formula (1).
  • the grafted polymer may include a structure represented by the following formula (2).
  • Q, n, p, m and o each independently represent an integer of 0? Q? 20,000, 1? N? 22,000, 2? P? 230, 1? M? 200 and 2? )
  • the alkylene oxide may be ethylene oxide or propylene oxide.
  • the crosslinkable functional group may be any one selected from the group consisting of a hydroxyl group, a carboxyl group and an isocyanate group.
  • the monomer may include an alkylene oxide and a crosslinkable functional group in a molar ratio of 99.5: 0.5 to 80:20.
  • the fluoropolymer may be contained in an amount of 0.2 to 40 parts by weight based on 100 parts by weight of the total composition.
  • the composition may further comprise a polyfunctional crosslinking agent having two or more functional groups capable of reacting with the crosslinkable functional group.
  • the polyfunctional crosslinking agent may be any one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.
  • the polyfunctional crosslinking agent may be included in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the total electrolyte composition.
  • the present invention also provides a solid electrolyte for a secondary battery formed by thermally curing the solid electrolyte composition for a secondary battery.
  • the electrolyte may have a thickness of 50 to 400 mu m.
  • the electrolyte may further comprise 30 to 70 parts by weight of a lithium salt based on 100 parts by weight of the electrolyte composition.
  • the electrolyte is LiCl, LiBr, LiI, LiClO 4 , LiBF 4, LiTFSI, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, (CF 3 SO 2) 2 NLi, LiN (SO 2 F) 2, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl lithium borate and lithium already selected from the group consisting of draw And may further include a lithium salt of a species or more.
  • the electrolyte may have an ionic conductivity of 1 ⁇ 10 -6 S / cm to 4 ⁇ 10 -5 S / cm.
  • the solid electrolyte composition for a secondary battery according to the present invention comprises a polymer produced by grafting an alkylene oxide and a monomer containing a crosslinkable functional group on a fluoropolymer having a high dielectric constant, And the chemical stability can be improved.
  • the fluorine-based polymer has a dielectric constant of about 9 to 40 and a very high lithium ion dissociation degree. When used in a lithium secondary battery, the fluorine-based polymer has an electrochemical stability even at a high voltage (5.0 V). However, There are low disadvantages.
  • the present invention provides a solid electrolyte composition for a secondary battery comprising a polymer formed by graft copolymerizing a monomer containing an alkylene oxide and a crosslinkable functional group on a fluorinated polymer having a high dielectric constant to overcome the disadvantage of the fluorinated polymer do.
  • the fluoropolymer according to one embodiment of the present invention may be a poly (vinylidene fluoride-Chlorotrifluoroethylene-Trifluoroethylene) (P (VDF-CTFE-TrFE)
  • the fluorine-based polymer may be a compound represented by the following general formula (1).
  • the fluoropolymer according to one embodiment may be a trimer of VDF, CTFE, and TrFE, and the polymer may necessarily comprise CTFE.
  • an alkylene oxide and a monomer containing a crosslinkable functional group can be graft copolymerized.
  • One embodiment according to the present invention is an atomic transfer radical polymerization , Hereinafter referred to as ATRP).
  • the fluoropolymer according to the present invention is a polymer capable of grafting a branched chain by atom transfer radical polymerization. Any polymer may be used as long as it is a fluoropolymer containing such a fluorine atom, But are not limited to, polyvinylidene fluoride, polyvinyl fluoride, polychloro trifluoroethylene, polytetrafluoroethylene, polytrifluoroethylene ethylene, poly-1,2-difluoro ethylene, or a copolymer containing at least one of these, is preferably used, and polychloro-tri-fluoroethylene trifluoroethylene), more preferably poly (vinylidene fluoride-chlorotrifluoroethylene-trifluoro An ethylene) (Poly (vinylidene fluoride-Chlorotrifluoroethylene-Trifluoroethylene), or less P (VDF-TrFE-CTFE)) can be used.
  • an ion conductive alkylene oxide is introduced into the Cl group on the CTFE through atom transfer radical polymerization to lower the crystallinity of the fluorinated polymer electrolyte, thereby improving the fluidity of the polymer chain .
  • a fluorine-based polymer having a large dielectric constant it is possible to dissociate more lithium ions and exhibit higher ionic conductivity and electrochemical stability than conventional alkylene oxide-based polymers
  • the alkylene oxide according to one embodiment of the present invention is a material capable of improving the ionic conductivity of the fluorine-based polymer, and may be ethylene oxide or propylene oxide, and preferably ethylene oxide.
  • the polymer in which the alkylene oxide is grafted to the fluorine-based polymer is in the form of a gel, it can not realize a polymer 'solid' electrolyte and still has a problem of electrochemical stability. Therefore, in the present invention, a crosslinkable functional group
  • the present invention provides a solid electrolyte composition for a secondary battery that solves the disadvantages of the gel electrolyte.
  • the monomer having a crosslinkable functional group has a moiety that can be copolymerized with a fluorine-based polymer such as poly (ethylene glycol methacrylate) (hereinafter referred to as " PEGMA ") monomer, And may be a functional group capable of maintaining the mechanical strength of the electrolyte after crosslinking.
  • a fluorine-based polymer such as poly (ethylene glycol methacrylate) (hereinafter referred to as " PEGMA ") monomer
  • &quot poly (ethylene glycol methacrylate)
  • the crosslinkable functional group may be any one selected from the group consisting of a hydroxyl group, a carboxyl group and an isocyanate group, and preferably a hydroxy group.
  • the monomer according to an embodiment of the present invention may include an alkylene oxide and a crosslinkable functional group in a molar ratio of 99.5: 0.5 to 80:20. If the alkylene oxide is in the above range, a cross-linking reaction between the polymers is difficult and a gel type polymer electrolyte is formed instead of the solid polymer electrolyte. If the alkylene oxide is less than the above range, the content of the alkylene oxide is low, It should be selected as appropriate in the above range.
  • the fluoropolymer according to one embodiment of the present invention may be contained in an amount of 0.2 to 40 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the total electrolyte composition. If the content of the fluorine polymer is higher than the above range, the mechanical strength of the electrolyte is increased. However, ionic conductivity is lowered due to crystallinity in the polymer. If the content of the fluorine polymer is less than the above range, high electrochemical stability of the fluorine polymer and high lithium ion dissociation Characteristics can not be implemented. Therefore, it is appropriately selected in the above range.
  • the solid electrolyte composition for a secondary battery according to an embodiment of the present invention includes a polyfunctional crosslinking agent having at least two functional groups capable of reacting with an alkylene oxide and a polymer grafted with a monomer containing a crosslinkable functional group, May be further included.
  • the polyfunctional crosslinking agent may further react with the functional group of the polymer to form a crosslinking structure between polymers, and the solid electrolyte formed by the crosslinking structure can overcome the problem of electrochemical stability of the gel polymer electrolyte.
  • the type of polyfunctional crosslinking agent is not particularly limited, and any one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent and a metal chelate crosslinking agent may be used.
  • isocyanate crosslinking agent examples include diisocyanate compounds such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate or naphthalene diisocyanate, or diisocyanate compounds such as diisocyanate
  • a compound obtained by reacting a compound with a polyol can be used.
  • the polyol for example, trimethylolpropane and the like can be used.
  • epoxy crosslinking agent examples include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidylethylenediamine and glycerin diglycidyl And the like.
  • aziridine crosslinking agent examples include N, N'-toluene-2,4-bis (1-aziridine carboxamide), N, N'-diphenyl (2-methylaniline) and tri-1-aziridinylphosphine oxides, which are composed of methane-4,4'-bis (1-aziridine carboxamide), triethylene melamine, bisisopropanoyl- But is not limited thereto.
  • the metal chelate crosslinking agent include compounds in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and / or vanadium is coordinated to acetylacetone or ethyl acetoacetate, But is not limited thereto.
  • the polyfunctional crosslinking agent may be contained in an amount of 0.1 to 6 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the electrolyte composition.
  • the content of the crosslinking agent may be controlled within the above-mentioned range so that the physical properties of the electrolyte can be appropriately represented at a desired level.
  • the present invention provides a solid electrolyte for a secondary battery formed by thermally curing the above-described solid electrolyte composition for a secondary battery.
  • the solid electrolyte can exhibit the above-described effects.
  • the thickness of the electrolyte may be 50 to 400 mu m, specifically 100 to 250 mu m.
  • the electrolyte has a thickness of 100 to 250 ⁇ ⁇ , the electric short and the cross over of the electrolyte material are reduced, and excellent lithium ion conductivity characteristics can be exhibited.
  • the ionic conductivity of the polymer electrolyte may be 1 ⁇ 10 -6 S / cm to 4 ⁇ 10 -5 S / cm.
  • the solid electrolyte according to an embodiment of the present invention may further include 30 to 70 parts by weight of a lithium salt, preferably 35 to 60 parts by weight, based on 100 parts by weight of the electrolyte composition. If the content of the lithium salt exceeds the above range, side reactions within the electrolyte occur excessively during charging and discharging of the battery. When the amount is less than the above range, the output and cycle characteristics of the lithium secondary battery are not improved.
  • the lithium salt can be used without limitation as long as it is commonly used in an electrolyte for a lithium secondary battery.
  • LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiTFSI, LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li At least one lithium salt selected from the group consisting of (CF 3 SO 2 ) 2 NLi, LiN (SO 2 F) 2 , chloroborane lithium, lithium lower aliphatic carboxylate, lithium 4-phenylborate and lithium imide And may further preferably include LiTFSI.
  • the method for producing the solid electrolyte composition according to the present invention may include a mixing step and a polymerization step.
  • the mixing step may be a step of mixing a raw material for preparing a polymer in which a monomer containing an alkylene oxide and a crosslinkable functional group is grafted on a fluorine-containing polymer to form a mixture, and one exemplary mixing step And mixing the fluoropolymer with the monomer to be polymerized. Thereafter, additional catalyst and ligand may be mixed with the solvent.
  • the fluoropolymer is a part which becomes the main chain of the grafted polymer. Specific examples thereof are as described above.
  • poly (vinylidene-co-chlorodrifluoroethylene) VDF-co-CTFE.
  • the alkylene oxide and the monomer having a crosslinkable functional group may be poly (ethylene glycol methacrylate) (hereinafter referred to as PEGMA) or hydroxy ethyl methacrylate (hereinafter referred to as HEMA ).
  • a monomer having an alkylene oxide group and a crosslinkable functional group may be mixed in a solution in which the fluorine-based polymer is dissolved.
  • the solvent may be any of various solvents known in the art, and examples thereof include N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL) dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), and the like, but the present invention is not limited thereto.
  • the catalyst and the ligand can be mixed together with the solvent.
  • the catalysts include, for example, Cu (II) Cl 2, Cu (II) Br 2, Cu (II) I 2, Fe (II) Cl 2, Fe (III) Cl 3 or mixtures thereof may be exemplified Cu (II) Cl 2 , Cu (II) Br 2 , Cu (II) I 2 or a mixture thereof can be exemplified, and more preferably Cu (II) Cl 2 can be used.
  • the content of the catalyst may be 0.001 to 1 part by weight, 0.005 to 0.75 part by weight or 0.01 to 0.5 part by weight based on 100 parts by weight of the total composition.
  • the content of the catalyst is less than 0.001 part by weight, the reaction rate is very retarded.
  • the amount of the catalyst is more than 1 part by weight, the molecular weight of the polymerized copolymer may be excessively low.
  • the catalysts can use various types of catalysts known in the art. For example, it may be in the form of powder, wire or mesh, but is not limited thereto.
  • the ligand is not particularly limited as long as it can be used in the polymerization reaction by binding with the catalyst.
  • the ligand may contain a ligand having at least one nitrogen, oxygen, phosphorus and sulfur atom capable of coordinating with the catalyst via a sigma-bond, or a ligand containing at least two carbon atoms capable of coordinating with the catalyst through a [ But is not limited thereto.
  • TPMA tris (2-pyridylmethyl) amine
  • the content of the ligand may be 100 to 2000 parts by weight, 150 to 1000 parts by weight or 200 to 500 parts by weight based on 100 parts by weight of the catalyst. If the content of the ligand is less than 100 parts by weight, the formation of the metal complex due to the bond with the catalyst is so small that the reaction does not proceed very slowly or progresses. When the amount exceeds 2,000 parts by weight, the production cost rises, There is a problem that appears.
  • the polymer according to an embodiment of the present invention may be PVDF-co- (PCTFE-g- (PEGMA-co-HEMA)) as shown in the following Chemical Formula 2.
  • Q, n, p, m and o each independently represent an integer of 0? Q? 20,000, 1? N? 22,000, 2? P? 230, 1? M? 200 and 2? )
  • the step of immersing the polymer produced in the graft polymerization reaction in an ether solvent to remove unreacted monomers may be further performed. Thereafter, the polymer is dried under vacuum conditions to obtain a gel-type polymer electrolyte composition.
  • the polyfunctional crosslinking agent described above is added to the solid electrolyte composition at a molar ratio of 1: 1 to 1: 0.01, relative to the crosslinking functional groups present in the total polymer, dissolved in a solvent and stirred for 1 to 6 hours .
  • the solution may then be cast on a Teflon plate and heat treated at 50-150 ° C to crosslink the polymer to form a film. After drying the Teflon plate under vacuum condition for 3 days, the solid film is removed from the Teflon plate to form a polymer solid electrolyte for a lithium secondary battery.
  • P (VDF-co-CTFE) polymer having a weight average molecular weight (Mw) of 600,000 without grafting copolymerization of PEGMA and HEMA as monomers was prepared in Preparation Examples 1 and 2.
  • a polymer having a weight average molecular weight (Mw) of 230,000 obtained by polymerizing PEGMA and HEMA in a molar ratio of 9: 1 without using P (VDF-co-CTFE) as a main chain in the preparation examples 1 and 2 was prepared.
  • DSC discovery 250 (TA instruments)
  • Polymer P (VDF-co-CTFE): PEGMA: HEMA (molar ratio) Fluorine content in polymer Mw (PDI) Glass transition temperature (Tg, ° C) H Tm (J / g) A1 1: 13.5: 1.5 10% 1.8 million (6.7) -64 0.58 A2 1: 6.3: 0.7 25% 101 (5.7) -58 4.28 B1 1: 0: 0 100% 600,000 (-) -25 16.18 B2 0: 9: 1 0% 23 (3.2) -73 -
  • a solution prepared by dissolving 5 g of the polymer prepared in Comparative Preparation Examples 1 and 2, difunctional toluene diisocyanate as a polyfunctional crosslinking agent and LiTFSI as a lithium salt in 50 ml of THF solvent as shown in Table 2 was stirred for 6 hours A uniform solution was prepared.
  • the solution was cast in a 2 cm x 2 cm Teflon plate, dried in a dry room at room temperature for 6 hours, and then heated at 120 ° C for 1 hour to effect a thermal curing reaction. Thereafter, the solid film was detached from the Teflon plate using a knife to obtain a solid electrolyte for a secondary battery.
  • crosslinkable functional group in polymer crosslinkable functional group (mol ratio) in polyfunctional crosslinking agent
  • a film sample of the solid electrolyte having a certain width and thickness was prepared for measurement.
  • An SUS substrate having excellent electron conductivity was brought into contact with an ion blocking electrode on both sides of a plate-shaped sample, and an AC voltage was applied through the electrodes on both sides of the sample.
  • the amplitude of the measurement frequency was set to 0.1 Hz to 10 MHz under the applied conditions.
  • the resistance of the bulk electrolyte was obtained from the intersection point (R b ) where the semicircle or the straight line of the measured impedance trajectory meets the real axis, and the ionic conductivity of the polymer solid electrolyte membrane was calculated from the width and thickness of the sample.
  • Example 1 O 2.7 x 10 -7
  • Example 2 O 1.9 x 10 -6
  • Example 3 O 3.2 x 10 -5
  • Example 4 O 4.5 x 10 -5
  • Example 5 O 2.4 x 10 -5
  • Comparative Example 1 O 8.5 x 10 -7
  • Comparative Example 2 O 2.1 x 10 -6 Comparative Example 3
  • Comparative Example 4 O 3.5 x 10 -6
  • Comparative Example 5 O 6.7 x 10 -6 Comparative Example 6 O 9.8 x 10 -7
  • the ionic conductivity of a solid electrolyte for a secondary battery including a polymer grafted with an alkylene oxide and a monomer containing a crosslinking functional group on a fluorine polymer was measured to be high, It was found that the conductivity was improved. In the case of Comparative Example 3, it was found that the ionic conductivity was high, but the electrolyte membrane according to the present invention was not formed.

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Abstract

본 발명은 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 리튬 이차전지용 고체 전해질 조성물 및 상기 조성물을 열경화하여 형성되는 이차전지용 고체 전해질에 관한 발명이다. 본 발명에 고체 전해질은 리튬 이온전도도가 높은 불소계 중합체에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체를 그라프팅 공중합함으로써, 고체 전해질의 이온전도도와 전기화학적 안정성이 크게 향상된 이차전지용 고체 전해질을 제공할 수 있다.The present invention relates to a solid electrolyte composition for a lithium secondary battery in which a monomer containing an alkylene oxide and a crosslinkable functional group is grafted on a fluorine polymer, and a solid electrolyte for a secondary battery formed by thermosetting the composition. The solid electrolyte according to the present invention provides a solid electrolyte for a secondary battery in which ionic conductivity and electrochemical stability of a solid electrolyte are greatly improved by grafting and copolymerizing a monomer containing an alkylene oxide and a crosslinkable functional group to a fluorine polymer having a high lithium ion conductivity .

Description

이차전지용 고체 전해질 조성물 및 이로부터 제조된 고체 전해질Solid electrolyte compositions for secondary batteries and solid electrolytes prepared therefrom

본 출원은 2017년 09월 14일자 한국 특허 출원 제10-2017-0118035호 및 2018년 07월 10일자 한국 특허 출원 제10-2018-0080139호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함한다.This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0118035, filed on Sep. 14, 2017, and Korean Patent Application No. 10-2018-0080139, filed on July 10, 2018, All of which are incorporated herein by reference.

본 발명은 이차전지용 고체 전해질 조성물 및 이로부터 제조된 고체 전해질에 관한 것이다.The present invention relates to a solid electrolyte composition for a secondary battery and a solid electrolyte prepared therefrom.

현재 노트북, 스마트폰에 주로 사용되고 있는 고(高) 에너지 밀도의 리튬 이차전지는 리튬 산화물로 이루어진 양극과 탄소계의 음극, 분리막, 및 액상 또는 고상의 전해질로 구성되어 있다. 하지만 액상 전해질로 구성된 리튬 이차전지는 누액, 폭발과 같은 안정성 문제가 있고, 이를 막기 위하여 전지 설계가 복잡해지는 단점을 가지고 있다.Lithium secondary batteries, which are mainly used in notebook computers and smart phones, are composed of a cathode made of lithium oxide, a carbon-based cathode, a separator, and a liquid or solid electrolyte. However, a lithium secondary battery composed of a liquid electrolyte has a problem of stability such as leakage and explosion, and has a disadvantage in that the battery design becomes complicated in order to prevent it.

이러한 액체 전해질의 문제를 해결하고자 고분자 전해질에 대한 연구가 활발히 진행되고 있다. 고분자 전해질은 크게 겔형과 고체형으로 구분된다. 겔형 고분자 전해질은 고분자 필름 내에 비점이 높은 액체 전해질을 함침시키고 이를 리튬염과 함께 고정하여 전도도를 나타내는 전해질로써 액체 전해질을 다량 함유하고 있어 순수 액체 전해질과 유사한 이온전도도를 갖지만, 여전히 전기 화학적 안정성의 문제가 남아있다.In order to solve the problem of the liquid electrolyte, researches on polymer electrolytes have been actively conducted. Polymer electrolytes are classified into gel type and solid type. The gel-type polymer electrolyte is an electrolyte exhibiting conductivity by impregnating a liquid electrolyte having a high boiling point in a polymer film and fixing it with a lithium salt, and thus has a similar ionic conductivity to that of a pure liquid electrolyte because it contains a large amount of liquid electrolyte. Is left.

반면에 고체 고분자 전해질의 경우 액체 전해질이 포함되어 있지 않아 누액과 관련한 안정성 문제가 개선되었을 뿐만 아니라 화학적, 전기화학적 안정성이 높다는 장점이 있다. 하지만 상온에서의 이온전도도가 액체 전해질 대비 약 100배 정도 낮아 이를 개선하기 위한 연구가 많이 진행되고 있다.On the other hand, the solid polymer electrolyte contains no liquid electrolyte, which improves the stability problem related to leakage, and has a high chemical and electrochemical stability. However, the ion conductivity at room temperature is about 100 times lower than that of the liquid electrolyte, so that much research has been conducted to improve the ion conductivity.

현재 고체 고분자 전해질에 가장 많이 사용되고 있는 물질을 폴리에틸렌옥사이드(PEO)로, 고체상임에도 불구하고 리튬 이온을 전도시키는 능력을 가지고 있다. 하지만 선형의 PEO 고분자 전해질의 경우 높은 결정성으로 인해 사슬의 유동성이 제한되고, 유전상수(5.0)가 낮아 많은 양의 리튬 이온을 해리시키지 못해 상온에서 전도도가 매우 낮아 리튬 이차전지에 적용하기 어렵다.Currently, the most widely used solid polymer electrolyte is polyethylene oxide (PEO), which has the ability to conduct lithium ions despite being solid. However, the linear PEO polymer electrolyte has a limited fluidity of the chain due to its high crystallinity and has a low dielectric constant (5.0), which makes it difficult to dissolve a large amount of lithium ions and thus has a very low conductivity at room temperature.

이에 폴리에틸렌옥사이드에 결정성이 없는 고분자를 블렌드하거나 또는 가소제를 첨가하여 고분자 주사슬의 유연성을 증가시키는 방법, 비정질의 고분자 주사슬에 저분자량의 에틸렌 옥사이드 곁가지를 결합하여 결정화도를 낮추는 방법 또는 가교 구조를 갖는 고분자에 분자량이 낮은 폴리에틸렌옥사이드를 고정화시켜 폴리에틸렌옥사이드가 가지고 있는 결정성을 낮추어 전도도를 향상시키는 방법 등이 연구되고 있으나 여전히 한계가 있는 실정이다.A method of blending a polymer having no crystallinity in polyethylene oxide or adding a plasticizer to increase the flexibility of the polymer main chain, a method of lowering the crystallinity by bonding a low molecular weight ethylene oxide side chain to an amorphous polymer main chain, And a method of improving the conductivity by lowering the crystallinity of polyethylene oxide by immobilizing polyethylene oxide having a low molecular weight on a polymer having a low molecular weight has been studied.

[선행기술문헌][Prior Art Literature]

[특허문헌][Patent Literature]

(특허문헌 1) 대한민국 등록특허 제10-0796989호(2008.01.16), "수소이온 전도성 가교형 불소계 공중합체 전해질막"(Patent Document 1) Korean Patent No. 10-0796989 (Jan. 16, 2008), " Hydrogen-ion conductive crosslinked fluoropolymer electrolyte membrane "

(특허문헌 2) 대한민국 등록특허 제10-0796990호(2008.01.16), "친수성 및 술폰화 그룹이 도입된 가지형 불소계 공중합체전해질막"(Patent Document 2) Korean Patent No. 10-0796990 (Jan. 16, 2008), " Organic fluorine-based copolymer electrolyte membrane into which hydrophilic and sulfonation group is introduced "

이에 본 발명자들은 상기 문제를 해결하고자 다각적으로 연구를 수행한 결과, 유전상수가 높은 불소계 중합체 상에 이온전도성이 있는 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체를 그라프트 공중합시켜 리튬 이차전지용 고체 전해질을 제조하는 경우, 전해질의 이온전도도와 전기화학적 안정성이 향상된 것을 확인하여 본 발명을 완성하였다.Accordingly, the present inventors have conducted various studies to solve the above problems. As a result, they have found that an alkylene oxide having ionic conductivity and a monomer containing a crosslinkable functional group are graft copolymerized on a fluoride polymer having a high dielectric constant to form a solid electrolyte for a lithium secondary battery It was confirmed that the ionic conductivity and the electrochemical stability of the electrolyte were improved, thereby completing the present invention.

따라서, 본 발명의 목적은 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 고분자를 포함하는 이차전지용 고체 전해질 조성물을 제공하는데 있다.Accordingly, an object of the present invention is to provide a solid electrolyte composition for a secondary battery, which comprises a polymer on which an alkylene oxide and a monomer containing a crosslinkable functional group are grafted, on a fluorinated polymer.

또한, 본 발명의 또 다른 목적은 상기 조성물을 열경화하여 형성되는 이차전지용 고체 전해질을 제공하는데 있다.It is still another object of the present invention to provide a solid electrolyte for a secondary battery formed by thermally curing the composition.

상기 목적을 달성하기 위해, 본 발명은 In order to achieve the above object,

불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 고분자를 포함하는 이차전지용 고체 전해질 조성물을 제공한다.There is provided a solid electrolyte composition for a secondary battery, which comprises a polymer obtained by grafting an alkylene oxide and a monomer containing a crosslinkable functional group onto a fluorine polymer.

본 발명의 일 구현예에 있어서 상기 불소계 중합체는 하기 화학식 1의 구조를 포함할 수 있다.In one embodiment of the present invention, the fluorine-based polymer may include a structure represented by the following formula (1).

[화학식 1][Chemical Formula 1]

Figure PCTKR2018008244-appb-I000001
Figure PCTKR2018008244-appb-I000001

(상기 화학식 1에서 p,q,r 은 각각 독립적으로 0≤p≤20,000, 1≤q≤22,000 및 0≤r≤15,000의 정수이다).(Wherein p, q and r each independently represent an integer of 0? P? 20,000, 1? Q? 22,000 and 0? R? 15,000).

본 발명의 일 구현예에 있어서 상기 그라프팅 된 고분자는 하기 화학식 2의 구조를 포함할 수 있다.In one embodiment of the present invention, the grafted polymer may include a structure represented by the following formula (2).

[화학식 2](2)

Figure PCTKR2018008244-appb-I000002
Figure PCTKR2018008244-appb-I000002

(상기 화학식 2에서 q, n, p, m 및 o는 각각 독립적으로 0≤q≤20,000, 1≤n≤22,000, 2≤p≤230, 1≤m≤200 및 2≤o≤50 의 정수이다)Q, n, p, m and o each independently represent an integer of 0? Q? 20,000, 1? N? 22,000, 2? P? 230, 1? M? 200 and 2? )

본 발명의 일 구현예에 있어서 상기 알킬렌 옥사이드는 에틸렌 옥사이드 또는 프로필렌 옥사이드일 수 있다.In one embodiment of the present invention, the alkylene oxide may be ethylene oxide or propylene oxide.

본 발명의 일 구현예에 있어서 상기 가교성 관능기는 하이드록시기, 카복실기 및 이소시아네이트기로 이루어진 군에서 선택되는 어느 하나인 것일 수 있다.In one embodiment of the present invention, the crosslinkable functional group may be any one selected from the group consisting of a hydroxyl group, a carboxyl group and an isocyanate group.

본 발명의 일 구현예에 있어서 상기 단량체는 알킬렌 옥사이드와 가교성 관능기를 99.5:0.5 내지 80:20의 몰비로 포함하는 것일 수 있다.In one embodiment of the present invention, the monomer may include an alkylene oxide and a crosslinkable functional group in a molar ratio of 99.5: 0.5 to 80:20.

본 발명의 일 구현예에 있어서 상기 불소계 중합체는 전체 조성물 100 중량부 대비 0.2 내지 40 중량부로 포함되는 것일 수 있다.In one embodiment of the present invention, the fluoropolymer may be contained in an amount of 0.2 to 40 parts by weight based on 100 parts by weight of the total composition.

본 발명의 일 구현예에 있어서 상기 조성물은 상기 가교성 관능기와 반응할 수 있는 관능기를 2개 이상 가지는 다관능 가교제를 추가로 포함하는 것일 수 있다.In one embodiment of the present invention, the composition may further comprise a polyfunctional crosslinking agent having two or more functional groups capable of reacting with the crosslinkable functional group.

본 발명의 일 구현예에 있어서 상기 다관능 가교제는 이소시아네이트 가교제, 에폭시 가교제, 아지리딘 가교제 및 금속 킬레이트 가교제로 이루어진 군에서 선택되는 어느 하나인 것일 수 있다.In one embodiment of the present invention, the polyfunctional crosslinking agent may be any one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent.

본 발명의 일 구현예에 있어서 상기 다관능 가교제는 전체 전해질 조성물 100 중량부 대비 0.1 내지 6 중량부로 포함될 수 있다.In one embodiment of the present invention, the polyfunctional crosslinking agent may be included in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the total electrolyte composition.

또한 본 발명은 상기 이차전지용 고체 전해질 조성물을 열경화하여 형성되는 이차전지용 고체 전해질을 제공한다.The present invention also provides a solid electrolyte for a secondary battery formed by thermally curing the solid electrolyte composition for a secondary battery.

본 발명의 일 구현예에 있어서 상기 전해질은 그 두께가 50 내지 400 ㎛일 수 있다.In one embodiment of the present invention, the electrolyte may have a thickness of 50 to 400 mu m.

본 발명의 일 구현예에 있어서 상기 전해질은 상기 전해질 조성물 100 중량부 대비 30 내지 70 중량부의 리튬염을 더 포함할 수 있다.In one embodiment of the present invention, the electrolyte may further comprise 30 to 70 parts by weight of a lithium salt based on 100 parts by weight of the electrolyte composition.

본 발명의 일 구현예에 있어서 상기 전해질은 LiCl, LiBr, LiI, LiClO4, LiBF4, LiTFSI, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, (CF3SO2)2NLi, LiN(SO2F)2, 클로로 보란 리튬, 저급 지방족 카르본산 리튬, 4-페닐 붕산 리튬 및 리튬 이미드로 이루어지는 군에서 선택되는 1종 이상의 리튬염을 더 포함할 수 있다.In one embodiment of the invention the electrolyte is LiCl, LiBr, LiI, LiClO 4 , LiBF 4, LiTFSI, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, (CF 3 SO 2) 2 NLi, LiN (SO 2 F) 2, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4-phenyl lithium borate and lithium already selected from the group consisting of draw And may further include a lithium salt of a species or more.

본 발명의 일 구현예에 있어서 상기 전해질은 이온전도도가 1 × 10-6 S/cm 내지 4 × 10-5 S/cm 일 수 있다.In one embodiment of the present invention, the electrolyte may have an ionic conductivity of 1 × 10 -6 S / cm to 4 × 10 -5 S / cm.

본 발명에 따른 이차전지용 고체 전해질 조성물은 유전상수가 높은 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체를 그라프팅 시켜 제조되는 고분자를 포함함에 따라 리튬 이차전지의 전해질의 이온전도도와 전기화학적 안정성을 향상시킬 수 있는 효과가 있다.The solid electrolyte composition for a secondary battery according to the present invention comprises a polymer produced by grafting an alkylene oxide and a monomer containing a crosslinkable functional group on a fluoropolymer having a high dielectric constant, And the chemical stability can be improved.

이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

본 발명에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 발명에서, '포함하다' 또는 '가지다'등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하여는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present invention, terms such as "comprises" or "having" designate the presence of stated features, integers, steps, operations, components, parts, or combinations thereof, But do not preclude the presence or addition of features, numbers, steps, operations, components, parts, or combinations thereof.

이차전지용 고체 전해질 조성물Solid electrolyte composition for secondary battery

불소계 고분자는 유전상수가 9 내지 40 정도로 리튬 이온 해리도가 매우 높고, 리튬 이차전지에 사용될 경우 고전압(5.0V)에서도 전기화학적 안정성을 가진다는 장점이 있으나, 높은 결정성으로 인하여 상온에서 이온전도도가 매우 낮은 단점이 있다.The fluorine-based polymer has a dielectric constant of about 9 to 40 and a very high lithium ion dissociation degree. When used in a lithium secondary battery, the fluorine-based polymer has an electrochemical stability even at a high voltage (5.0 V). However, There are low disadvantages.

따라서 본 발명에서는 불소계 고분자의 이러한 단점을 극복하고자, 유전상수가 높은 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체를 그라프트 공중합하여 형성되는 고분자를 포함하는 이차전지용 고체 전해질 조성물을 제공한다.Accordingly, the present invention provides a solid electrolyte composition for a secondary battery comprising a polymer formed by graft copolymerizing a monomer containing an alkylene oxide and a crosslinkable functional group on a fluorinated polymer having a high dielectric constant to overcome the disadvantage of the fluorinated polymer do.

본 발명의 일구현에 따른 불소계 중합체는 폴리(비닐리덴플루오라이드-클로로 트리플루오로에틸렌-트리플루오로에틸렌)(Poly(vinylidene fluoride-Chlorotrifluoroethylene-Trifluoroethylene), 이하 P(VDF-CTFE-TrFE))계 고분자일 수 있으며, 상기 불소계 중합체는 하기 화학식 1로 표시되는 화합물일 수 있다.The fluoropolymer according to one embodiment of the present invention may be a poly (vinylidene fluoride-Chlorotrifluoroethylene-Trifluoroethylene) (P (VDF-CTFE-TrFE) And the fluorine-based polymer may be a compound represented by the following general formula (1).

[화학식 1][Chemical Formula 1]

Figure PCTKR2018008244-appb-I000003
Figure PCTKR2018008244-appb-I000003

(상기 화학식 1에서 p,q,r 은 각각 독립적으로 0≤p≤20,000, 1≤q≤22,000 및 0≤r≤15,000의 정수이다)(Wherein p, q and r each independently represent an integer of 0? P? 20,000, 1? Q? 22,000 and 0? R? 15,000)

상기 일 구현예에 따른 불소계 중합체는 VDF, CTFE 및 TrFE의 삼량체일 수 있으며, 상기 중합체는 CTFE를 반드시 포함하는 것 일 수 있다.The fluoropolymer according to one embodiment may be a trimer of VDF, CTFE, and TrFE, and the polymer may necessarily comprise CTFE.

상기 불소계 중합체의 이온전도성과 전기화학적 안정성을 향상시키기 위해 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체를 그라프트 공중합할 수 있고, 본 발명에 따른 일 구현예는 원자 전달 라디칼 중합 (atomic transfer radical polymerization, 이하 ATRP)을 이용한 그라프트 공중합일 수 있다.In order to improve ionic conductivity and electrochemical stability of the fluoropolymer, an alkylene oxide and a monomer containing a crosslinkable functional group can be graft copolymerized. One embodiment according to the present invention is an atomic transfer radical polymerization , Hereinafter referred to as ATRP).

본 발명에 따른 불소계 중합체는 원자 전달 라디칼 중합반응에 의해 가지형 사슬이 그라프팅 될 수 있는 중합체로서, 이러한 불소원자를 포함하는 고분자 중합체라면 어떠한 중합체를 사용하여도 무방하지만, 바람직하게는 폴리 비닐리덴 플루오라이드(poly vinylidene fluoride), 폴리 비닐 플루오라이드(poly vinyl fluoride), 폴리 클로로 트리플루오로 에틸렌(poly chloro trifluoro ethylene), 폴리 테트라플루오로 에틸렌(poly tetrafluoro ethylene), 폴리 트리플루오로 에틸렌(poly triluoro ethylene), 폴리-1,2-디플루오로 에틸렌(poly-1,2-difluoro ethylene), 또는 이들을 하나 이상 포함하는 공중합체를 사용하는 것이 좋으며, 바람직하게는 폴리 클로로 트리플루오로 에틸렌(poly chloro trifluoro ethylene), 더욱 바람직하게는 폴리(비닐리덴플루오라이드-클로로 트리플루오로에틸렌-트리플루오로에틸렌)(Poly(vinylidene fluoride-Chlorotrifluoroethylene-Trifluoroethylene), 이하 P(VDF-CTFE-TrFE))을 사용할 수 있다.The fluoropolymer according to the present invention is a polymer capable of grafting a branched chain by atom transfer radical polymerization. Any polymer may be used as long as it is a fluoropolymer containing such a fluorine atom, But are not limited to, polyvinylidene fluoride, polyvinyl fluoride, polychloro trifluoroethylene, polytetrafluoroethylene, polytrifluoroethylene ethylene, poly-1,2-difluoro ethylene, or a copolymer containing at least one of these, is preferably used, and polychloro-tri-fluoroethylene trifluoroethylene), more preferably poly (vinylidene fluoride-chlorotrifluoroethylene-trifluoro An ethylene) (Poly (vinylidene fluoride-Chlorotrifluoroethylene-Trifluoroethylene), or less P (VDF-TrFE-CTFE)) can be used.

본 발명의 일 구현예는, 원자 전달 라디칼 중합을 통해 상기 CTFE 상의 Cl group에 이온전도성을 가진 알킬렌 옥사이드를 도입하여 불소계 고분자 전해질의 결정성을 낮출 수 있고, 이에 따라 고분자 사슬의 유동성을 향상시킬 수 있다. 뿐만 아니라 유전상수가 큰 불소계 고분자를 적용함으로써 더 많은 리튬 이온을 해리하여 기존 알킬렌 옥사이드계 고분자 대비 높은 이온전도도 및 전기화학적 안정성을 나타낼 수 있다In one embodiment of the present invention, an ion conductive alkylene oxide is introduced into the Cl group on the CTFE through atom transfer radical polymerization to lower the crystallinity of the fluorinated polymer electrolyte, thereby improving the fluidity of the polymer chain . In addition, by applying a fluorine-based polymer having a large dielectric constant, it is possible to dissociate more lithium ions and exhibit higher ionic conductivity and electrochemical stability than conventional alkylene oxide-based polymers

본 발명의 일 구현예에 따른 상기 알킬렌 옥사이드는 불소계 중합체의 이온전도성을 향상시킬 수 있는 물질로써, 에틸렌 옥사이드 또는 프로필렌 옥사이드일 수 있고, 바람직하게는 에틸렌 옥사이드일 수 있다.The alkylene oxide according to one embodiment of the present invention is a material capable of improving the ionic conductivity of the fluorine-based polymer, and may be ethylene oxide or propylene oxide, and preferably ethylene oxide.

그러나 상기 불소계 중합체에 알킬렌 옥사이드가 그라프팅 된 고분자는 겔(gel) 형태로써, 고분자 '고체' 전해질을 구현할 수 없고 전기화학적 안정성의 문제를 여전히 가지고 있으므로 본 발명에서는 추가적으로 고분자 내에 가교성 관능기를 더 포함하여, 상기 겔 형 전해질의 단점을 해결한 이차전지용 고체 전해질 조성물을 제공한다.However, since the polymer in which the alkylene oxide is grafted to the fluorine-based polymer is in the form of a gel, it can not realize a polymer 'solid' electrolyte and still has a problem of electrochemical stability. Therefore, in the present invention, a crosslinkable functional group The present invention provides a solid electrolyte composition for a secondary battery that solves the disadvantages of the gel electrolyte.

상기 가교성 관능기를 갖는 단량체는 예를 들면, 상기 폴리(에틸렌 글리콜 메타크릴레이트)(Poly(ethylene glycol methacrylate), 이하 PEGMA) 단량체와 같이 불소계 중합체에 공중합될 수 있는 부위를 가지고, 후술할 열경화 후 가교되어 전해질의 기계적 강도를 유지할 수 있는 관능기일 수 있다.The monomer having a crosslinkable functional group has a moiety that can be copolymerized with a fluorine-based polymer such as poly (ethylene glycol methacrylate) (hereinafter referred to as " PEGMA ") monomer, And may be a functional group capable of maintaining the mechanical strength of the electrolyte after crosslinking.

상기 가교성 관능기는 하이드록시기, 카복실기 및 이소시아네이트기로 이루어진 군에서 선택되는 어느 하나일 수 있으며, 바람직하게는 하이드록시기일 수 있다.The crosslinkable functional group may be any one selected from the group consisting of a hydroxyl group, a carboxyl group and an isocyanate group, and preferably a hydroxy group.

본 발명의 일 구현예에 따른 상기 단량체는 알킬렌 옥사이드와 가교성 관능기를 99.5:0.5 내지 80:20의 몰비로 포함하는 것일 수 있다. 만일 알킬렌 옥사이드가 상기 범위 이상일 경우에는 고분자간의 가교반응이 어려워 고체 고분자 전해질 대신 겔 형 고분자 전해질을 생성하는 문제점이 있으며, 상기 범위 이하일 경우에는 알킬렌 옥사이드의 함량이 적어 전해질의 이온 전달 능력이 떨어질 수 있으므로 상기 범위에서 적절히 선택한다.The monomer according to an embodiment of the present invention may include an alkylene oxide and a crosslinkable functional group in a molar ratio of 99.5: 0.5 to 80:20. If the alkylene oxide is in the above range, a cross-linking reaction between the polymers is difficult and a gel type polymer electrolyte is formed instead of the solid polymer electrolyte. If the alkylene oxide is less than the above range, the content of the alkylene oxide is low, It should be selected as appropriate in the above range.

본 발명의 일 구현예에 따른 상기 불소계 중합체는 전체 전해질 조성물 100 중량부 대비 0.2 내지 40 중량부로 포함될 수 있고, 바람직하게는 5 내지 25 중량부로 포함될 수 있다. 만일 불소계 중합체의 함량이 상기 범위 이상이면 전해질의 기계적 강도는 높아지나, 고분자 내 결정성으로 인해 이온전도도가 떨어지며, 불소계 중합체의 함량이 상기 범위 미만일 경우 불소계 중합체의 높은 전기화학적 안정성 및 높은 리튬 이온 해리 특성을 구현할 수 없게 되므로 상기 범위에서 적절히 선택한다.The fluoropolymer according to one embodiment of the present invention may be contained in an amount of 0.2 to 40 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the total electrolyte composition. If the content of the fluorine polymer is higher than the above range, the mechanical strength of the electrolyte is increased. However, ionic conductivity is lowered due to crystallinity in the polymer. If the content of the fluorine polymer is less than the above range, high electrochemical stability of the fluorine polymer and high lithium ion dissociation Characteristics can not be implemented. Therefore, it is appropriately selected in the above range.

본 발명의 일 구현예에 따른 이차전지용 고체 전해질 조성물은 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 고분자와 반응할 수 있는 관능기를 적어도 2개 이상 가지는 다관능 가교제를 추가로 포함할 수 있다. The solid electrolyte composition for a secondary battery according to an embodiment of the present invention includes a polyfunctional crosslinking agent having at least two functional groups capable of reacting with an alkylene oxide and a polymer grafted with a monomer containing a crosslinkable functional group, May be further included.

상기 다관능 가교제는 상기 고분자의 관능기와 추가적으로 반응하여 고분자 간 가교 구조를 형성할 수 있으며, 상기 가교 구조로 형성된 고체 전해질은 겔 형 고분자 전해질의 전기 화학적 안정성의 문제를 극복할 수 있다. The polyfunctional crosslinking agent may further react with the functional group of the polymer to form a crosslinking structure between polymers, and the solid electrolyte formed by the crosslinking structure can overcome the problem of electrochemical stability of the gel polymer electrolyte.

다관능 가교제의 종류로는, 특별히 제한되지 않으며, 이소시아네이트 가교제, 에폭시 가교제, 아지리딘 가교제 및 금속 킬레이트 가교제로 이루어진 군에서 선택되는 어느 하나를 사용할 수 있다.The type of polyfunctional crosslinking agent is not particularly limited, and any one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent and a metal chelate crosslinking agent may be used.

이소시아네이트 가교제의 구체적인 예로는 톨루엔 디이소시아네이트, 크실렌 디이소시아네이트, 디페닐메탄 디이소시아네이트, 헥사메틸렌 디이소시아네이트, 이소보론 디이소시아네이트, 테트라메틸크실렌 디이소시아네이트 또는 나프탈렌 디이소시아네이트 등의 디이소시아네이트 화합물이나, 또는 상기 디이소시아네이트 화합물을 폴리올과 반응시킨 화합물을 사용할 수 있으며, 상기에서 폴리올로는, 예를 들면, 트리메틸올 프로판 등을 사용할 수 있다.Specific examples of the isocyanate crosslinking agent include diisocyanate compounds such as toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate or naphthalene diisocyanate, or diisocyanate compounds such as diisocyanate A compound obtained by reacting a compound with a polyol can be used. As the polyol, for example, trimethylolpropane and the like can be used.

또한, 에폭시 가교제의 구체적인 예로는 에틸렌글리콜 디글리시딜에테르, 트리글리시딜에테르, 트리메틸올프로판 트리글리시딜에테르, N,N,N',N'-테트라글리시딜 에틸렌디아민 및 글리세린 디글리시딜에테르로 이루어진 군으로부터 선택된 하나 이상을 들 수 있으며, 아지리딘 가교제의 구체적인 예로는 N,N'-톨루엔-2,4-비스(1-아지리딘카르복사미드), N,N'-디페닐메탄-4,4'-비스(1-아지리딘카르복사미드), 트리에틸렌 멜라민, 비스이소프로탈로일-1-(2-메틸아지리딘) 및 트리-1-아지리디닐포스핀옥시드로 이루어진 군으로부터 선택된 하나 이상을 들 수 있으나, 이에 제한되는 것은 아니다. 또한, 상기 금속 킬레이트 가교제의 구체적인 예로는, 알루미늄, 철, 아연, 주석, 티탄, 안티몬, 마그네슘 및/또는 바나듐과 같은 다가 금속이 아세틸 아세톤 또는 아세토초산 에틸 등에 배위하고 있는 화합물 등을 들 수 있으나, 이에 제한되는 것은 아니다.Specific examples of the epoxy crosslinking agent include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidylethylenediamine and glycerin diglycidyl And the like. Specific examples of the aziridine crosslinking agent include N, N'-toluene-2,4-bis (1-aziridine carboxamide), N, N'-diphenyl (2-methylaniline) and tri-1-aziridinylphosphine oxides, which are composed of methane-4,4'-bis (1-aziridine carboxamide), triethylene melamine, bisisopropanoyl- But is not limited thereto. Specific examples of the metal chelate crosslinking agent include compounds in which a polyvalent metal such as aluminum, iron, zinc, tin, titanium, antimony, magnesium and / or vanadium is coordinated to acetylacetone or ethyl acetoacetate, But is not limited thereto.

상기 다관능 가교제는 전해질 조성물 100 중량부 대비 0.1 내지 6 중량부, 바람직하게는 0.5 내지 5 중량부의 비율로 포함될 수 있다. 상기 가교제의 함량을 전술한 범위 내에서 조절하여 전해질의 물성을 목적하는 수준으로 적절하게 나타낼 수 있다.The polyfunctional crosslinking agent may be contained in an amount of 0.1 to 6 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the electrolyte composition. The content of the crosslinking agent may be controlled within the above-mentioned range so that the physical properties of the electrolyte can be appropriately represented at a desired level.

본 발명은 상술한 이차전지용 고체 전해질 조성물을 열경화하여 형성되는 이차전지용 고체 전해질을 제공한다. 상기 고체 전해질은 전술한 효과를 나타낼 수 있다.The present invention provides a solid electrolyte for a secondary battery formed by thermally curing the above-described solid electrolyte composition for a secondary battery. The solid electrolyte can exhibit the above-described effects.

본 명세서의 일 구현예에 따르면, 상기 전해질의 두께는 50 내지 400 ㎛일 수 있고, 구체적으로 100 내지 250 ㎛일 수 있다. 전해질의 두께가 100 내지 250 ㎛일 때, 전기적 쇼트(Electric Short) 및 전해질 물질의 크로스오버(Cross Over)를 저하시키고, 우수한 리튬 이온 전도도 특성을 나타낼 수 있다.According to an embodiment of the present invention, the thickness of the electrolyte may be 50 to 400 mu m, specifically 100 to 250 mu m. When the electrolyte has a thickness of 100 to 250 占 퐉, the electric short and the cross over of the electrolyte material are reduced, and excellent lithium ion conductivity characteristics can be exhibited.

본 명세서의 일 구현예에 따르면, 상기 고분자 전해질의 이온 전도도는 1 X 10-6 S/cm 내지 4 X 10-5 S/cm일 수 있다.According to an embodiment of the present invention, the ionic conductivity of the polymer electrolyte may be 1 × 10 -6 S / cm to 4 × 10 -5 S / cm.

본 발명의 일 구현예에 따른 상기 고체 전해질은 전해질 조성물 100 중량부 대비 30 내지 70 중량부의 리튬염을 더 포함할 수 있으며, 바람직하게는 35 내지 60 중량부를 더 포함할 수 있다. 만일 리튬염이 함량이 상기 범위 이상일 경우 전지의 충, 방전 시 전해질 내의 부반응이 과도하게 발생하며, 상기 범위 미만인 경우 리튬 이차전지의 출력 개선 및 사이클 특성 개선 효과가 미미하므로 상기 범위에서 적절히 선택한다.The solid electrolyte according to an embodiment of the present invention may further include 30 to 70 parts by weight of a lithium salt, preferably 35 to 60 parts by weight, based on 100 parts by weight of the electrolyte composition. If the content of the lithium salt exceeds the above range, side reactions within the electrolyte occur excessively during charging and discharging of the battery. When the amount is less than the above range, the output and cycle characteristics of the lithium secondary battery are not improved.

상기 리튬염은 리튬 이차전지용 전해질에 통상적으로 사용되는 것이라면 제한 없이 사용될 수 있다. 예를 들어, LiCl, LiBr, LiI, LiClO4, LiBF4, LiTFSI, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, (CF3SO2)2NLi, LiN(SO2F)2, 클로로 보란 리튬, 저급 지방족 카르본산 리튬, 4-페닐 붕산 리튬 및 리튬 이미드로 이루어지는 군에서 선택되는 1종 이상의 리튬염을 더 포함할 수 있으며, 바람직하게는 LiTFSI를 더 포함할 수 있다.The lithium salt can be used without limitation as long as it is commonly used in an electrolyte for a lithium secondary battery. For example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiTFSI, LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li , At least one lithium salt selected from the group consisting of (CF 3 SO 2 ) 2 NLi, LiN (SO 2 F) 2 , chloroborane lithium, lithium lower aliphatic carboxylate, lithium 4-phenylborate and lithium imide And may further preferably include LiTFSI.

고체 전해질 조성물의 제조방법Method for producing solid electrolyte composition

본 발명에 따른 고체 전해질 조성물의 제조방법은 혼합단계 및 중합단계를 포함할 수 있다.The method for producing the solid electrolyte composition according to the present invention may include a mixing step and a polymerization step.

상기에서 혼합단계는 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 고분자를 제조하기 위한 원료를 혼합하여 혼합물을 형성하는 단계일 수 있으며, 하나의 예시적인 상기 혼합단계는 불소계 중합체와 중합하고자 하는 상기 단량체를 혼합하는 단계일 수 있다. 이후 추가적으로 촉매 및 리간드를 용매와 함께 혼합하는 단계를 거칠 수 있다.The mixing step may be a step of mixing a raw material for preparing a polymer in which a monomer containing an alkylene oxide and a crosslinkable functional group is grafted on a fluorine-containing polymer to form a mixture, and one exemplary mixing step And mixing the fluoropolymer with the monomer to be polymerized. Thereafter, additional catalyst and ligand may be mixed with the solvent.

상기 불소계 중합체는 상기 그라프팅 된 고분자의 주쇄가 되는 부분이며, 이의 구체적인 예시는 전술한 바와 같고, 본 발명에 따른 일 구현예로 폴리(비닐리덴-co-클로로드리플루오로에틸렌)(이하, P(VDF-co-CTFE))일 수 있다. 또한 상기 알킬렌 옥사이드 및 가교성 관능기를 갖는 단량체는 폴리(에틸렌 글리콜 메타크릴레이트)(Poly(ethylene glycol methacrylate))(이하, PEGMA) 또는 하이드록시 에틸 메타크릴레이트(Hydroxy ethyl methacrylate)(이하, HEMA)일 수 있다.The fluoropolymer is a part which becomes the main chain of the grafted polymer. Specific examples thereof are as described above. In one embodiment of the present invention, poly (vinylidene-co-chlorodrifluoroethylene) (VDF-co-CTFE). The alkylene oxide and the monomer having a crosslinkable functional group may be poly (ethylene glycol methacrylate) (hereinafter referred to as PEGMA) or hydroxy ethyl methacrylate (hereinafter referred to as HEMA ).

불소계 중합체를 극성 용매에 녹여 준 후 알킬렌 옥사이드기 및 가교성 관능기를 갖는 단량체를 불소계 중합체가 녹아있는 용액에 넣어 혼합할 수 있다. 상기 용매는 기술 분야에서 공지된 다양한 용매를 사용할 수 있으며, 예를 들어, N-메틸-2-피롤리돈(NMP), 감마-부티로락톤(GBL) 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc) 또는 테트라하이드로퓨란(THF) 등을 사용할 수 있으나, 이에 제한되는 것은 아니다.After the fluorine-based polymer is dissolved in a polar solvent, a monomer having an alkylene oxide group and a crosslinkable functional group may be mixed in a solution in which the fluorine-based polymer is dissolved. The solvent may be any of various solvents known in the art, and examples thereof include N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone (GBL) dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), and the like, but the present invention is not limited thereto.

상기 혼합 용액에 추가적으로 촉매 및 리간드를 용매와 함께 혼합할 수 있다.In addition to the mixed solution, the catalyst and the ligand can be mixed together with the solvent.

상기 촉매는 예를 들어, Cu(Ⅱ)Cl2, Cu(Ⅱ)Br2, Cu(Ⅱ)I2, Fe(Ⅱ)Cl2, Fe(Ⅲ)Cl3 또는 이들의 혼합물 등이 예시될 수 있으나, 바람직하게는 Cu(Ⅱ)Cl2, Cu(Ⅱ)Br2, Cu(Ⅱ)I2 또는 이들의 혼합물이 예시될 수 있고, 더욱 바람직하게는 Cu(Ⅱ)Cl2를 사용할 수 있다.The catalysts include, for example, Cu (Ⅱ) Cl 2, Cu (Ⅱ) Br 2, Cu (Ⅱ) I 2, Fe (Ⅱ) Cl 2, Fe (Ⅲ) Cl 3 or mixtures thereof may be exemplified Cu (II) Cl 2 , Cu (II) Br 2 , Cu (II) I 2 or a mixture thereof can be exemplified, and more preferably Cu (II) Cl 2 can be used.

또한, 상기 촉매의 함량은 전체 조성물 100 중량부 대비 0.001 내지 1 중량부, 0.005 내지 0.75 중량부 또는 0.01 내지 0.5 중량부일 수 있다. 상기 촉매의 함량이 0.001 중량부 미만인 경우 반응속도가 매우 지체되고, 1 중량부 초과인 경우 중합된 공중합체의 분자량이 지나치게 낮아질 수 있는 문제가 있으므로 상기 범위에서 적절히 선택한다. 또한, 상기 촉매는 동일 기술 분야에서 공지된 다양한 형태의 촉매를 사용할 수 있다. 예를 들어, 파우더, 와이어 또는 메쉬 등의 형태일 수 있으나, 이에 제한되는 것은 아니다.The content of the catalyst may be 0.001 to 1 part by weight, 0.005 to 0.75 part by weight or 0.01 to 0.5 part by weight based on 100 parts by weight of the total composition. When the content of the catalyst is less than 0.001 part by weight, the reaction rate is very retarded. When the amount of the catalyst is more than 1 part by weight, the molecular weight of the polymerized copolymer may be excessively low. In addition, the catalysts can use various types of catalysts known in the art. For example, it may be in the form of powder, wire or mesh, but is not limited thereto.

상기 리간드는 상기 촉매와 결합하여 중합 반응에 사용될 수 있는 것이라면 특별히 제한되지 않는다.The ligand is not particularly limited as long as it can be used in the polymerization reaction by binding with the catalyst.

일례로, 상기 리간드는 σ-결합을 통하여 촉매와 배위할 수 있는 질소, 산소, 인 및 황 원자를 1개 이상 갖는 리간드 또는 π-결합을 통하여 촉매와 배위할 수 있는 2개 이상의 탄소 원자를 함유하는 리간드 등이 예시될 수 있으나, 이에 제한되지 않으며, 구체적으로는 TPMA(tris(2-pyridylmethyl)amine) 리간드를 사용할 수 있다.For example, the ligand may contain a ligand having at least one nitrogen, oxygen, phosphorus and sulfur atom capable of coordinating with the catalyst via a sigma-bond, or a ligand containing at least two carbon atoms capable of coordinating with the catalyst through a [ But is not limited thereto. Specifically, TPMA (tris (2-pyridylmethyl) amine) ligand can be used.

상기 리간드의 함량은, 상기 촉매 100 중량부 대비 100 내지 2000 중량부, 150 내지 1000 중량부 또는 200 내지 500 중량부일 수 있다. 상기 리간드의 함량이 100 중량부 미만인 경우 촉매와의 결합에 의한 금속복합체 형성이 너무 적어 반응이 매우 느리거나 진행되지 않으며, 2000 중량부 초과인 경우 제조 원가의 상승하고, 과량의 리간드 사용으로 인한 발색이 나타나는 문제가 있다.The content of the ligand may be 100 to 2000 parts by weight, 150 to 1000 parts by weight or 200 to 500 parts by weight based on 100 parts by weight of the catalyst. If the content of the ligand is less than 100 parts by weight, the formation of the metal complex due to the bond with the catalyst is so small that the reaction does not proceed very slowly or progresses. When the amount exceeds 2,000 parts by weight, the production cost rises, There is a problem that appears.

ATRP 반응의 촉매, 리간드, 라디칼 개시제를 혼합하여 50 내지 70 ℃에서 교반하면, ATRP 반응이 일어나 그라프팅 된 고분자를 수득할 수 있다. 본 발명의 일 구현예에 따른 고분자는 하기 화학식 2와 같은 PVDF-co-(PCTFE-g-(PEGMA-co-HEMA))일 수 있다.When the ATRP reaction catalyst, the ligand and the radical initiator are mixed and stirred at 50 to 70 ° C, an ATRP reaction occurs to obtain a grafted polymer. The polymer according to an embodiment of the present invention may be PVDF-co- (PCTFE-g- (PEGMA-co-HEMA)) as shown in the following Chemical Formula 2.

[화학식 2](2)

Figure PCTKR2018008244-appb-I000004
Figure PCTKR2018008244-appb-I000004

(상기 화학식 2에서 q, n, p, m 및 o는 각각 독립적으로 0≤q≤20,000, 1≤n≤22,000, 2≤p≤230, 1≤m≤200 및 2≤o≤50 의 정수이다)Q, n, p, m and o each independently represent an integer of 0? Q? 20,000, 1? N? 22,000, 2? P? 230, 1? M? 200 and 2? )

상기 그라프팅 중합 반응을 진행한 이후에 생성된 고분자를 에테르 용매에 담가 미반응 단량체를 제거하는 단계를 더 거칠 수도 있다. 그 이후 상기 고분자를 진공 조건에서 건조시키는 단계를 거쳐 젤 형태의 고분자 전해질 조성물을 수득할 수 있다.The step of immersing the polymer produced in the graft polymerization reaction in an ether solvent to remove unreacted monomers may be further performed. Thereafter, the polymer is dried under vacuum conditions to obtain a gel-type polymer electrolyte composition.

고체 전해질의 제조방법Method for producing solid electrolyte

본 발명에 따른 전해질은 상기 고체 전해질 조성물에 전술한 다관능 가교제를 총 고분자 내에 존재하는 가교 관능기 대비 1:1~1:0.01 몰비로 투입하고 용매에 녹여 1 내지 6시간 동안 교반하는 단계를 포함할 수 있다. 이후 상기 용액을 테플론 판에 캐스팅 한 후 50 내지 150 ℃에서 열처리 과정을 거쳐 고분자를 가교시켜 필름 형태로 제조할 수 있다. 상기 테플론 판을 진공 조건에서 3일 동안 건조 시킨 후, 테플론 판에서 고체 필름을 떼어내면 리튬 이차전지용 고분자 고체 전해질이 형성된다.In the electrolyte according to the present invention, the polyfunctional crosslinking agent described above is added to the solid electrolyte composition at a molar ratio of 1: 1 to 1: 0.01, relative to the crosslinking functional groups present in the total polymer, dissolved in a solvent and stirred for 1 to 6 hours . The solution may then be cast on a Teflon plate and heat treated at 50-150 ° C to crosslink the polymer to form a film. After drying the Teflon plate under vacuum condition for 3 days, the solid film is removed from the Teflon plate to form a polymer solid electrolyte for a lithium secondary battery.

이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나 본 발명에 따른 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예에 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예는 당업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되는 것이다.BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

제조예 1. ATRP법에 의해 그라프팅 공중합된 PVDF-co-(PCTFE-g-(PEGMA-co-HEMA)의 제조(A1)Production Example 1. Preparation of PVDF-co- (PCTFE-g- (PEGMA-co-HEMA) Grafted Copolymerized by ATRP Method (A1)

1000ml 플라스크에 불소계 중합체로 중량 평균 분자량(이하 Mw) 600,000의 P(VDF-co-CTFE) 10g, 중합하고자 하는 단량체인 PEGMA 116g 및 HEMA 3.35g을 용매 Acetone 450ml에 넣고 질소 조건하에서 1시간 교반하였다.10 g of P (VDF-co-CTFE) having a weight average molecular weight (Mw) of 600,000 as a fluorine polymer, 116 g of PEGMA as a monomer to be polymerized and 3.35 g of HEMA were placed in a 1000 ml flask and stirred in a solvent Acetone for 450 minutes.

그 후 ATRP 반응 촉매로 CuCl2 0.00266g, 리간드로 TPMA 0.0091g, 개시제로 Sn(EH)2 (Tin(II) 2-ethylhexanoate) 0.245g을 상기 플라스크에 투입한 후 질소 조건하에서 30시간 교반하여 ATRP 반응을 진행하였다.Thereafter, 0.00266 g of CuCl 2, 0.0091 g of TPMA as a ligand and 0.245 g of Sn (EH) 2 (Tin (II) 2-ethylhexanoate) as an initiator were added to the flask and stirred under nitrogen for 30 hours to obtain ATRP The reaction proceeded.

반응을 완료한 후, 생성된 고분자를 에테르 용매에 3회 담가 반응에 참여하지 않은 단량체를 제거하였다. 최종적으로 얻은 고분자를 진공 조건에서 1주일 건조시켜, 젤 형태의 PVDF-co-(PCTFE-g-(PEGMA-co-HEMA) 고분자를 수득하였다.After completion of the reaction, the resulting polymer was immersed in an ether solvent three times to remove unreacted monomers. The finally obtained polymer was dried under vacuum for 1 week to obtain PVDF-co- (PCTFE-g- (PEGMA-co-HEMA) polymer in gel form.

제조예 2. ATRP법에 의해 그라프팅 공중합된 PVDF-co-(PCTFE-g-(PEGMA-co-HEMA)의 제조(A2)Production Example 2 (Preparation of PVDF-co- (PCTFE-g- (PEGMA-co-HEMA) (A2) Grafted Copolymerized by ATRP Method [

1000ml 플라스크에 불소계 중합체로 중량 평균 분자량(이하 Mw) 600,000의 P(VDF-co-CTFE) 10g, 중합하고자 하는 단량체인 PEGMA 54g 및 HEMA 1.5g을 용매 Acetone 300ml에 넣고 질소 조건하에서 1시간 교반하였다. 10 g of P (VDF-co-CTFE) having a weight average molecular weight (Mw) of 600,000 as a fluorine polymer, 54 g of PEGMA as a monomer to be polymerized and 1.5 g of HEMA were placed in a 1000 ml flask and stirred in a solvent Acetone for 300 minutes.

그 후 ATRP 반응 촉매로 CuCl2 0.002g, 리간드로 TPMA 0.0051g, 개시제로 Sn(EH)2 0.231g을 상기 플라스크에 투입한 후 질소 조건하에서 30시간 교반하여 ATRP 반응을 진행하였다. Then, 0.002 g of CuCl 2 , 0.0051 g of TPMA as a ligand, and 0.231 g of Sn (EH) 2 as an initiator were added to the flask, and the mixture was stirred under a nitrogen atmosphere for 30 hours to conduct an ATRP reaction.

반응을 완료한 후, 생성된 고분자를 에테르 용매에 3회 담가 반응에 참여하지 않은 단량체를 제거하였다. 최종적으로 얻은 고분자를 진공 조건에서 1주일 건조시켜, 젤 형태의 PVDF-co-(PCTFE-g-(PEGMA-co-HEMA) 고분자를 수득하였다.After completion of the reaction, the resulting polymer was immersed in an ether solvent three times to remove unreacted monomers. The finally obtained polymer was dried under vacuum for 1 week to obtain PVDF-co- (PCTFE-g- (PEGMA-co-HEMA) polymer in gel form.

비교 제조예 1. P(VDF-co-CTFE) 단독 사용한 고분자의 제조 (B1)Comparative Preparation Example 1. Preparation of P (VDF-co-CTFE) singly used polymer (B1)

상기 제조예 1 및 2에서 단량체인 PEGMA 및 HEMA를 그라프팅 공중합 하지 않은 중량 평균 분자량(이하 Mw) 600,000의 단독의 P(VDF-co-CTFE) 고분자를 제조하였다.P (VDF-co-CTFE) polymer having a weight average molecular weight (Mw) of 600,000 without grafting copolymerization of PEGMA and HEMA as monomers was prepared in Preparation Examples 1 and 2.

비교 제조예 2. P(VDF-co-CTFE)를 사용하지 않은 고분자의 제조 (B2)Comparative Preparation Example 2. Preparation of polymer without use of P (VDF-co-CTFE) (B2)

상시 제조예 1 및 2에서 주쇄로 P(VDF-co-CTFE)를 사용하지 않고 PEGMA와 HEMA를 9:1의 몰비로 중합한 중량 평균 분자량(이하 Mw) 230,000의 고분자를 제조하였다.A polymer having a weight average molecular weight (Mw) of 230,000 obtained by polymerizing PEGMA and HEMA in a molar ratio of 9: 1 without using P (VDF-co-CTFE) as a main chain in the preparation examples 1 and 2 was prepared.

상기 제조예 1 내지 2 및 비교 제조예 1 내지 2를 하기 표 1에 나타내었다.The above Production Examples 1 to 2 and Comparative Production Examples 1 to 2 are shown in Table 1 below.

실험 예 - 유리전이온도 및 HTm 측정Experimental Example - Measurement of Glass Transition Temperature and H Tm

측정 장비: DSC discovery 250 (TA instruments 社)Measuring equipment: DSC discovery 250 (TA instruments)

측정 조건: 20 ℃ 내지 100 ℃(1st cycle), -90 ℃ 내지 200 ℃(2nd cycle), 10 ℃/min, N2 atmMeasurement conditions: 20 캜 to 100 캜 (1st cycle), -90 캜 to 200 캜 (2nd cycle), 10 캜 / min, N 2 atm

상기 제조예 1 및 2, 비교 제조예 1 및 2에서 제조된 고분자를 각각 10 mg을 취하여 상기 DSC 샘플 팬에 담고 장비의 cell에 주입하였다. 위의 온도조건에서 측정한 뒤, 온도와 열용량의 그래프에서부터 기울기가 변하는 부분의 변곡점을 잡아 유리전이온도(Tg)로 측정하였다. 온도와 열용량의 그래프에서 유리전이온도 후에 또 한번의 흡열 peak가 나타나는데 이 지점이 Tm(녹는점)이며, Tm이 나타나는 peak의 넓이를 HTm으로 측정하였다. HTm이 크다는 것은 결정이 녹기 위해 많은 에너지가 필요하다는 뜻으로 HTm이 클수록 고분자의 결정성이 큰 것을 의미한다.10 mg of each of the polymers prepared in Preparative Examples 1 and 2 and Comparative Preparative Examples 1 and 2 was taken in the DSC sample pan and injected into the cell of the instrument. After measuring at the above temperature, the inflection point of the portion where the slope was changed from the graph of the temperature and the heat capacity was measured and the glass transition temperature (T g ) was measured. In the graph of temperature and heat capacity, another endothermic peak appears after the glass transition temperature. This point is Tm (melting point), and the width of the peak at which Tm appears is measured by H Tm . The large H Tm means that a large amount of energy is needed to melt the crystal, and the larger the H Tm , the greater the crystallinity of the polymer.

고분자Polymer P(VDF-co-CTFE) :PEGMA : HEMA(mol비)P (VDF-co-CTFE): PEGMA: HEMA (molar ratio) 고분자 내불소계 함량Fluorine content in polymer Mw(PDI)Mw (PDI) 유리전이온도(Tg, ℃)Glass transition temperature (Tg, ° C) HTm(J/g)H Tm (J / g) A1A1 1 : 13.5 : 1.51: 13.5: 1.5 10%10% 180만 (6.7)1.8 million (6.7) -64-64 0.58 0.58 A2A2 1 : 6.3 : 0.71: 6.3: 0.7 25%25% 101만 (5.7)101 (5.7) -58-58 4.28 4.28 B1B1 1: 0 : 01: 0: 0 100%100% 60만 (-)600,000 (-) -25-25 16.18 16.18 B2B2 0 : 9 : 10: 9: 1 0%0% 23만 (3.2)23 (3.2) -73-73 --

(PDI: 분산도)(PDI: dispersion degree)

실시예 - 고체 전해질의 제조Example - Preparation of Solid Electrolyte

상기 제조예 1 및 2에서 제조된 고분자 PVDF-co-(PCTFE-g-(PEGMA-co-HEMA) 5g, 다관능 가교제로 3관능 톨루엔 디이소시아네이트, 리튬염으로 LiTFSI의 함량을 하기 표 2와 같이 달리하여 테트라하이드로퓨란(이하 THF)용매 50ml에 용해시킨 용액을 6시간 동안 교반하여 균일한 용액을 제조하였다. 상기 용액을 2cm x 2cm 사이즈의 테플론 판에 캐스팅한 후 dry room에서 6시간 상온 건조한 뒤, 120 ℃ 온도에서 1시간동안 가열해 열경화 반응을 진행하였다. 그 후, 칼을 사용하여 고체 필름을 상기 테플론 판으로부터 떼어내어 이차전지용 고체 전해질을 수득하였다.5 g of the polymer PVDF-co- (PCTFE-g- (PEGMA-co-HEMA) prepared in Preparation Examples 1 and 2, the content of LiTFSI as a trifunctional toluene diisocyanate and the lithium salt as a polyfunctional crosslinking agent, (THF) solvent was stirred for 6 hours to prepare a homogeneous solution. The solution was cast on a 2 cm x 2 cm Teflon plate, dried in a dry room for 6 hours at room temperature , And heated at 120 DEG C for 1 hour to perform a thermal curing reaction. Then, a solid film was detached from the Teflon plate using a knife to obtain a solid electrolyte for a secondary battery.

비교예 - 고체 전해질의 제조Comparative Example - Preparation of Solid Electrolyte

상기 비교 제조예 1 및 2에서 제조된 고분자 5g, 다관능 가교제로 3관능 톨루엔 디이소시아네이트, 리튬염으로 LiTFSI의 함량을 하기 표 2와 같이 달리하여 THF용매 50ml에 용해시킨 용액을 6시간 동안 교반하여 균일한 용액을 제조하였다. 상기 용액을 2cm x 2cm 사이즈의 테플론 판에 캐스팅한 후 dry room에서 6시간 상온 건조한 뒤, 120℃ 온도에서 1시간 동안 가열해 열경화 반응을 진행하였다. 그 후, 칼을 사용하여 고체 필름을 상기 테플론 판으로부터 떼어내어 이차전지용 고체 전해질을 수득하였다. A solution prepared by dissolving 5 g of the polymer prepared in Comparative Preparation Examples 1 and 2, difunctional toluene diisocyanate as a polyfunctional crosslinking agent and LiTFSI as a lithium salt in 50 ml of THF solvent as shown in Table 2 was stirred for 6 hours A uniform solution was prepared. The solution was cast in a 2 cm x 2 cm Teflon plate, dried in a dry room at room temperature for 6 hours, and then heated at 120 ° C for 1 hour to effect a thermal curing reaction. Thereafter, the solid film was detached from the Teflon plate using a knife to obtain a solid electrolyte for a secondary battery.

실시예 1 내지 5 및 비교예 1 내지 6을 하기 표 2에 나타내었다.Examples 1 to 5 and Comparative Examples 1 to 6 are shown in Table 2 below.

고분자Polymer LiTFSI 함량(wt%)LiTFSI content (wt%) 다관능 가교제 함량A Polyfunctional crosslinking agent content A 실시예1Example 1 A1A1 2020 1 : 0.51: 0.5 실시예2Example 2 A1A1 3030 1 : 0.51: 0.5 실시예3Example 3 A1A1 4040 1 : 0.51: 0.5 실시예4Example 4 A1A1 5050 1 : 0.51: 0.5 실시예5Example 5 A2A2 4040 1 : 0.51: 0.5 비교예1Comparative Example 1 B1B1 3030 -- 비교예2Comparative Example 2 B1B1 4040 -- 비교예3Comparative Example 3 B2B2 3030 1 : 0.51: 0.5 비교예4Comparative Example 4 B2B2 2020 1 : 11: 1 비교예5Comparative Example 5 B2B2 3030 1 : 11: 1 비교예6Comparative Example 6 B2B2 4040 1 : 11: 1

(A: 고분자 내 가교성 관능기 : 다관능 가교제 내 가교성 관능기 (mol비))(A: crosslinkable functional group in polymer: crosslinkable functional group (mol ratio) in polyfunctional crosslinking agent)

실험예 - 전해질의 이온전도도 측정Experimental Example - Measurement of ionic conductivity of electrolyte

상기 실시예 1 내지 5 및 비교예 1 내지 6에서 제조된 고체 전해질의 이온전도도는 그 임피던스를 측정한 뒤 하기 수학식 1을 이용하여 구하였다. The ion conductivities of the solid electrolytes prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were measured using the following Equation 1 after measuring the impedance thereof.

측정을 위해 일정한 넓이와 두께를 가지는 상기 고체 전해질의 필름 샘플을 준비하였다. 판상의 샘플 양면에 이온 차단 전극 (ion blocking electrode)으로 전자 전도성이 우수한 서스(SUS) 기판을 접촉시킨 후 샘플 양면의 전극을 통하여 교류전압을 인가하였다. 이 때, 인가되는 조건으로 측정 주파수 0.1Hz 내지 10MHz의 진폭 범위로 설정하였다. 측정된 임피던스 궤적의 반원이나 직선이 실수축과 만나는 교점 (Rb) 로부터 벌크 전해질의 저항을 구하고 샘플의 넓이와 두께로부터 고분자 고체 전해질막의 이온 전도도를 계산하여 하기 표 3에 나타내었다.A film sample of the solid electrolyte having a certain width and thickness was prepared for measurement. An SUS substrate having excellent electron conductivity was brought into contact with an ion blocking electrode on both sides of a plate-shaped sample, and an AC voltage was applied through the electrodes on both sides of the sample. At this time, the amplitude of the measurement frequency was set to 0.1 Hz to 10 MHz under the applied conditions. The resistance of the bulk electrolyte was obtained from the intersection point (R b ) where the semicircle or the straight line of the measured impedance trajectory meets the real axis, and the ionic conductivity of the polymer solid electrolyte membrane was calculated from the width and thickness of the sample.

[수학식 1] [Equation 1]

Figure PCTKR2018008244-appb-I000005
Figure PCTKR2018008244-appb-I000005

σ: 이온전도도σ: ion conductivity

Rb: 임피던스 궤적이 실수축과의 교점R b : Impedance trajectory intersects the real axis

A: 샘플의 넓이A: Width of sample

t: 샘플의 두께t: thickness of the sample

Film 형성 여부Whether the film is formed 이온전도도(S/cm)Ion conductivity (S / cm) 실시예1Example 1 OO 2.7 x 10-7 2.7 x 10 -7 실시예2Example 2 OO 1.9 x 10-6 1.9 x 10 -6 실시예3Example 3 OO 3.2 x 10-5 3.2 x 10 -5 실시예4Example 4 OO 4.5 x 10-5 4.5 x 10 -5 실시예5Example 5 OO 2.4 x 10-5 2.4 x 10 -5 비교예1Comparative Example 1 OO 8.5 x 10-7 8.5 x 10 -7 비교예2Comparative Example 2 OO 2.1 x 10-6 2.1 x 10 -6 비교예3Comparative Example 3 XX 2.7 x 10-5 2.7 x 10 -5 비교예4Comparative Example 4 OO 3.5 x 10-6 3.5 x 10 -6 비교예5Comparative Example 5 OO 6.7 x 10-6 6.7 x 10 -6 비교예6Comparative Example 6 OO 9.8 x 10-7 9.8 x 10 -7

상기 표 3에서 보듯이, 그라프팅 되지 않은 비교예에 비해 불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 고분자를 포함하는 이차전지용 고체 전해질의 이온전도도가 높게 측정되어 이온전도도가 향상되었음을 알 수 있었다. 비교예 3의 경우에는 이온전도도는 높지만 본 발명에 따른 전해질막이 형성되지 않음을 알 수 있었다.As shown in Table 3, in comparison with the non-grafted comparative example, the ionic conductivity of a solid electrolyte for a secondary battery including a polymer grafted with an alkylene oxide and a monomer containing a crosslinking functional group on a fluorine polymer was measured to be high, It was found that the conductivity was improved. In the case of Comparative Example 3, it was found that the ionic conductivity was high, but the electrolyte membrane according to the present invention was not formed.

Claims (15)

불소계 중합체 상에 알킬렌 옥사이드 및 가교성 관능기를 포함하는 단량체가 그라프팅 된 고분자를 포함하는 이차전지용 고체 전해질 조성물.A solid electrolyte composition for a secondary battery, comprising a fluorine-based polymer on which an alkylene oxide and a monomer containing a crosslinkable functional group are grafted. 제1항에 있어서,The method according to claim 1, 상기 불소계 중합체는 하기 화학식 1의 구조를 포함하는 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the fluorine-based polymer has a structure represented by the following formula (1). [화학식 1][Chemical Formula 1]
Figure PCTKR2018008244-appb-I000006
Figure PCTKR2018008244-appb-I000006
 (상기 화학식 1에서 p,q,r 은 각각 독립적으로 0≤p≤20,000, 1≤q≤22,000 및 0≤r≤15,000의 정수이다)(Wherein p, q and r each independently represent an integer of 0? P? 20,000, 1? Q? 22,000 and 0? R? 15,000) 제1항에 있어서,The method according to claim 1, 상기 그라프팅 된 고분자는 하기 화학식 2의 구조를 포함하는 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the grafted polymer comprises a structure represented by the following formula (2). [화학식 2](2)
Figure PCTKR2018008244-appb-I000007
Figure PCTKR2018008244-appb-I000007
 (상기 화학식 2에서 q, n, p, m 및 o는 각각 독립적으로 0≤q≤20,000, 1≤n≤22,000, 2≤p≤230, 1≤m≤200 및 2≤o≤50 의 정수이다)Q, n, p, m and o each independently represent an integer of 0? Q? 20,000, 1? N? 22,000, 2? P? 230, 1? M? 200 and 2? ) 제1항에 있어서,The method according to claim 1, 상기 알킬렌 옥사이드는 에틸렌 옥사이드 또는 프로필렌 옥사이드인 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the alkylene oxide is ethylene oxide or propylene oxide. 제1항에 있어서,The method according to claim 1, 상기 가교성 관능기는 하이드록시기, 카복실기 및 이소시아네이트기로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the crosslinkable functional group is any one selected from the group consisting of a hydroxyl group, a carboxyl group and an isocyanate group. 제1항에 있어서,The method according to claim 1, 상기 단량체는 알킬렌 옥사이드와 가교성 관능기를 99.5:0.5 내지 80:20의 몰비로 포함하는 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the monomer comprises an alkylene oxide and a crosslinkable functional group in a molar ratio of 99.5: 0.5 to 80:20. 제1항에 있어서,The method according to claim 1, 상기 불소계 중합체는 전체 조성물 100 중량부 대비 0.2 내지 40 중량부로 포함되는 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the fluoropolymer is contained in an amount of 0.2 to 40 parts by weight based on 100 parts by weight of the total composition. 제1항에 있어서,The method according to claim 1, 상기 조성물은 상기 가교성 관능기와 반응할 수 있는 관능기를 2개 이상 가지는 다관능 가교제를 추가로 포함하는 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the composition further comprises a polyfunctional crosslinking agent having two or more functional groups capable of reacting with the crosslinkable functional group. 제8항에 있어서,9. The method of claim 8, 상기 다관능 가교제는 이소시아네이트 가교제, 에폭시 가교제, 아지리딘 가교제 및 금속 킬레이트 가교제로 이루어진 군에서 선택되는 어느 하나인 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the polyfunctional crosslinking agent is any one selected from the group consisting of an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. 제8항에 있어서,9. The method of claim 8, 상기 다관능 가교제는 전체 전해질 조성물 100 중량부 대비 0.1 내지 6 중량부로 포함되는 것을 특징으로 하는 이차전지용 고체 전해질 조성물.Wherein the polyfunctional crosslinking agent is contained in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the total electrolyte composition. 제1항 내지 제10항 중 어느 한 항의 이차전지용 고체 전해질 조성물을 열경화하여 형성되는 이차전지용 고체 전해질.A solid electrolyte for a secondary battery formed by thermally curing a solid electrolyte composition for a secondary battery according to any one of claims 1 to 10. 제11항에 있어서,12. The method of claim 11, 상기 전해질은 그 두께가 50 내지 400 ㎛인 것을 특징으로 하는 이차전지용 고체 전해질.Wherein the electrolyte has a thickness of 50 to 400 占 퐉. 제11항에 있어서,12. The method of claim 11, 상기 전해질은 상기 전해질 조성물 100 중량부 대비 30 내지 70 중량부의 리튬염을 더 포함하는 것을 특징으로 하는 이차전지용 고체 전해질.Wherein the electrolyte further comprises 30 to 70 parts by weight of a lithium salt based on 100 parts by weight of the electrolyte composition. 제13항에 있어서,14. The method of claim 13, 상기 리튬염은 LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiTFSI, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, (CF3SO2)2NLi, LiN(SO2F)2, 클로로 보란 리튬, 저급 지방족 카르본산 리튬, 4-페닐 붕산 리튬 및 리튬 이미드로 이루어지는 군에서 선택되는 1종 이상인 것을 특징으로 하는 이차전지용 고체 전해질.The lithium salt is LiCl, LiBr, LiI, LiClO 4 , LiBF 4, LiB 10 Cl 10, LiPF 6, LiCF 3 SO 3, LiTFSI, LiCF 3 CO 2, LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li , At least one selected from the group consisting of (CF 3 SO 2 ) 2 NLi, LiN (SO 2 F) 2 , chloroborane lithium, lithium lower aliphatic carboxylate, lithium 4-phenylborate and lithium imide Solid electrolytes for batteries. 제11항에 있어서,12. The method of claim 11, 상기 전해질은 이온전도도가 1 X 10-6 S/cm 내지 4 X 10-5 S/cm 인 것을 특징으로 하는 이차전지용 고체 전해질.Wherein the electrolyte has an ionic conductivity of 1 X 10 < -6 > S / cm to 4 X 10 < -5 > S / cm.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021507464A (en) * 2018-07-27 2021-02-22 エルジー・ケム・リミテッド Polymer for electrode protection layer and secondary battery to which this is applied
CN113113671A (en) * 2021-04-12 2021-07-13 清华大学深圳国际研究生院 Polyvinylidene fluoride-based solid electrolyte, preparation method thereof and lithium ion battery
CN113993920A (en) * 2019-08-08 2022-01-28 株式会社Lg新能源 Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery comprising the same
US20220340702A1 (en) * 2019-08-08 2022-10-27 Lg Energy Solution, Ltd. Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery which include the same
US20230178802A1 (en) * 2020-05-01 2023-06-08 Daikin Industries, Ltd. Composite, polymer electrolyte, electrochemical device, polymer-based solid-state battery, and actuator
CN119275369A (en) * 2024-12-11 2025-01-07 帕瓦(诸暨)固态钠能有限公司 A method for preparing a solid-state battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010033974A1 (en) * 1999-12-20 2001-10-25 Patrik Gavelin Polymer electrolyte, a battery cell comprising the electrolyte and method of producing the electrolyte
US20050170255A1 (en) * 2002-10-03 2005-08-04 Daikin Industries, Ltd. Solid electrolyte comprising fluorine-containing polymer having fluorine-containing ether chains
KR20050092722A (en) * 2002-12-25 2005-09-22 다이킨 고교 가부시키가이샤 Solid electrolyte containing fluoropolymer having fluorinated ether chain
KR100796989B1 (en) 2006-09-20 2008-01-22 연세대학교 산학협력단 Hydrogen ion conductive crosslinked fluorine copolymer electrolyte membrane
KR100796990B1 (en) 2006-09-20 2008-01-22 연세대학교 산학협력단 Branched fluorinated copolymer electrolyte membrane with hydrophilic and sulfonated groups
KR20170118035A (en) 2014-11-24 2017-10-24 테크닙 이 앤드 씨 리미티드 Process for preparing ethene
KR20180080139A (en) 2017-01-02 2018-07-11 황창훈 Framed large size plane type evaporation source apparatus

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010033974A1 (en) * 1999-12-20 2001-10-25 Patrik Gavelin Polymer electrolyte, a battery cell comprising the electrolyte and method of producing the electrolyte
US20050170255A1 (en) * 2002-10-03 2005-08-04 Daikin Industries, Ltd. Solid electrolyte comprising fluorine-containing polymer having fluorine-containing ether chains
KR20050092722A (en) * 2002-12-25 2005-09-22 다이킨 고교 가부시키가이샤 Solid electrolyte containing fluoropolymer having fluorinated ether chain
KR100796989B1 (en) 2006-09-20 2008-01-22 연세대학교 산학협력단 Hydrogen ion conductive crosslinked fluorine copolymer electrolyte membrane
KR100796990B1 (en) 2006-09-20 2008-01-22 연세대학교 산학협력단 Branched fluorinated copolymer electrolyte membrane with hydrophilic and sulfonated groups
KR20170118035A (en) 2014-11-24 2017-10-24 테크닙 이 앤드 씨 리미티드 Process for preparing ethene
KR20180080139A (en) 2017-01-02 2018-07-11 황창훈 Framed large size plane type evaporation source apparatus

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
GAVELIN, P. ET AL.: "Amphiphilic Polymer Gel Electrolytes. 3. Influence of the Ionophobic-ionophilic Balance on the Ion Conductive Properties", ELECTROCHIMICA ACTA, vol. 46, 2001, pages 1439 - 1446, XP004231549, DOI: doi:10.1016/S0013-4686(00)00737-4 *
GAVELIN, P. ET AL.: "Amphiphilic Solid Polymer Electrolytes", SOLID STATE IONICS, vol. 147, 2002, pages 325 - 332, XP004347366, DOI: doi:10.1016/S0167-2738(02)00020-6 *
See also references of EP3664210A4 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7044883B2 (en) 2018-07-27 2022-03-30 エルジー エナジー ソリューション リミテッド Polymer for electrode protective layer and secondary battery to which it is applied
EP3716377A4 (en) * 2018-07-27 2021-05-05 Lg Chem, Ltd. ELECTRODE PROTECTIVE LAYER POLYMER AND SECONDARY BATTERY TO WHICH THIS IS APPLIED
US11518836B2 (en) 2018-07-27 2022-12-06 Lg Energy Solution, Ltd. Electrode protective layer polymer and secondary battery to which same is applied
JP2021507464A (en) * 2018-07-27 2021-02-22 エルジー・ケム・リミテッド Polymer for electrode protection layer and secondary battery to which this is applied
US20220340702A1 (en) * 2019-08-08 2022-10-27 Lg Energy Solution, Ltd. Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery which include the same
JP2022540359A (en) * 2019-08-08 2022-09-15 エルジー エナジー ソリューション リミテッド Copolymer for polymer electrolyte, gel polymer electrolyte containing the same, and lithium secondary battery
CN113993920A (en) * 2019-08-08 2022-01-28 株式会社Lg新能源 Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery comprising the same
CN113993920B (en) * 2019-08-08 2024-03-26 株式会社Lg新能源 Copolymer for polymer electrolyte, gel polymer electrolyte including the same, and lithium secondary battery
JP7463009B2 (en) 2019-08-08 2024-04-08 エルジー エナジー ソリューション リミテッド Copolymer for polymer electrolyte, gel polymer electrolyte containing same and lithium secondary battery
US12374719B2 (en) 2019-08-08 2025-07-29 Lg Energy Solution, Ltd. Copolymer for polymer electrolyte, and gel polymer electrolyte and lithium secondary battery which include the same
US20230178802A1 (en) * 2020-05-01 2023-06-08 Daikin Industries, Ltd. Composite, polymer electrolyte, electrochemical device, polymer-based solid-state battery, and actuator
US12512512B2 (en) * 2020-05-01 2025-12-30 Daikin Industries, Ltd. Polymer electrolyte including amorphous fluorine-containing elastomer and alkali metal salt, electrochemical device, polymer-based solid-state battery, and actuator including the same
CN113113671A (en) * 2021-04-12 2021-07-13 清华大学深圳国际研究生院 Polyvinylidene fluoride-based solid electrolyte, preparation method thereof and lithium ion battery
CN119275369A (en) * 2024-12-11 2025-01-07 帕瓦(诸暨)固态钠能有限公司 A method for preparing a solid-state battery

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