WO2019054622A1 - Composition d'électrolyte solide de batterie secondaire et électrolyte solide préparé à partir de celle-ci - Google Patents

Composition d'électrolyte solide de batterie secondaire et électrolyte solide préparé à partir de celle-ci Download PDF

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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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polymer
solid electrolyte
crosslinking agent
electrolyte
secondary battery
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PCT/KR2018/008244
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English (en)
Korean (ko)
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권수지
윤정애
윤성수
김경오
채종현
이연주
김대일
김루시아
곽종헌
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주식회사 엘지화학
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Priority claimed from KR1020180080139A external-priority patent/KR102183663B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18856085.8A priority Critical patent/EP3664210B1/fr
Priority to CN201880057969.9A priority patent/CN111095654B/zh
Priority to ES18856085T priority patent/ES2976141T3/es
Priority to JP2020514998A priority patent/JP6976422B2/ja
Priority to US16/646,982 priority patent/US11417909B2/en
Publication of WO2019054622A1 publication Critical patent/WO2019054622A1/fr

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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

La présente invention concerne : une composition d'électrolyte solide de batterie secondaire au lithium dans laquelle un oxyde d'alkylène et un monomère contenant un groupe fonctionnel de réticulation sont greffés sur un polymère à base de fluor; et un électrolyte solide de batterie secondaire formé par thermodurcissement de la composition. La présente invention peut fournir un électrolyte solide de batterie secondaire ayant une conductivité ionique et une stabilité électrochimique considérablement améliorées, par copolymérisation par greffage d'un oxyde d'alkylène et d'un monomère contenant un groupe fonctionnel de réticulation sur un polymère à base de fluor ayant une conductivité ionique au lithium élevée.
PCT/KR2018/008244 2017-09-14 2018-07-20 Composition d'électrolyte solide de batterie secondaire et électrolyte solide préparé à partir de celle-ci WO2019054622A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP18856085.8A EP3664210B1 (fr) 2017-09-14 2018-07-20 Composition d'électrolyte solide de batterie secondaire et électrolyte solide préparé à partir de celle-ci
CN201880057969.9A CN111095654B (zh) 2017-09-14 2018-07-20 二次电池固体电解质组合物和由其制备的固体电解质
ES18856085T ES2976141T3 (es) 2017-09-14 2018-07-20 Composición de electrolito sólido para batería secundaria y electrolito sólido preparada a partir de la misma
JP2020514998A JP6976422B2 (ja) 2017-09-14 2018-07-20 二次電池用固体電解質組成物及びこれより製造された固体電解質
US16/646,982 US11417909B2 (en) 2017-09-14 2018-07-20 Secondary battery solid electrolyte composition and solid electrolyte prepared therefrom

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KR20170118035 2017-09-14
KR10-2018-0080139 2018-07-10
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Cited By (3)

* Cited by examiner, † Cited by third party
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JP2021507464A (ja) * 2018-07-27 2021-02-22 エルジー・ケム・リミテッド 電極保護層用高分子及びこれを適用した二次電池
CN113113671A (zh) * 2021-04-12 2021-07-13 清华大学深圳国际研究生院 一种聚偏氟乙烯基固态电解质、其制备方法及锂离子电池
CN113993920A (zh) * 2019-08-08 2022-01-28 株式会社Lg新能源 用于聚合物电解质的共聚物以及包括该共聚物的凝胶聚合物电解质和锂二次电池

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JP2021507464A (ja) * 2018-07-27 2021-02-22 エルジー・ケム・リミテッド 電極保護層用高分子及びこれを適用した二次電池
EP3716377A4 (fr) * 2018-07-27 2021-05-05 Lg Chem, Ltd. Polymère de couche de protection d'électrode et batterie secondaire à laquelle celui-ci est appliqué
JP7044883B2 (ja) 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 電極保護層用高分子及びこれを適用した二次電池
US11518836B2 (en) 2018-07-27 2022-12-06 Lg Energy Solution, Ltd. Electrode protective layer polymer and secondary battery to which same is applied
CN113993920A (zh) * 2019-08-08 2022-01-28 株式会社Lg新能源 用于聚合物电解质的共聚物以及包括该共聚物的凝胶聚合物电解质和锂二次电池
JP2022540359A (ja) * 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 高分子電解質用共重合体、これを含むゲルポリマー電解質及びリチウム二次電池
CN113993920B (zh) * 2019-08-08 2024-03-26 株式会社Lg新能源 用于聚合物电解质的共聚物以及包括该共聚物的凝胶聚合物电解质和锂二次电池
JP7463009B2 (ja) 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 高分子電解質用共重合体、これを含むゲルポリマー電解質及びリチウム二次電池
CN113113671A (zh) * 2021-04-12 2021-07-13 清华大学深圳国际研究生院 一种聚偏氟乙烯基固态电解质、其制备方法及锂离子电池

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