WO2019022522A1 - Électrolyte polymère pour batterie secondaire et batterie secondaire au lithium le comprenant - Google Patents

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

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Publication number
WO2019022522A1
WO2019022522A1 PCT/KR2018/008450 KR2018008450W WO2019022522A1 WO 2019022522 A1 WO2019022522 A1 WO 2019022522A1 KR 2018008450 W KR2018008450 W KR 2018008450W WO 2019022522 A1 WO2019022522 A1 WO 2019022522A1
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Prior art keywords
polymer electrolyte
polymer
weight
formula
poly
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English (en)
Korean (ko)
Inventor
박솔지
안경호
이철행
한준혁
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020180086713A external-priority patent/KR102657448B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18839191.6A priority Critical patent/EP3605705B1/fr
Priority to US16/610,592 priority patent/US12278335B2/en
Priority to CN201880026669.4A priority patent/CN110574209B/zh
Publication of WO2019022522A1 publication Critical patent/WO2019022522A1/fr
Anticipated expiration legal-status Critical
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a polymer electrolyte for a secondary battery and a lithium secondary battery comprising the polymer electrolyte.
  • the lithium secondary battery can be divided into a lithium ion battery using a liquid electrolyte and a lithium polymer battery using a polymer electrolyte according to an applied electrolyte.
  • the solid or gel polymer electrolyte exhibits a lower ionic conductivity than the liquid electrolyte, which is not suitable for commercialization.
  • polyethylene oxide which is widely used as a polymer electrolyte
  • the cation of the alkali metal salt is stabilized while forming a complex by coordination bond with the oxygen atoms present in the polyethylene oxide, And can exist in a stable ion state.
  • the polyethylene oxide has a semi-crystalline structure at room temperature, it interferes with the movement of the dissociated metal salt. As a result, it has a low ion conductivity value of about 1.0 x 10 -8 S / cm at room temperature, and not only the energy characteristic is reduced but also the mechanical properties are lowered, which is not suitable for commercialization.
  • the present invention provides a polymer electrolyte for a secondary battery, which has improved mechanical strength and improved ion transport capability.
  • the present invention also provides a polymer electrolyte composition for forming the polymer electrolyte for a secondary battery.
  • the present invention also provides a method for manufacturing a secondary battery using the polymer electrolyte for a secondary battery.
  • the present invention also provides a lithium secondary battery improved in electrochemical stability at high voltage and high temperature, which is produced by the above method.
  • a first polymer comprising a repeating unit represented by the following formula (1);
  • a second polymer comprising repeating units derived from monomers having at least one ethylenically unsaturated group or an oligomer thereof,
  • first polymer and the second polymer form a semi-interpenetrating polymer network (semi-IPN) structure.
  • R & lt ; 1 &gt is an alkylene group having 1 to 5 carbon atoms
  • n is an integer of 10 to 10,000.
  • the first polymer may include at least one selected from the group consisting of repeating units represented by the following general formulas (1a) to (1c).
  • n 1 is an integer of 10 to 10,000.
  • n 2 is an integer of 10 to 10,000.
  • n 3 is an integer of 10 to 10,000.
  • the second polymer may be at least one selected from the group consisting of polyacetylene, polyethylene, polypropylene, polystyrene, poly (p-phenylene), polythiophene, polypyrrole, poly (p- phenylene sulfide) Poly (vinylidene chloride), poly (vinylidene chloride), poly (vinylidene chloride), poly (vinylidene fluoride), poly (Polyether sulfone), poly (ether ether ketone), polyamideimide, and polyvinylene fluoride, from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene oxide, polyphenylene oxide, polyether sulfone, polyarylate, And may include at least one selected.
  • the second polymer may be included in an amount of 1 part by weight to 100 parts by weight based on 100 parts by weight of the first polymer.
  • the polymer electrolyte includes a lithium salt, and may be contained in the polymer electrolyte for the secondary battery at a concentration of 0.5M to 5M.
  • the polymer electrolyte of the present invention may be a free-standing solid polymer electrolyte.
  • a first polymer comprising a repeating unit represented by the following formula (1);
  • a composition for a polymer electrolyte of the present invention comprising a polymerization initiator is provided.
  • R & lt ; 1 &gt is an alkylene group having 1 to 5 carbon atoms
  • n is an integer of 10 to 10,000.
  • the monomer having an ethylenically unsaturated group may be at least one monomer selected from the group consisting of acetylene, ethylene, propylene, styrene, p-phenylene, thiophene, pyrrole, p-phenylene sulfide, p- Vinylidene chloride, methyl methacrylate, ethylene terephthalate, butylene terephthalate, ethylene oxide, phenylene oxide, ether sulfone, aryl ether, ether ketone, vinyl chloride, acrylonitrile, vinyl acetate, An amide imide, and vinylene fluoride.
  • the first polymer comprising the repeating unit represented by Formula 1 may be contained in an amount of 50 to 95 wt% based on the total weight of the reactants in the polymer electrolyte composition.
  • the monomer having an ethylenically unsaturated group or its oligomer may be included in an amount of 1 part by weight to 100 parts by weight based on 100 parts by weight of the first polymer containing the repeating unit represented by the formula (1).
  • composition for a polymer electrolyte may further include an oxygen inhibitor (O 2 inhibitor), and the oxygen inhibitor may be included in an amount of 0.1 wt% to 10 wt% based on the total weight of the composition for a polymer electrolyte.
  • O 2 inhibitor oxygen inhibitor
  • the present invention also provides a method for preparing a polymer electrolyte for a secondary battery.
  • a polymer electrolyte formed on at least one surface of the anode and the cathode, wherein the polymer electrolyte is capable of providing a lithium secondary battery comprising the polymer electrolyte for a secondary battery of the present invention.
  • the present invention relates to a first polymer comprising a repeating unit represented by formula (1); And a second polymer containing a repeating unit derived from a monomer having at least one ethylenic unsaturated group, it is possible to secure an excellent mechanical strength and to maintain the ion transfer ability inherent to the poly (alkylene carbonate)
  • the polymer electrolyte for a secondary battery can be produced. Also, by including it, a lithium secondary battery having enhanced electrochemical stability at high voltage and high temperature can be manufactured.
  • the weight average molecular weight (Mw) can be measured by Gel Permeation Chromatography (GPC).
  • GPC Gel Permeation Chromatography
  • the GPC measurement system alliance 4 apparatus is stabilized.
  • the chromatogram can be obtained by injecting the standard and sample samples into the instrument and then calculating the molecular weight according to the analytical method (system: Alliance 4, column: Ultrahydrogel linear ⁇ 2, eluent: 0.1M NaNO 3 7.0 phosphate buffer, flow rate: 0.1 mL / min, temp: 40 ° C, injection: 100 ⁇ L).
  • the ion conductivity can be measured using an alternating current impedance measurement method.
  • the ionic conductivity can be measured at frequencies ranging from 1 MHz to 0.01 Hz using a VMP3 measuring instrument and 4294A.
  • the electrochemical (oxidation) stability of a secondary battery was measured at 60 ° C using a linear sweep voltammetry (LSV) using a potentiostat (EG & G, model 270A) .
  • the electrolyte specimens prepared through ASTM standard D638 (Type V specimens) were measured at a rate of 5 mm / min at 25 ° C and about 30% relative humidity using Lloyd LR-10K.
  • the electrolyte used in the lithium polymer secondary battery can be divided into a gel polymer electrolyte or a solid polymer electrolyte.
  • the gel polymer electrolyte has a disadvantage in that when the plasticizer content is increased to realize a high ion conductivity, the mechanical strength is lowered or the film thickness is difficult to control.
  • the secondary battery including the solid polymer electrolyte since the secondary battery including the solid polymer electrolyte has no leakage of the solution as compared with the secondary battery using the liquid electrolyte as the ion transport medium, reliability and stability of the battery are improved and thinning, simplification of package, have.
  • the solid polymer electrolyte has good processability, it is easy to form a laminated structure with an electrode when it is used in an electrochemical device such as a battery, and a solid polymer electrolyte due to the change in the volume of the electrode due to ion- There is an advantage that the shape of the electrolyte interface can be changed.
  • the secondary battery using the same since the ionic conductivity of the solid polymer electrolyte is relatively low as compared with the gel polymer electrolyte, the secondary battery using the same has a disadvantage that the battery resistance is increased due to the low charging / discharging current density at room temperature.
  • a first polymer comprising a repeating unit represented by the following formula (1);
  • a second polymer comprising repeating units derived from monomers having at least one ethylenically unsaturated group or an oligomer thereof,
  • first polymer and the second polymer form a structure similar to a semi-interpenetrating polymer network (semi-IPN) structure.
  • R & lt ; 1 &gt is an alkylene group having 1 to 5 carbon atoms
  • n is an integer of 10 to 10,000, preferably 50 to 7,000, more preferably 50 to 5,000.
  • the first polymer may include at least one selected from the group consisting of repeating units represented by the following general formulas (1a) to (1c).
  • n 1 is an integer of 10 to 10,000, preferably 50 to 7,000, more preferably 50 to 5,000.
  • n 2 is an integer of 10 to 10,000, preferably 50 to 7,000, more preferably 50 to 5,000.
  • n 3 is an integer of 10 to 10,000, preferably 50 to 7,000, more preferably 50 to 5,000.
  • the first polymer may have a weight average molecular weight (Mw) of 1,000 g / mol to 1,000,000 g / mol, specifically 5,000 g / mol to 700,000 g / mol, more specifically 5,000 g / mol to 500,000 g /
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the first polymer can be measured by Gel Permeation Chromatography (GPC). For example, after a sample of a certain concentration is prepared, the GPC measurement system alliance 4 apparatus is stabilized. Once the instrument is stabilized, the chromatogram can be obtained by injecting standard and sample samples into the instrument and then calculating the molecular weight according to the analytical method (system: Alliance 4, column: Ultrahydrogel linear X 2, eluent: 0.1M NaNO 3 pH 7.0 phosphate buffer, flow rate: 0.1 mL / min, temp: 40 ° C, injection: 100 ⁇ L)
  • the second polymer may be at least one selected from the group consisting of polyacetylene, polyethylene, polypropylene, polystyrene, poly (p-phenylene), polythiophene, polypyrrole, poly (p- phenylene sulfide) Poly (vinylidene chloride), poly (vinylidene chloride), poly (vinylidene chloride), poly (vinylidene fluoride), poly (Polyether sulfone), poly (ether ether ketone), polyamideimide, and polyvinylene fluoride, from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene oxide, polyphenylene oxide, polyether sulfone, polyarylate, And may include at least one selected.
  • the second polymer may be selected from the group consisting of polyacetylene, polystyrene, poly (p-phenylene), polythiophene, polypyrrole, poly (p-phenylene sulfide) Poly (vinylidene chloride), poly (methyl methacrylate), poly (vinylidene chloride), poly (vinylidene chloride), polyaniline, polyisothianaphthalene, polytetrafluoroethylene, poly (vinyl chloride), polyacrylonitrile, At least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polyarylate, poly (ether ether ketone), polyamideimide, and polyvinylene fluoride.
  • the second polymer has a weight average molecular weight (Mw) of 1,000,000 g / mol or less, specifically 1,000 g / mol to 1,000,000 g / mol, more specifically 1,000 g / mol to 700,000 g / mol, To 500,000 g / mol.
  • Mw weight average molecular weight
  • the oxidation potential window of the polymer electrolyte can be increased and the mechanical strength can be ensured to increase the stability under high voltage, it is possible to suppress the occurrence of a short due to melting. Therefore, the physical and electrochemical stability of the lithium secondary battery including the polymer electrolyte can be improved.
  • the weight average molecular weight (Mw) of the second polymer can be measured using gel permeation chromatography (GPC) as described above.
  • the second polymer may be included in an amount of 1 part by weight to 100 parts by weight, specifically 5 parts by weight to 90 parts by weight, more specifically 10 parts by weight to 30 parts by weight, based on 100 parts by weight of the first polymer have.
  • the mechanical strength can be ensured and the electrochemical stability of the secondary battery can be improved by improving the oxidation potential window and ion transporting ability.
  • the first polymer since the first polymer is superior in ion transferring ability to the second polymer, the first polymer should be contained in an amount equal to or greater than that of the second polymer. Due to the network (network) structure of the second polymer, Can be prevented from lowering, and the oxidation potential can be improved.
  • the second polymer is contained in an amount of 1 part by weight or more based on the first polymer, the mechanical strength can be ensured, and cell driving at high voltage and high temperature can be achieved.
  • the polymer matrix structure composed of the first polymer having excellent ion transfer characteristics and the polymer matrix structure composed of the monomer having the ethylenically unsaturated group or the second polymer formed by the cross-linking polymerization of the oligomers thereof are entangled it is possible to further improve the mechanical strength and the oxidation potential window.
  • the polymer electrolyte of the present invention includes a lithium salt, so that the lithium ion transfer characteristic can be improved.
  • the lithium salt includes Li + as a cation and anions such as F - , Cl - , Br - , I - , NO 3 - , N (CN) 2 - , BF 4 - , ClO 4 - , AlO 4 - AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, B (C 2 O 4) 2 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 -, ( CF 3 SO 2) 2 N - , (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 N -, (SF 5) 3 C -, (
  • the lithium salt can be appropriately changed within a usable range.
  • the lithium salt may be contained in the polymer electrolyte in a concentration of 0.5M to 5M, specifically 0.5M to 3M have.
  • the polymer electrolyte of the present invention may be a free-standing solid polymer electrolyte formed by mixing a first polymer, a second polymer, and optionally a lithium salt.
  • the ionic conductivity of such a solid polymer electrolyte may be 3.0 ⁇ 10 -5 S / cm to 3.0 ⁇ 10 -4 S / cm, specifically 3.0 ⁇ 10 -5 S / cm to 2.5 ⁇ 10 -4 S / cm.
  • the ionic conductivity can be measured using an alternating current impedance measurement method.
  • the ionic conductivity can be measured at frequencies ranging from 1 MHz to 0.01 Hz using a VMP3 measuring instrument and 4294A.
  • a first polymer comprising a repeating unit represented by the following formula (1);
  • composition for a polymer electrolyte of the present invention containing a polymerization initiator can be provided.
  • R & lt ; 1 &gt is an alkylene group having 1 to 5 carbon atoms
  • n is an integer of 10 to 10,000, preferably 50 to 7,000, more preferably 50 to 5,000.
  • the first polymer comprising the repeating unit represented by Formula 1 includes a first polymer, a monomer having an ethylenic unsaturated group, and a polymerization initiator in a composition for a polymer electrolyte Based on the total weight of the reactants to be reacted, in an amount of from 50 wt% to 95 wt%, more specifically 70 wt% to 92 wt%. If the amount of the first polymer is 50% by weight or more, the polymer electrolyte can be formed more easily, and the polymer electrolyte having better mechanical strength and ion transfer characteristics can be realized. When the amount of the first polymer is 95% by weight or less, deterioration of the ion transporting effect due to the excess polymer is prevented, and battery performance deterioration at high temperature and high voltage can be prevented.
  • the monomer having an ethylenically unsaturated group is a polymerizable compound.
  • Typical examples thereof include acetylene, ethylene, propylene, styrene, p-phenylene, thiophene, , p-phenylene sulfide, p-phenylenevinylene, thienylenevinylene, aniline, isothianaphthalene, tetrafluoroethylene, vinyl chloride, acrylonitrile, vinyl acetate (VAc), vinylidene chloride, methyl methacryl (MMA), at least one compound selected from the group consisting of ethylene terephthalate, butylene terephthalate, ethylene oxide, phenylene oxide, ether sulfone, arylate, ether ether ketone, amideimide, and vinylene fluoride can do.
  • the oligomer composed of the monomer having an ethylenically unsaturated group may be an oligomer having a weight average molecular weight (Mw) of 100 g / mol to 5,000 g / mol, specifically 200 g / mol to 1,000 g / mol.
  • Mw weight average molecular weight
  • the oxidation stability and the mechanical strength are improved without significantly lowering the ionic conductivity by a stronger crosslinking structure .
  • the weight average molecular weight (Mw) of the oligomer can be measured by Gel Permeation Chromatography (GPC). For example, after a sample of a certain concentration is prepared, the GPC measurement system alliance 4 apparatus is stabilized. Once the instrument is stabilized, the chromatogram can be obtained by injecting standard and sample samples into the instrument and then calculating the molecular weight according to the analytical method (system: Alliance 4, column: Ultrahydrogel linear X 2, eluent: 0.1M NaNO 3 pH 7.0 phosphate buffer, flow rate: 0.1 mL / min, temp: 40 ° C, injection: 100 ⁇ L)
  • the monomer having an ethylenically unsaturated group or its oligomer is added in an amount of 1 part by weight to 100 parts by weight, specifically 5 parts by weight to 90 parts by weight, more specifically 10 parts by weight To 30 parts by weight.
  • the mechanical strength can be secured and the ion transport capability can be improved.
  • a composition for a polymer electrolyte comprising a first polymer containing a repeating unit represented by the formula (1) and a monomer having at least one ethylenic unsaturated group or an oligomer thereof ,
  • a semi-interpenetrating polymer network is intermixed with the first polymer, the second polymer comprising a crosslinked structure realized by cross-linking polymerization of the ethylenically unsaturated monomer or its oligomers, IPN (interpenetrating polymer network)) structure.
  • the first polymer existing in the polymer electrolyte and the second polymer do not form a three-dimensional network by chemical bonding with each other, that is, they are not crosslinked, and the free polymer of the polymer matrix composed of the first polymer volume of the second polymer forms a supplementary polymer network structure, it can compensate for the weak durability of the polymer matrix composed of the first polymer.
  • the battery can be driven in the form of an all solid-ion battery.
  • the organic solvent in which the lithium salt is dissolved can minimize decomposition due to an oxidation reaction or the like during charging / discharging of the secondary battery, There is no restriction as long as it can demonstrate.
  • a low boiling point volatile organic solvent or a nonvolatile organic solvent can be used.
  • Typical examples thereof include N, N'-dimethylacetamide, N-methyl-2-pyrrolidone ), Dimethylsulfoxide (DMSO), N, N-dimethylformamide (DMF), acetonitrile (AN), propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), fluoroethylene carbonate (FEC), gamma-butyrolactone (GBL), 1,2-dimethoxyethane, tetrahydroxyfuran, But are not limited to, tetrahydrofuran (THF), dimethylsulfoxide, 1,3-dioxolane (DOL), 1,4-dioxane, formamide, dimethylformamide, dioxolane, acetonitrile, , Methyl formate (EA), ethyl propionate (EP), methyl acetate (MA), methyl propionate (
  • the organic solvent preferably includes an organic solvent having a low boiling point, such as acetonitrile, or an organic solvent having excellent volatility such as N-methyl-2-pyrrolidone, for easy removal.
  • an organic solvent having a low boiling point such as acetonitrile
  • an organic solvent having excellent volatility such as N-methyl-2-pyrrolidone
  • the organic solvent may be nonvolatile such as tetraglyme to maintain the shape of the solid-liquid hybrid polymer electrolyte by swelling the polymer electrolyte well. It is preferable that an organic solvent is used.
  • the amount of the organic solvent to be used is not particularly limited as long as it is an amount capable of easily dissolving the monomer having the first polymer and the ethylenic unsaturated group.
  • the amount of the organic solvent is 100 parts by weight to 10,000 parts by weight, the organic solvent can be easily removed, the mechanical strength of the polymer electrolyte due to the residual organic solvent can be prevented, and the composition for a polymer electrolyte can be uniformly applied So that uniformity of the film can be ensured in forming the polymer electrolyte membrane.
  • a polymer electrolyte having a polymer matrix structure composed of a second polymer formed by cross-linking between monomers having an ethylenically unsaturated group is formed between polymer matrices composed of a first polymer by using a polymerization reaction using a conventionally known polymerization initiator Can be prepared.
  • the polymerization initiator may be at least one selected from the group consisting of a UV polymerization initiator, a photopolymerization initiator, and a thermal polymerization initiator, which is a conventional polymerization initiator known in the art.
  • UV polymerization initiator examples include 2-hydroxy-2-methylpropiophenone, 1-hydroxy-cyclohexylphenyl-ketone, benzophenone, 2-hydroxy- Phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, (2-hydroxyethoxy) ethyl ester, alpha-dimethoxy-alpha-phenylacetophenone, 2-benzyl- 2- (dimethylamino) -1- [4- (4-morpholinyl) (2, 4, 6-trimethylbenzoyl) -phosphine, 2-methyl-1- [4- (methylthio) phenyl] -2- Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (eta 5-2,4-cyclopentadien-1-yl), bis [2,6-difluoro-3- 1-yl) phenyl] titanium, 4-isobutyl
  • the photopolymerization initiator or the thermal polymerization initiator may be exemplified by benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert-butylperoxide, butyl peroxide, t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide and hydrogen peroxide, 2-ethylhexanoate, Azobis (isobutyronitrile) (AIBN; 2,2'-azobis (2-cyanobutane), 2'-azobis and at least one selected from the group consisting of iso-butyronitrile and 2,2'-azobisdimethyl-valeronitrile (AMVN).
  • benzoyl peroxide acetyl peroxide, dilauryl peroxide, di-tert-butylperoxide, butyl peroxide, t-butyl peroxy-2-ethyl-hexano
  • the polymerization initiator may be decomposed by heat in UV or 30 ° C to 100 ° C in a battery or decomposed by light at a room temperature (5 ° C to 30 ° C) to generate free radicals, and by the free radical polymerization, Crosslinking between monomers having an ethylenic unsaturated group is formed and a polymer electrolyte can be formed.
  • the polymerization initiator may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the monomer having an ethylenic unsaturated group.
  • the polymerization initiator is contained in an amount of 10 parts by weight or less, it is possible to control the polymerization rate in the polymer electrolyte, and the disadvantage that the unreacted polymerization initiator remains and adversely affects battery performance can be prevented.
  • the polymerization initiator is contained in an amount of 0.1 part by weight or more, the polymerization reaction between monomers having an ethylenically unsaturated group is smoothly carried out, so that a polymer electrolyte having a uniform thickness can be produced.
  • the oxygen inhibitor may include tris (2,2,2-trifluoroethyl) phosphite as a representative example thereof.
  • the oxygen inhibitor may be contained in an amount of 0.1 wt% to 10 wt% based on the total weight of the composition for a polymer electrolyte.
  • the oxygen inhibitor may be contained in an amount of 0.1 wt% to 10 wt% based on the total weight of the composition for a polymer electrolyte.
  • the secondary battery of the present invention may be manufactured by forming a polymer electrolyte according to a conventional solution casting method known in the art.
  • the polymer electrolyte composition of the present invention is directly coated (applied) on at least one side of the prepared negative electrode, positive electrode and separator, and then dried and cured to form a free- A secondary battery including a polymer electrolyte can be produced.
  • the composition for a polymer electrolyte of the present invention is cast on a support substrate such as a glass substrate, PET (polyethylene terephthalate), Teflon, or FEP film (casting film formation) to form a coating film Separating the polymer electrolyte membrane formed from the supporting substrate, placing the separated polymer electrolyte membrane on at least one side of the prepared negative electrode, positive electrode, and separating membrane, drying (removing organic solvent)
  • a support substrate such as a glass substrate, PET (polyethylene terephthalate), Teflon, or FEP film (casting film formation) to form a coating film
  • a support substrate such as a glass substrate, PET (polyethylene terephthalate), Teflon, or FEP film (casting film formation) to form a coating film Separating the polymer electrolyte membrane formed from the supporting substrate, placing the separated polymer electrolyte membrane on at least one side of the prepared negative electrode, positive electrode, and separating membrane, drying (removing organic solvent)
  • the polymer electrolyte comprises the polymer electrolyte of the present invention.
  • the polymer electrolyte may be a free-standing solid polymer electrolyte.
  • the thickness of the membrane-type polymer electrolyte may be about 0.5 ⁇ to 300 ⁇ in consideration of ion conductivity.
  • the thickness of the polymer electrolyte is 0.5 mu m or more, mechanical strength can be secured.
  • the thickness is 300 mu m or less, a proton (H + ) as an ion transporter can easily pass through the secondary battery, Performance secondary battery can be manufactured.
  • the lithium secondary battery of the present invention may further include a separator if necessary.
  • the positive electrode and the negative electrode constituting the lithium secondary battery of the present invention can be manufactured and used by a conventional method.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on the positive electrode current collector.
  • the positive electrode mixture layer may be formed by coating a positive electrode slurry containing a positive electrode active material, a binder, a conductive material and a solvent on a positive electrode collector, followed by drying and rolling.
  • the positive electrode collector is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the positive electrode collector may be formed of a metal such as carbon, stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode active material is a compound capable of reversibly intercalating and deintercalating lithium, and may specifically include a lithium composite metal oxide including lithium and at least one metal such as cobalt, manganese, nickel, or aluminum have. More specifically, the lithium composite metal oxide may be at least one selected from the group consisting of lithium-manganese-based oxides (for example, LiMnO 2 and LiMn 2 O 4 ), lithium-cobalt oxides (for example, LiCoO 2 ), lithium- (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.
  • LiMnO 2 and LiMn 2 O 4 lithium-cobalt oxides
  • LiCoO 2 lithium-
  • lithium-manganese-cobalt oxide e. g., (in which LiCo 1-Y2 Mn Y2 O 2 , 0 ⁇ Y2 ⁇ 1), LiMn 2-z1 Co z1 O 4 ( here, 0 ⁇ z1 ⁇ 2) and the like
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (for example, Li (Ni 1/3 Mn 1/3 Co 1 / 3 ) O 2 , Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 , Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2, Li (Ni 0.7 Mn 0.15 Co 0.15) O 2 and Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 ), or lithium nickel cobalt aluminum oxide (e.g., Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.) and the like.
  • lithium nickel cobalt aluminum oxide e.g., Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.
  • the cathode active material may be contained in an amount of 80% by weight to 99% by weight based on the total weight of solids in the cathode slurry.
  • the binder is a component that assists in bonding of the active material to the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the solid content in the positive electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene (Ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM tetrafluoroethylene
  • EPDM tetrafluoroethylene
  • EPDM sulfonated EPDM
  • the conductive material is usually added in an amount of 1% by weight to 30% by weight based on the total weight of the solid content in the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the conductive material include carbon black, acetylene black (or denka black), ketjen black, channel black, furnace black, lamp black, Or carbon black such as thermal black; Graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that provides a preferable viscosity when the positive electrode active material and optionally a binder and a conductive material are included.
  • NMP N-methyl-2-pyrrolidone
  • the solid content in the slurry containing the positive electrode active material, and optionally the binder and the conductive material may be in the range of 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the negative electrode may be manufactured by forming a negative electrode mixture layer on the negative electrode collector.
  • the negative electrode material mixture layer may be formed by coating an anode current collector with a negative electrode slurry including a negative electrode active material, a binder, a conductive material, and a solvent, followed by drying and rolling.
  • the anode current collector generally has a thickness of 3 to 500 mu m.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • Examples of the negative electrode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used.
  • fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
  • the negative electrode active material may be a lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, lithium capable of doping and dedoping lithium Materials, and transition metal oxides.
  • the carbonaceous material capable of reversibly intercalating / deintercalating lithium ions is not particularly limited as long as it is a carbonaceous anode active material generally used in a lithium ion secondary battery.
  • the carbonaceous material include crystalline carbon, Amorphous carbon or any combination thereof.
  • the crystalline carbon include graphite such as natural graphite or artificial graphite in the form of amorphous, plate-like, flake, spherical or fiber, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.
  • the metal or an alloy of these metals and lithium may be selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, And Sn, or an alloy of these metals and lithium may be used.
  • metal composite oxide is PbO, PbO 2, Pb 2 O 3, Pb 3 O 4, Sb 2 O 3, Sb 2 O 4, Sb 2 O 5, GeO, GeO 2, Bi 2 O 3, Bi 2 O 4 , Bi 2 O 5 , Li x Fe 2 O 3 (0? X? 1), Li x WO 2 (0? X? 1), and Sn x Me 1-x Me y y z , Pb, Ge, Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, Halogen: 0 ⁇ x? 1; 1? Y? May be used.
  • Si As the material capable of doping and dedoping lithium, Si, SiO x (0 ⁇ x? 2), Si-Y alloy (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element and an element selected from the group consisting of combinations thereof, and not Sn), and at least one of them may be mixed with SiO 2 .
  • Si-Y alloy Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si
  • Sn, SnO 2 Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element
  • the element Y may be at least one element selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Se, Te, Po, and combinations thereof.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be contained in an amount of 80% by weight to 99% by weight based on the total weight of the solid content in the negative electrode slurry.
  • the binder is a component that assists in bonding between the conductive material, the active material and the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the solid content in the negative electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various copolymers thereof.
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of the solid content in the negative electrode slurry.
  • Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the conductive material examples include carbon black, acetylene black (or denka black), ketjen black, channel black, furnace black, lamp black, Or carbon black such as thermal black; Graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include water or an organic solvent such as NMP, alcohol, etc., and may be used in an amount in which the negative electrode active material and, optionally, a binder, a conductive material, and the like are contained in a desired viscosity.
  • the slurry containing the negative electrode active material and, optionally, the binder and the conductive material may be contained to have a solid concentration of 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the separation membrane blocks the internal short circuit of both electrodes and impregnates the electrolyte.
  • the separation membrane composition is prepared by mixing a polymer resin, a filler and a solvent, and then the separation membrane composition is directly coated on the electrode and dried Or may be formed by casting and drying the separation membrane composition on a support, and then laminating the separation membrane film peeled off from the support on the electrode.
  • the separator may be a porous polymer film commonly used, such as a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer
  • the polymer film may be used alone or as a laminate thereof, or may be a nonwoven fabric made of a conventional porous nonwoven fabric, for example, glass fiber of high melting point, polyethylene terephthalate fiber or the like, but is not limited thereto.
  • the pore diameter of the porous separation membrane is generally 0.01 to 50 ⁇ m, and the porosity may be 5 to 95%.
  • the thickness of the porous separator may be generally in the range of 5 to 300 mu m.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but can be variously applied, such as a cylindrical shape, a square shape, a pouch shape, or a coin shape, depending on the purpose to be performed.
  • the lithium secondary battery according to an embodiment of the present invention may be a pouch type secondary battery.
  • NMP N-methyl-2-pyrrolidone
  • the cathode active material slurry was coated on the surface of an aluminum (Al) thin film having a thickness of 20 ⁇ to a thickness of 10 ⁇ and then dried to prepare a cathode plate.
  • Lithium metal was coated on the Cu thin film and then rolled to prepare a negative electrode plate having a thickness of 20 mu m.
  • the cathode active material composition was coated on at least one surface of the anode plate, dried, and then cured by UV curing to prepare a solid polymer electrolyte membrane having a thickness of 50 ⁇ (see Table 1 below).
  • An electrode assembly was manufactured through a polyolefin-based separator (thickness: 20 ⁇ ⁇ ) between the cathode and the anode including the polymer electrolyte.
  • a polymer electrolyte membrane and a pouch-type secondary battery comprising the polymer electrolyte membrane were prepared in the same manner as in Example 1, except that methyl methacrylate (MMA) was used instead of the vinyl acetate in the preparation of the polymer electrolyte See Table 1).
  • MMA methyl methacrylate
  • a polymer electrolyte membrane and a pouch-type secondary battery comprising the same were prepared in the same manner as in Example 1 except that 20 g of the vinyl acetate was used in the production of the polymer electrolyte (see Table 1 below).
  • a polymer electrolyte membrane and a pouch-type secondary battery including the polymer electrolyte membrane were prepared in the same manner as in Example 4, except that 20 g of styrene was used instead of the vinyl acetate in the production of the polymer electrolyte (see Table 1 below).
  • a polymer electrolyte membrane and a pouch-type secondary battery including the polymer electrolyte membrane were prepared in the same manner as in Example 1 except that the vinyl acetate (VAc) was not included in the preparation of the polymer electrolyte (see Table 1 below) .
  • VAc vinyl acetate
  • a polymer electrolyte membrane and a pouch-type secondary battery including the polymer electrolyte membrane were prepared in the same manner as in Example 1 except that the first polymer was not included in the preparation of the polymer electrolyte (see Table 1 below).
  • the first polymer A monomer having an ethylenically unsaturated group for forming a second polymer or an oligomer thereof The second polymer Oxygen inhibitor
  • the Molecular Weight Content (g) designation Content (g) designation Content (g) (g) (g) Example 1 1a 50,000 100 VAc 10 - - - Example 2 1a 50,000 100 MMA 10 - - - Example 3 1a 50,000 100 VAc 20 - - - Example 4 1b 100,000 100 VAc 10 - - - Example 5 1b 100,000 100 Styrene 20 - - - Example 6 1c 5,000 100 VAc 30 - - - Example 7 1a 50,000 100 VAc 10 - - One Example 8 1a 50,000 100 VAc oligomer 10 One Comparative Example 1 1a 50,000 100 - - - - Comparative Example 2 - - - VAc 10 - - - Comparative Example 3 PEO 100,000 100 VAc 10 - - - Comparative Example 4 1a
  • the secondary batteries manufactured in Examples 1 to 8 of the present invention showed an oxidation starting voltage at about 5.1 V or more, indicating excellent electrochemical (oxidation) stability.
  • the specimens were prepared using the polymer electrolyte compositions of Examples 1 to 8 and the polymer electrolyte compositions of Comparative Examples 1, 3 and 4, and then the tensile strengths of the specimens were measured.
  • the specimens were fabricated collectively through ASTM standard D638 (Type V specimens) and tensile strength was measured using Lloyd LR-10K at a rate of 5 mm per minute at 25 ° C and 30% relative humidity. The results are shown in Table 3 below.
  • Example 1 8.7
  • Example 2 6.6
  • Example 3 12.4
  • Example 4 9.1
  • Example 5 15.4
  • Example 6 18.0
  • Example 7 9.2
  • Example 8 16.5 Comparative Example 1 4.2 Comparative Example 3 5.2 Comparative Example 4 3.8
  • the tensile strengths of the polymer electrolytes prepared in Comparative Examples 1, 3 and 4 were 5.2 MPa or less in most cases, while the tensile strengths of the polymer electrolytes prepared in Examples 1 to 8 were 6.6 MPa or more . Furthermore, when the oligomer was used as the compound having an ethylenically unsaturated group for forming the second polymer, the tensile strength was improved as compared with the polymer electrolyte prepared in Example 7 to which the monomer was applied.
  • the polymer electrolyte prepared according to Examples 1 to 8 of the present invention has improved mechanical strength.
  • a gold (Au) electrode was coated on the polymer electrolyte membrane prepared in Examples 1 to 8 and the polymer electrolyte membrane prepared in Comparative Examples 1 to 3 using a sputter method in a circular shape with a diameter of 1 mm, And the measurement was performed using the alternating current impedance measurement method.
  • the ionic conductivity was measured using a VMP3 measuring instrument and 4294A at a frequency band of 100 MHz to 0.1 Hz. The measurement results are shown in Table 4 below.
  • Example 1 25 1.5 x 10 -4
  • Example 2 25 1.2 ⁇ 10 -4
  • Example 3 25 9.1 ⁇ 10 -5
  • Example 4 25 8.5 ⁇ 10 -5
  • Example 5 25 4.6 ⁇ 10 -5
  • Example 6 25 3.8 ⁇ 10 -5
  • Example 7 25 2.2 x 10 -4
  • Example 8 25 2.0 x 10 -4 Comparative Example 1 25 1.5 x 10 -4 Comparative Example 2 25 1.6 ⁇ 10 -5 Comparative Example 3 25 2.8 x 10 -5
  • Example 7 the polymer electrolyte prepared in Example 1, Example 7, and Example 8 has improved ionic conductivity as compared to the polymer electrolyte of Comparative Example 2 and Comparative Example 3.
  • the polymer electrolyte of Comparative Example 1 contains a polymer network composed only of the first polymer, the electrochemical stability and the tensile strength, etc. of the polymer electrolyte prepared in Examples 2 to 6 are deteriorated Able to know.

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Abstract

La présente invention concerne un électrolyte polymère pour une batterie secondaire et une batterie secondaire au lithium le comprenant et, spécifiquement, un électrolyte polymère pour une batterie secondaire, l'électrolyte polymère comprenant : un premier polymère comprenant une unité de répétition représentée par la formule chimique 1 ci-dessous; et un second polymère comprenant une unité de répétition dérivée d'un monomère ayant au moins un groupe insaturé à base d'éthylène ou un oligomère de celui-ci, et une batterie secondaire au lithium le comprenant.
PCT/KR2018/008450 2017-07-26 2018-07-26 Électrolyte polymère pour batterie secondaire et batterie secondaire au lithium le comprenant Ceased WO2019022522A1 (fr)

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EP18839191.6A EP3605705B1 (fr) 2017-07-26 2018-07-26 Électrolyte polymère pour batterie secondaire et batterie secondaire au lithium l'incluant
US16/610,592 US12278335B2 (en) 2017-07-26 2018-07-26 Polymer electrolyte for secondary battery and lithium secondary battery including the same
CN201880026669.4A CN110574209B (zh) 2017-07-26 2018-07-26 用于二次电池的聚合物电解质和包括该聚合物电解质的锂二次电池

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