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WO2018044129A1 - Électrolyte de polymère de type gel et batterie rechargeable au lithium comprenant celui-ci - Google Patents

Électrolyte de polymère de type gel et batterie rechargeable au lithium comprenant celui-ci Download PDF

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Publication number
WO2018044129A1
WO2018044129A1 PCT/KR2017/009622 KR2017009622W WO2018044129A1 WO 2018044129 A1 WO2018044129 A1 WO 2018044129A1 KR 2017009622 W KR2017009622 W KR 2017009622W WO 2018044129 A1 WO2018044129 A1 WO 2018044129A1
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Prior art keywords
integer
formula
carbon atoms
polymer electrolyte
gel polymer
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PCT/KR2017/009622
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English (en)
Korean (ko)
Inventor
안경호
이정훈
오정우
이철행
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LG Chem Ltd
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LG Chem Ltd
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Priority to EP17847054.8A priority Critical patent/EP3361546B1/fr
Priority to US15/771,773 priority patent/US10714791B2/en
Priority to ES17847054T priority patent/ES2950099T3/es
Priority to PL17847054.8T priority patent/PL3361546T3/pl
Priority to CN201780003933.8A priority patent/CN108352569B/zh
Priority claimed from KR1020170112055A external-priority patent/KR102133384B1/ko
Publication of WO2018044129A1 publication Critical patent/WO2018044129A1/fr
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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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 gel polymer electrolyte and a lithium secondary battery comprising the same.
  • lithium secondary batteries having high energy density and voltage have been commercialized and widely used.
  • the lithium secondary battery may be coated with a positive electrode active material and a negative electrode active material to a current collector with an appropriate thickness, or the active material itself may be formed into a film of an appropriate length, and then wound or laminated together with a separator, which is an insulator, to prepare an electrode assembly. After putting the electrode assembly in a similar container, it is prepared by the process of injecting the electrolyte.
  • Lithium metal oxide is used as the positive electrode active material, and lithium metal, lithium alloy, crystalline or amorphous carbon or carbon composite material is used as the negative electrode active material.
  • a liquid electrolyte particularly an ion conductive liquid electrolyte in which salts are dissolved in a non-aqueous organic solvent, has been mainly used.
  • the gel polymer electrolyte has a disadvantage in that the conductivity of lithium ions is lower than that of a liquid electrolyte composed only of an electrolyte solution.
  • a method of reducing the thickness of the gel polymer electrolyte has been proposed.
  • the first technical problem to be solved by the present invention is to provide a gel polymer electrolyte that can implement a high voltage stability increase and battery resistance reduction effect.
  • a second object of the present invention is to provide a composition for the gel polymer electrolyte.
  • Another object of the present invention is to provide a lithium secondary battery including the gel polymer electrolyte.
  • the matrix polymer provides a gel polymer electrolyte in which a first oligomer including a unit A represented by Formula 1 and a unit B represented by Formula 2 is polymerized to form a three-dimensional network structure.
  • R 1 and R 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • M, n and o are the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500.
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 4 is an alkylene group having 1 to 6 carbon atoms, -CH 2 -R 6 -CH 2- , or -CH 2 -R 7 -OR 8 -CH 2-, wherein R 6 , R 7 and R 8 are at least 1
  • the above acrylate group is a substituted alkylene group having 1 to 3 carbon atoms
  • R 5 is an alkylene group having 1 to 5 carbon atoms or-(CO-R 9 -O-) r -CO-NH-R 10 -NH-CO-O-, wherein R 9 is an alkylene group having 1 to 10 carbon atoms R 10 is an aliphatic, alicyclic or aromatic hydrocarbon group,
  • r is an integer of any one of 0-3.
  • the aliphatic hydrocarbon group is an alkylene group having 1 to 20 carbon atoms; C1-C20 alkylene group containing an isocyanate group (NCO); An alkoxylene group having 1 to 20 carbon atoms; Alkenylene groups having 2 to 20 carbon atoms; Or an alkynylene group having 2 to 20 carbon atoms, wherein the alicyclic hydrocarbon group is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A cycloalkenylene group having 4 to 20 carbon atoms; Or a heterocycloalkylene group having 2 to 20 carbon atoms, wherein the aromatic hydrocarbon group is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms.
  • NCO
  • Unit A represented by Formula 1 may be at least one selected from the group consisting of those represented by Formula 1a to Formula 1c.
  • M, n and o are the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500.
  • Unit B represented by Formula 2 may include at least one selected from the group consisting of those represented by Formulas 2a to 2l.
  • r1 is an integer of any one of 1-3.
  • r2 is an integer of any one of 1-3.
  • r3 is an integer of any one of 1-3.
  • r4 is an integer of any one of 1-3.
  • r5 is an integer of any one of 1-3.
  • r6 is an integer of any one of 1-3.
  • r7 is an integer of any one of 1-3.
  • r8 is an integer of any one of 1-3.
  • the molar ratio of unit A to unit B may be 1:90 to 90: 1.
  • the first oligomer may be a compound represented by the following formula (3).
  • R 1 and R 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 4 is an alkylene group having 1 to 6 carbon atoms, -CH 2 -R 6 -CH 2- , or -CH 2 -R 7 -OR 8 -CH 2-, wherein R 6 , R 7 and R 8 are at least 1
  • the above acrylate group is a substituted alkylene group having 1 to 3 carbon atoms
  • R 5 is an alkylene group having 1 to 5 carbon atoms or-(CO-R 9 -O-) r -CO-NH-R 10 -NH-CO-O-, wherein R 9 is an alkylene group having 1 to 10 carbon atoms R 10 is an aliphatic, alicyclic or aromatic hydrocarbon group,
  • M1, n1, and o1 are the number of repeating units
  • n 1 to 10
  • n1 is an integer of any one of 1 to 10,
  • o1 is an integer of any one of 1 to 500
  • r is an integer of any one of 0-3.
  • the oligomer represented by Formula 3 may be at least one compound selected from the group consisting of compounds represented by Formulas 3a to 3f.
  • n2, o2 are the number of repeat units
  • n2 is an integer of any one of 1 to 10,
  • n2 is an integer of any one of 1 to 10,
  • o2 is an integer of any one of 1-500.
  • n3, n3, and o3 are the number of repeat units
  • n3 is an integer of any one of 1 to 10,
  • n3 is an integer of any one of 1 to 10,
  • o3 is an integer of any one of 1-500.
  • n4, n4, and o4 are the number of repeat units
  • n4 is an integer of any one of 1 to 10,
  • n4 is an integer of any one of 1 to 10,
  • o4 is an integer of any one of 1 to 500
  • r9 is an integer of any one of 1-3.
  • n5 and o5 are the number of repeat units
  • n 1 to 10
  • n5 is an integer of any one of 1 to 10,
  • o5 is an integer of any one of 1 to 500
  • r10 is an integer of any one of 1-3.
  • n6 and o6 are the number of repeat units
  • n 1 to 10
  • n6 is an integer of any one of 1 to 10,
  • o6 is an integer of any one of 1 to 500
  • r11 is an integer of any one of 1-3.
  • n7, n7 and o7 are the number of repeat units
  • n 1 to 10
  • n7 is an integer of any one of 1 to 10,
  • o7 is an integer of any one of 1 to 500,
  • r12 is an integer of any one of 1-3.
  • the gel polymer electrolyte may be methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate.
  • the unit C may be included in less than 50% by weight based on the total content of the first oligomer.
  • the gel polymer electrolyte may further include inorganic particles.
  • Lithium salts Lithium salts, electrolyte solvents, polymerization initiators, and
  • composition for a gel polymer electrolyte of the present invention comprising a first oligomer comprising a unit A represented by the formula (1) and a unit B represented by the formula (2).
  • the first oligomer may be included in an amount of 0.5% to 20% by weight based on the total weight of the composition for gel polymer electrolyte.
  • the gel polymer electrolyte provides a lithium secondary battery including the gel polymer electrolyte of the present invention.
  • the gel polymer electrolyte of the present invention includes a matrix polymer composed of a fluorine-substituted polyether unit and an oligomer including at least one acrylate unit at its end, thereby increasing the degree of freedom of Li ions by anion immobilization and stabilization, thereby improving battery resistance. Higher lithium ion conductivity can be achieved by reducing the effect.
  • a lithium secondary battery having improved stability at high voltage and high temperature may be manufactured.
  • a "repeating unit” means the unit derived from the monomer formed by superposing
  • the repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
  • the gel polymer electrolyte has a high voltage safety and mechanical properties are weak compared to the solid polymer electrolyte, the battery resistance and the resulting ionic conductivity is lower than the liquid electrolyte.
  • studies have been conducted to improve Li + ion conductivity while at the same time securing high voltage stability using a copolymer such as an oligomer.
  • a copolymer such as an oligomer.
  • the oligomeric compound is used, not only is it difficult to control physical properties, but it is difficult to form a uniform polymer in the battery, which makes it difficult to apply to high capacity and large batteries.
  • the present invention has been made to solve these problems by providing a gel polymer electrolyte comprising a matrix polymer formed by oligomer compounds prepared by polymerizing compounds having physical properties that can complement the electrochemical and mechanical properties.
  • the matrix polymer provides a gel polymer electrolyte in which a first oligomer including a unit A represented by Formula 1 and a unit B represented by Formula 2 is polymerized to form a three-dimensional network structure.
  • R 1 and R 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • M, n and o are the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of either 1 or 500.
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 4 is an alkylene group having 1 to 6 carbon atoms, -CH 2 -R 6 -CH 2- , or -CH 2 -R 7 -OR 8 -CH 2-, wherein R 6 , R 7 and R 8 are at least 1
  • the above acrylate group is a substituted alkylene group having 1 to 3 carbon atoms
  • R 5 is an alkylene group having 1 to 5 carbon atoms or-(CO-R 9 -O-) r -CO-NH-R 10 -NH-CO-O-, wherein R 9 is an alkylene group having 1 to 10 carbon atoms R 10 is an aliphatic, alicyclic or aromatic hydrocarbon group,
  • r is an integer of any one of 0-3.
  • the aliphatic hydrocarbon group is an alkylene group having 1 to 20 carbon atoms; C1-C20 alkylene group containing an isocyanate group (NCO); An alkoxylene group having 1 to 20 carbon atoms; Alkenylene groups having 2 to 20 carbon atoms; Or an alkynylene group having 2 to 20 carbon atoms;
  • the alicyclic hydrocarbon group is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A cycloalkenylene group having 4 to 20 carbon atoms; Or a heterocycloalkylene group having 2 to 20 carbon atoms,
  • the aromatic hydrocarbon group is substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms.
  • the first oligomer comprises the unit A derived from a monomer containing a fluorine-substituted ether in the structure, thereby improving the anion stabilization and oxidative safety High voltage safety and battery resistance can be reduced and the ion conductivity can be improved.
  • the unit represented by Formula 1 may be at least one selected from the group consisting of those represented by Formula 1a to Formula 1c as a representative example.
  • M, n and o are the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500, specifically o is an integer of any one of 1 to 100.
  • n, m and o respectively mean the number of repetitions, and the repeating units n, m and o each have a predetermined rule or alternately with no rule. ), Or may be arranged in a graft form or randomly.
  • the first oligomer includes a unit B represented by Chemical Formula 2 in order to improve the mechanical properties by forming a matrix polymer through a polymerization reaction. can do.
  • the unit B represented by Formula 2 may be at least one selected from the group consisting of those represented by Formulas 2a to 2l.
  • r1 is an integer of any one of 1-3.
  • r2 is an integer of any one of 1-3.
  • r3 is an integer of any one of 1-3.
  • r4 is an integer of any one of 1-3.
  • r5 is an integer of any one of 1-3.
  • r6 is an integer of any one of 1-3.
  • r7 is an integer of any one of 1-3.
  • r8 is an integer of any one of 1-3.
  • the first oligomer may include a compound represented by the following Chemical Formula 3 as a representative example.
  • R 1 and R 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 4 is an alkylene group having 1 to 6 carbon atoms, -CH 2 -R 6 -CH 2- , or -CH 2 -R 7 -OR 8 -CH 2-, wherein R 6 , R 7 and R 8 are at least 1
  • the above acrylate group is a substituted alkylene group having 1 to 3 carbon atoms
  • R 5 is an alkylene group having 1 to 5 carbon atoms or-(CO-R 9 -O-) r -CO-NH-R 10 -NH-CO-O-, wherein R 9 is an alkylene group having 1 to 10 carbon atoms R 10 is an aliphatic, alicyclic or aromatic hydrocarbon group,
  • M1, n1, and o1 are the number of repeating units
  • n 1 to 10
  • n1 is an integer of any one of 1 to 10,
  • o1 is an integer of any one of 1 to 500
  • r is an integer of any one of 1-3.
  • the oligomer represented by Chemical Formula 3 may include at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas 3a to 3f as a representative example.
  • n2, o2 are the number of repeat units
  • n2 is an integer of any one of 1 to 10,
  • n2 is an integer of any one of 1 to 10,
  • o2 is an integer of any one of 1-500.
  • n3, n3, and o3 are the number of repeat units
  • n3 is an integer of any one of 1 to 10,
  • n3 is an integer of any one of 1 to 10,
  • o3 is an integer of any one of 1-500.
  • n4, n4, and o4 are the number of repeat units
  • n4 is an integer of any one of 1 to 10,
  • n4 is an integer of any one of 1 to 10,
  • o4 is an integer of any one of 1 to 500
  • r9 is an integer of any one of 1-3.
  • n5 and o5 are the number of repeat units
  • n 1 to 10
  • n5 is an integer of any one of 1 to 10,
  • o5 is an integer of any one of 1 to 500
  • r10 is an integer of any one of 1-3.
  • n6 and o6 are the number of repeat units
  • n 1 to 10
  • n6 is an integer of any one of 1 to 10,
  • o6 is an integer of any one of 1 to 500
  • r11 is an integer of any one of 1-3.
  • n7, n7 and o7 are the number of repeat units
  • n 1 to 10
  • n7 is an integer of any one of 1 to 10,
  • o7 is an integer of any one of 1 to 500,
  • r12 is an integer of any one of 1-3.
  • the ratio of unit B: unit A for forming the matrix polymer in the oligomer is not particularly limited, but specifically, the molar ratio of unit B: unit A is 1:90 to 90: 1 days. Can be.
  • the weight average molecular weight of the oligomer for forming the gel polymer electrolyte of the present invention may be about 1,000 g / mol to 100,000 g / mol, specifically 1,000 g / mol to 50,000 g / mol.
  • the weight average molecular weight of the oligomer is in the above range, it is possible to effectively improve the mechanical strength of the battery comprising the same.
  • the weight average molecular weight may be measured using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the GPC measurement system alliance 4 instrument is stabilized. Once the instrument is stabilized, inject the standard sample and the sample sample into the instrument to obtain a chromatogram and calculate 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 gel polymer electrolyte of the present invention methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate to further improve the mechanical strength and curing effect ,
  • Butyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl meta Further comprise unit C derived from at least one selected from the group consisting of acrylate, 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3-tetrafluoropropyl methacrylate Can be.
  • the unit C is preferably included in 50 wt% or less, specifically 20 wt% or less based on the total content of the first oligomer. If the content of the unit C exceeds 50% by weight, since the oligomer is contained in an excessive amount to increase resistance, a disadvantage may occur in that the cycle characteristics and the like decrease.
  • the matrix polymer is added to the inorganic particles in the range of 5 to 700 parts by weight, specifically 100 to 400 parts by weight based on 100 parts by weight of the first oligomer. It may contain.
  • the inorganic particles are included in an amount of 700 parts by weight or less in order to effectively improve the electrode and the interface resistance.
  • the inorganic particles are included in an amount of more than 700 parts by weight, pores are formed in the electrolyte, thereby decreasing the ion conductivity effect. If the inorganic particle content is less than 5 parts by weight, the effect of improving the mechanical properties and improving the electrochemical stability is insignificant.
  • the inorganic particles may be impregnated into the matrix polymer to allow the high viscosity solvent to penetrate well through the pores formed by the void space between the inorganic particles. That is, by including the inorganic particles, it is possible to obtain an effect of further improving the wettability to a high viscosity solvent by affinity between the polar substances and capillary phenomenon.
  • inorganic particles having a high dielectric constant and which do not generate an oxidation and / or reduction reaction in an operating voltage range of the lithium secondary battery (for example, 0 to 5V based on Li / Li + ) may be used.
  • the inorganic particles may be BaTiO 3 , BaTiO 3 , Pb (Zr, Ti) O 3 (PZT), Pb 1 - x La x Zr 1 - y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), Pb (Mg 1/3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT), Hafnia (HfO 2 ), SrTiO 3 , SnO 2 , CeO 2 , MgO, NiO, CaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiC, Lithium Phosphate (Li 3 PO 4 ), Lithium Titanium Phosphate (Li x1 Ti y1 (PO 4 ) 3 , 0 ⁇ x1 ⁇ 2, 0 ⁇ y1 ⁇ 3), lithium aluminum titanium phosphate (Li
  • inorganic particles or a mixture thereof may be further included.
  • the average particle diameter of the inorganic particles is preferably in the range of about 0.001 to 10 ⁇ m in order to have a proper porosity in a uniform thickness in the gel polymer electrolyte. If the average particle size is less than 0.001 ⁇ m dispersibility may be lowered, if the average particle diameter is more than 10 ⁇ m not only can increase the thickness of the porous coating layer, but also agglomeration of inorganic particles occurs gel polymer electrolyte Exposure to the outside can lower the mechanical strength.
  • the gel polymer electrolyte of the present invention may realize Li + ion conductivity of 2.5 ⁇ 10 ⁇ 4 S / cm or more when measured by an impedance measurement analysis system at a temperature of 25 ° C.
  • the ion conductivity was sandwiched between the prepared gel polymer electrolyte between a pair of platinum electrode disc of 1cm in diameter.
  • the ionic conductivity of the gel polymer electrolyte was measured by AC impedance measurement.
  • the measuring instrument is Bio Logic's VMP3 model and the measurement conditions were performed at room temperature under 10,000-0.1Hz and 10mV amplitude conditions.
  • the gel polymer electrolyte may have a Li + ion migration coefficient of 0.3 or more based on the NMR measurement method at a temperature of 25 °C.
  • the Li + ion mobility factor is Li + ion diffusion also / can be defined as (Li + ion diffusivity + anion diffusivity), in which the Li + ion diffusivity and anion diffusivity is the following equipment and methods Can be measured.
  • a Varian 500 MHz NMR / dual probe was used, and Li + cation diffusion constant was measured by 7 Li diffusion NMR, and anion diffusion constant (anion diffusion constant) was measured by 19 F diffusion NMR.
  • the solvent used was acetone-d 6
  • the inner tube acetone-d 6
  • the pulse sequence was stimulated echo with gradient pulse. Gradient amplitude was adjusted so that the peak intensity at the highest gradient power was about 2 to 5% of the peak intensity at the lowest gradient power. This section was divided into 16 steps in the same way as the solution NMR. Different amplitudes were applied.
  • the gel polymer electrolyte may have a gel content of about 1% by weight or more, specifically about 20% by weight or more at 25 ° C.
  • the gel polymer electrolyte preferably has an unreacted oligomer content of 20 wt% or less relative to the total amount of the reactive oligomer at 25 ° C.
  • the content of the unreacted oligomer may be implemented by implementing a gel polymer electrolyte, then extracting the gel polymer electrolyte with a solvent (acetone), and then checking the extracted solvent through NMR measurement.
  • the electrolyte solution impregnated on the matrix polymer is composed of a conventional lithium salt-containing non-aqueous solvent, wherein the lithium salt is LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , CF 3 SO 3 Li, LiC (CF 3 SO 2 ) 3 , LiC 4 BO 8 , LiTFSI, LiFSI, and LiClO 4 It may include any one selected from the group consisting of or a mixture of two or more thereof, but is not limited thereto.
  • the lithium salt is LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , CF 3 SO 3 Li, LiC (CF 3 SO 2 ) 3 , LiC 4 BO 8 ,
  • the lithium salt may be included in the electrolyte solution in 1M to 2M, or may be included in 10% by weight to 50% by weight relative to the total content of the oligomer.
  • a non-aqueous solvent commonly used in a lithium secondary battery electrolyte may be used.
  • a cyclic carbonate compound, a linear carbonate compound, an alkyl ether compound, or an alkyl acetate compound may be used. It may include at least one or more of the alkyl propionate compound, and the nitrile compound.
  • the cyclic carbonate-based compound may include at least one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and fluoroethylene carbonate (FEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • FEC fluoroethylene carbonate
  • the linear carbonate compound is at least selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate It may include one or more.
  • the alkyl ether compound may include at least one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether.
  • the alkyl acetate-based compound may include at least one selected from the group consisting of methyl acetate, ethyl acetate and propyl acetate.
  • the alkyl propionate compound may include at least one selected from the group consisting of methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
  • the nitrile compound is acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile And at least one selected from the group consisting of difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.
  • propylene carbonate and ethylene carbonate which are cyclic carbonates in the carbonate electrolyte solvent, may be preferably used because they have high dielectric constants and dissociate lithium salts in the electrolyte well, such as ethylmethyl carbonate and diethyl carbonate.
  • a low viscosity, low dielectric constant linear carbonate such as dimethyl carbonate is mixed and used in an appropriate ratio, an electrolyte having high electrical conductivity can be made, and thus it can be used more preferably.
  • the electrolyte solvent may improve the performance by adding a conventional additive used in the electrolyte solution.
  • a conventional additive used in the electrolyte solution for example, vinylene carbonate (VC), 1,3-propane sultone (PS), succinitrile (SN), ethylene sulfate (ESa), 1,3-propenesultone (PRS), fluoroethylene carbonate (FEC) Adiponitrile (ADN), LiPO 2 F 2 , lithium difluoro bis (oxalato) phosphate (LiODFB), lithium bis (oxalato) borate (LiBOB), (trimethylsilyl) propyl phosphate (TMSPa), General additives such as (trimethylsilyl) propyl phosphite (TMSPi), TFEPa, and TFEPi may be further included without limitation.
  • the gel polymer electrolyte of the present invention includes a matrix polymer formed by the oligomer, thereby increasing not only mechanical properties but also high voltage safety and reducing battery resistance and thus The ion conductivity improvement effect can be ensured. Therefore, a lithium secondary battery having improved lifespan characteristics and capacity characteristics can be manufactured.
  • a protective layer composed of a polymer on the surface of the positive electrode and the negative electrode or by using a polymer structure to suppress side reactions through anion stabilization and to increase the adhesion between the electrodes can suppress the gas generation inside the battery at high temperature.
  • stability improvement effects such as overcharging through strengthening the separator through the gel polymer polymer, thereby improving penetration stability, flame retardancy, and volatility.
  • composition for a gel polymer electrolyte comprising a first oligomer comprising a unit A represented by the formula (1) and a unit B represented by the formula (2).
  • the first oligomer may be included in an amount of 0.5 wt% to 20 wt%, more preferably 0.5 wt% to 10 wt%, based on the total weight of the composition for gel polymer electrolyte. If less than 0.5% by weight of the gel polymer is difficult to be difficult to express the characteristics of the gel polymer electrolyte, if it exceeds 20% by weight may increase the resistance due to the excessive content of the oligomer may lower the battery performance.
  • the gel polymer electrolyte of the present invention can be produced from the gel polymer electrolyte composition using a polymerization method known in the art.
  • the polymerization initiator used for this reaction may be used conventional polymerization initiator known in the art.
  • Non-limiting examples of the polymerization initiator are benzoyl peroxide, acetyl peroxide, dilauryl peroxide, Di-tert-butyl peroxide, t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide And organic peroxides such as hydrogen peroxide, hydroperoxides, 2,2'-azobis (2-cyanobutane), 2,2'-azobis (methylbutyronitrile), AIBN ( Azo compounds such as 2,2'-Azobis (iso-butyronitrile) and AMVN (2,2'-Azobisdimethyl-Valeronitrile), and the like, but are not limited thereto.
  • organic peroxides such as hydrogen peroxide, hydroperoxides, 2,2'-azobis (2-cyanobutane), 2,2'-azobis (methylbutyronitrile), AIBN ( Azo compounds such as 2,2'-Azobis (iso-but
  • the polymerization initiator is decomposed by heat in a battery, such as, but not limited to, 30 ° C. to 100 ° C., or decomposed at room temperature (5 ° C. to 30 ° C.) to form radicals, and the polymerizable oligomer is acrylate by free radical polymerization.
  • the gel polymer electrolyte may be formed by reacting with the compound.
  • the polymerization initiator may be used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the oligomer. If the polymerization initiator exceeds 20 parts by weight, gelation may occur too quickly or the unreacted initiator remains after the gel polymer electrolyte composition is injected into the battery, which adversely affects battery performance. Conversely, if the polymerization initiator is less than 0.01 part by weight. There is a problem that gelation does not work well.
  • the lithium salt is LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , CF 3 SO It may include any one selected from the group consisting of 3 Li, LiC (CF 3 SO 2 ) 3 , LiC 4 BO 8 , LiTFSI, LiFSI, and LiClO 4 or a mixture of two or more thereof, but is not limited thereto. .
  • the solvent for the electrolyte may be a non-aqueous solvent commonly used in electrolytes for lithium secondary batteries, and examples thereof include cyclic carbonate compounds, linear carbonate compounds, alkyl ether compounds, and alkyl acetate compounds. It may include at least one or more of the alkyl propionate compound, and the nitrile compound.
  • carbonate compounds which are typically cyclic carbonates, linear carbonates or mixtures thereof may be included.
  • composition for a gel polymer electrolyte according to an embodiment of the present invention can implement such physical properties known in the art, in addition to the components described above, in order to further impart a performance such as an efficiency increase and a resistance reduction effect of the gel reaction. And other additives may optionally be further contained.
  • general additives such as VC, VEC, PS, SN, AdN, ESa, PRS, FEC, LiPO 2 F 2 , LiODFB, LiBOB, TMSPa, TMSPi, TFEPa, and TFEPi may be applied.
  • It provides a lithium secondary battery comprising the gel polymer electrolyte of the present invention as the polymer electrolyte.
  • the gel polymer electrolyte is formed by polymerizing the composition for gel polymer electrolyte according to a conventional method known in the art.
  • the gel polymer electrolyte may be formed by in-situ polymerization of the composition for gel polymer electrolyte in the secondary battery.
  • Injecting the composition for the gel polymer electrolyte according to the polymerization may include the step of forming a gel polymer electrolyte.
  • thermo polymerization reaction in the lithium secondary battery is possible through the E-BEAM, gamma rays, room temperature / high temperature aging process, according to one embodiment of the present invention can be carried out through thermal polymerization.
  • the polymerization time takes about 2 minutes to 12 hours, the thermal polymerization temperature may be 30 to 100 °C.
  • the in-situ polymerization reaction in a lithium secondary battery is added to a predetermined amount of the polymerization initiator and the oligomer in an electrolyte solution containing a lithium salt, and then injected into a battery cell.
  • the polymerization is carried out by heating to 40 to 80 °C for 1 to 20 hours, the gel polymer electrolyte contained in the form of a gel is prepared when the lithium salt-containing electrolyte is subjected to gelation.
  • the lithium secondary battery according to an embodiment of the present invention has a charge voltage of 3.0V to 5.0V, excellent capacity characteristics of the lithium secondary battery in both the normal voltage and the high voltage region.
  • the electrode constituting the lithium secondary battery can be manufactured by a conventional method known in the art.
  • a slurry may be prepared by mixing and stirring a solvent, a binder, a conductive material, and a dispersant in an electrode active material, and then applying the coating (coating) to a current collector of a metal material, compressing, and drying the electrode to prepare an electrode.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on a positive electrode current collector.
  • the cathode mixture layer may be formed by coating a cathode slurry including a cathode active material, a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y9 Mn Y9 O 2 (here, 0 ⁇ Y9 ⁇ 1), LiMn 2-z4 Ni z4 O 4 ( here, 0 ⁇ Z4 ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.g., LiNi 1-Y10 Co Y10 O 2 (here, 0 ⁇ Y10 ⁇ 1) and the like), lithium-man
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , or lithium nickel manganese cobalt oxide (for example, Li (Ni 1/3 Mn 1/3 Co 1). / 3) O 2, Li ( Ni 0.6 Mn 0.2 Co 0.2) O 2, Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2, and Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 , or the like, or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2 , and the like.
  • Li ( Ni 0.6 Mn 0.2 Co 0.2) O 2 Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2
  • the cathode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the cathode slurry.
  • the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of solids in the positive electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • the conductive material is typically added in an amount of 1 to 30% by weight based on the total weight of solids in the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack, and EC, which are acetylene black series. (Armak Company), Vulcan XC-72 (manufactured by Cabot Company), and Super P (manufactured by Timcal).
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the solids in the positive electrode active material and, optionally, the slurry including the binder and the conductive material may be 40 wt% to 60 wt%, preferably 40 wt% to 50 wt%.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a negative electrode slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material is lithium-containing titanium composite oxide (LTO); Carbon-based materials such as hardly graphitized carbon and graphite carbon; Li x10 Fe 2 O 3 (0 ⁇ x10 ⁇ 1 ), Li x11 WO 2 (0 ⁇ x11 ⁇ 1), Sn x12 Me 1 - x12 Me 'y12 O z (Me: Mn, Fe, Pb, Ge; Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0 ⁇ x12 ⁇ 1;1 ⁇ y12 ⁇ 3; 1 ⁇ z12 ⁇ 8) Metal complex oxides such as these; Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , 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
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the negative electrode slurry.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt% based on the total weight of solids in the negative electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • 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 solids in the negative electrode slurry.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include an organic solvent such as water or NMP, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including the negative electrode active material and, optionally, the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 65 wt%.
  • a separator is selectively introduced between the anode and the cathode.
  • the separator serves to block internal short circuits of both electrodes and to impregnate an electrolyte, to prepare a separator composition by mixing a polymer resin, a filler, and a solvent, and then directly coating and separating the separator composition on an electrode to separate the separator film.
  • the separator film separated from the support may be formed by laminating on the electrode.
  • the said polymer resin is not specifically limited, For example, Olefin type polymers, such as a chemical resistance and hydrophobic polypropylene; A composite porous separator in which an inorganic material is added to the porous separator substrate; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • Olefin type polymers such as a chemical resistance and hydrophobic polypropylene
  • a composite porous separator in which an inorganic material is added to the porous separator substrate Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • the pore diameter of the porous separator is generally 0.01 to 50 ⁇ m, porosity may be 5 to 95%.
  • the thickness of the porous separator may generally be in the range of 5 to 300 ⁇ m.
  • the external shape of the lithium secondary battery according to an embodiment of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • electrochromic device comprising the gel polymer electrolyte of the present invention.
  • the first electrode and the second electrode may have a structure in which a transparent conductive layer is formed on a substrate
  • the electrochromic device may include a flexible substrate and a rigid substrate on opposite surfaces of the electrolyte.
  • the gel polymer electrolyte of the present invention when applied for flexibility and durability of the color change device and freedom of design, it is possible to secure ion conductivity and durability required for driving the device.
  • the substrate and the transparent conductive layer are not particularly limited as long as they are known in the art.
  • the substrate include glass and transparent plastics (polymer), and conductive materials for forming the transparent conductive layer include indium doped tin oxide (ITO), antimony doped tin oxide (ATO), and fluorine doped tin oxide (FTO). ), IZO (Indium doped zinc oxide), ZnO and the like.
  • the conductive material may be deposited on the substrate by a known method such as sputtering, electron beam deposition, chemical vapor deposition, or sol-gel coating to form a transparent conductive layer.
  • the kind of electrochromic material is not particularly limited, and inorganic metal oxides such as WO 3 , MoO 3 , V 2 O 5 , TiO 2 , NiO; Conductive polymers such as polypyrrole, polyaniline, polyazulene, polypyridine, polyindole, polycarbazole, polyazine and polythiophene; Organic discoloring substances, such as viologen, anthraquinone, and phenocyazine, etc. are mentioned.
  • the method of laminating the electrochromic material on the electrode is not particularly limited as long as it can form a thin film at a constant height from the base surface along the surface profile, and examples thereof include vacuum deposition methods such as sputtering.
  • WO 3 is a material that is colored by a reduction reaction
  • NiO is a material that is colored by an oxidation reaction.
  • the electrochemical mechanism in which the electrochromic device occurs in the electrochromic device including the inorganic metal oxide is described as in Scheme 1. Specifically, when voltage is applied to the electrochromic device, protons (H + ) or lithium ions (Li + ) contained in the electrolyte are inserted into or desorbed from the electrochromic material according to the polarity of the current. In order to satisfy, by changing the oxidation number of the transition metal contained in the electrochromic material, the optical properties of the electrochromic material itself, such as transmittance (color), is changed.
  • M is a proton or an alkali metal cation such as Li + ).
  • the electrochromic device configured as described above may be manufactured according to a conventional method known in the art, such as (a) preparing a first electrode and a second electrode; (b) injecting and then sealing the gel polymer electrolyte composition according to the present invention between the prepared first and second electrodes; And (c) polymerizing the injected electrolyte composition to form a gel polymer electrolyte.
  • Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 3: 7, 1.0 M of LiPF 6 was added to prepare a mixed solvent, and then 94 g of the mixed solvent prepared above was prepared with an oligomer of Formula 3a (weight average The molar ratio of molecular weight 7,800, unit B: unit A is 1: 2) 5g and 0.5g of AIBN and 0.5% by weight of VC were added as a polymerization initiator to prepare a composition for a gel polymer electrolyte.
  • EC Ethylene carbonate
  • EMC ethyl methyl carbonate
  • a cathode active material LiNi 1/3 Co 1/ 3 Mn 1/3 O 2; NCM
  • the conductive material of carbon black carbon black
  • a solvent N- methyl PVDF 3% by weight of a binder
  • a positive electrode mixture slurry was prepared by adding to 2-pyrrolidone (NMP).
  • NMP 2-pyrrolidone
  • the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
  • a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVDF as a binder, and carbon black as a conductive material at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
  • the negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
  • Cu copper
  • the battery was assembled using a separator composed of the positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and 2 days after injecting the prepared gel polymer electrolyte composition into the assembled battery. After standing for 24 hours at 60 °C to prepare a secondary battery containing a gel polymer electrolyte.
  • a separator composed of the positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and 2 days after injecting the prepared gel polymer electrolyte composition into the assembled battery. After standing for 24 hours at 60 °C to prepare a secondary battery containing a gel polymer electrolyte.
  • Example 1 In the same manner as the secondary battery including a gel polymer electrolyte was prepared.
  • a secondary battery including a gel polymer electrolyte was manufactured in the same manner as in Example 1, except that 24g of inorganic particles (LLZO) was further included in the preparation of the gel polymer electrolyte composition in Example 1.
  • LLZO inorganic particles
  • Example 1 A method similar to that of Example 1 except for using an acrylate oligomer made of dipentaerythritol pentaacrylate instead of the oligomer of Formula 3a in preparing the gel polymer electrolyte composition in Example 1 As a secondary battery comprising a gel polymer electrolyte was prepared.
  • a secondary battery including a gel polymer electrolyte was prepared in the same manner as in Example 1 except that the oligomer of Formula 3a was used instead of the oligomer of Formula 3a in preparing the composition for the gel polymer electrolyte in Example 1. .
  • a secondary battery including a gel polymer electrolyte was prepared in the same manner as in Example 1, except that 22 g of the oligomer of Formula 3a was used in 77 g of the mixed solution in preparing the gel polymer electrolyte composition in Example 1.
  • a secondary battery including a gel polymer electrolyte was prepared in the same manner as in Example 1, except that 0.1g of the oligomer of Formula 3a was used to prepare the gel polymer electrolyte composition in Example 1.
  • the gel polymer electrolytes of Examples 1 to 7 and Comparative Examples 1 to 4 prepared by thermal polymerization at 60 ° C. for 24 hours were sandwiched between a pair of platinum electrode discs having a diameter of 1 cm. In this state, the Li + ion conductivity of the gel polymer electrolyte was measured by AC impedance measurement.
  • the measuring equipment is Bio Logic's VMP3 model, and the measurement conditions were performed at room temperature under 10,000-0.1Hz and 10mV amplitude conditions.
  • the gel polymer electrolyte composition prepared in Examples 1 to 7 and Comparative Examples 1 to 4 was placed outside the inner tube, and then Li + ion transfer coefficient was measured. It was measured using the method. The results are shown in Table 1 below.
  • Li + ion migration coefficient Li + ion diffusivity / (Li + ion diffusivity + anion diffusivity)
  • Solvent used acetone-d 6 (At this time, the inner tube (acetone-d 6 ) was used to prevent mixing of the sample and the deuterium solvent to measure the diffusion value in the sample itself.)
  • Pulse sequence Stimulated echo with gradient pulse
  • Gradient amplitude The peak intensity at the highest gradient power was adjusted to be about 2% to 5% of the peak intensity at the lowest gradient power. In each step, 16 different amplitudes were applied to each sample.
  • the constant current was charged at 60 ° C. until the voltage reached 4.35 V at 1.0 ° C., and then the current at the voltage.
  • the constant voltage charge was performed until the reduction decreased to reach 1 / 20C. It then discharged with constant current at 1.0C until the voltage reached 3.0V.
  • the charging and discharging was repeated 100 times.
  • the capacity retention rate was calculated from the result obtained above using the following formula, and the value is shown in Table 1 below.
  • Capacity maintenance rate at 100th cycle 100th cycle discharge capacity / 1st cycle discharge capacity
  • the ion conductivity of the gel polymer electrolyte of Comparative Example 1 was 6.1 ⁇ 10 ⁇ 4
  • the ion conductivity of the gel polymer electrolyte of Comparative Example 2 was 4.8 ⁇ 10 ⁇ 4
  • the present invention was practiced. It can be seen that the ion conductivity of the gel polymer electrolytes of Examples 1 to 7 is mostly improved by about 10% or more to 6.9 ⁇ 10 ⁇ 4 or more.
  • the Li + ion transfer coefficients of the secondary batteries of Examples 1 to 7 of the present invention are all 0.415 or more, and the Li + ion transfer coefficients of the secondary batteries of Comparative Example 1 are 0.375 and 0.410 of the secondary batteries of Comparative Example 2. It can be seen that compared with the improvement.
  • the 100 th cycle discharge capacity (mAh) of the secondary battery of Comparative Example 1 was 617
  • the capacity retention rate (%) at 100 th cycle was 82.5%
  • the 100 th cycle discharge capacity (mAh) of the secondary battery of Comparative Example 2 ) Is 430
  • the capacity retention rate (%) at 100 th cycle is 61.4%
  • the 100 th cycle discharge capacity (mAh) of the secondary batteries of Examples 1 to 7 of the present invention is 698 or more and 100 th cycle It can be seen that the capacity retention rate (%) at is better than 94.5%.
  • Li + ion transfer coefficient is 0.550 by anion immobilization, while the ion conductivity is 2.5 ⁇ 10 by increasing the resistance - it can be seen that as low as 4.
  • the 100 th cycle discharge capacity (mAh) was 117 and the capacity retention rate (100%) at 100 th cycle was significantly poor due to the kinetic degradation caused by low ion conductivity. Able to know.

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Abstract

La présente invention concerne un électrolyte de polymère de type gel et une batterie rechargeable au lithium comprenant celui-ci. L'électrolyte de polymère de type gel comprend : un polymère de matrice ; et une solution d'électrolyte imprégnée sur le polymère de matrice, le polymère de matrice étant formé sous la forme d'une structure de réseau tridimensionnel obtenue par polymérisation d'un premier oligomère comprenant le motif A, qui est représenté par la formule 1, et l'unité B, qui comporte un groupe fonctionnel de réticulation dérivé d'un composé comprenant au moins un groupe acrylate copolymérisable.
PCT/KR2017/009622 2016-09-02 2017-09-01 Électrolyte de polymère de type gel et batterie rechargeable au lithium comprenant celui-ci Ceased WO2018044129A1 (fr)

Priority Applications (5)

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EP17847054.8A EP3361546B1 (fr) 2016-09-02 2017-09-01 Électrolyte de polymère de type gel et batterie rechargeable au lithium comprenant celui-ci
US15/771,773 US10714791B2 (en) 2016-09-02 2017-09-01 Gel polymer electrolyte and lithium secondary battery including the same
ES17847054T ES2950099T3 (es) 2016-09-02 2017-09-01 Electrolito de polímero de gel y batería secundaria de litio que lo incluye
PL17847054.8T PL3361546T3 (pl) 2016-09-02 2017-09-01 Żelowy elektrolit polimerowy i zawierający go akumulator litowy
CN201780003933.8A CN108352569B (zh) 2016-09-02 2017-09-01 凝胶聚合物电解质和包括该凝胶聚合物电解质的锂二次电池

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US20210036365A1 (en) * 2018-07-02 2021-02-04 Lg Chem, Ltd. Lithium Secondary Battery Having Improved High-Temperature Characteristics
JP2021510448A (ja) * 2018-06-07 2021-04-22 エルジー・ケム・リミテッド 低温特性および高温特性が向上したリチウム二次電池
US20210151799A1 (en) * 2018-03-06 2021-05-20 Lg Chem, Ltd. Non-Aqueous Electrolyte Solution and Lithium Secondary Battery Including the Same
JP2021513188A (ja) * 2018-09-28 2021-05-20 エルジー・ケム・リミテッド 非水性電解液及びこれを含むリチウム二次電池
US20210384558A1 (en) * 2018-11-20 2021-12-09 Nippon Telegraph And Telephone Corporation Sodium Secondary Battery and Manufacturing Method Thereof
US20210399295A1 (en) * 2018-11-20 2021-12-23 Nippon Telegraph And Telephone Corporation Lithium Secondary Battery and Manufacturing Method Thereof
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US11581577B2 (en) * 2017-11-30 2023-02-14 Lg Energy Solution, Ltd. Composition for gel polymer electrolyte including fluoroalkylene oligomer, lithium salt, and phosphate or boran-based additive, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the gel polymer electrolyte
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US11870036B2 (en) * 2018-07-02 2024-01-09 Lg Energy Solution, Ltd. Lithium secondary battery having improved high-temperature characteristics
US20210036365A1 (en) * 2018-07-02 2021-02-04 Lg Chem, Ltd. Lithium Secondary Battery Having Improved High-Temperature Characteristics
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JP7055884B2 (ja) 2018-09-28 2022-04-18 エルジー エナジー ソリューション リミテッド 非水性電解液及びこれを含むリチウム二次電池
JP7408215B2 (ja) 2018-09-28 2024-01-05 エルジー エナジー ソリューション リミテッド 非水性電解液及びこれを含むリチウム二次電池
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US12027670B2 (en) 2018-09-28 2024-07-02 Lg Energy Solution, Ltd. Non-aqueous electrolyte solution and lithium secondary battery including the same
US20210399295A1 (en) * 2018-11-20 2021-12-23 Nippon Telegraph And Telephone Corporation Lithium Secondary Battery and Manufacturing Method Thereof
US20210384558A1 (en) * 2018-11-20 2021-12-09 Nippon Telegraph And Telephone Corporation Sodium Secondary Battery and Manufacturing Method Thereof

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