WO2016053064A1 - 젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지 - Google Patents
젤 폴리머 전해질 및 이를 포함하는 리튬 이차전지 Download PDFInfo
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- WO2016053064A1 WO2016053064A1 PCT/KR2015/010472 KR2015010472W WO2016053064A1 WO 2016053064 A1 WO2016053064 A1 WO 2016053064A1 KR 2015010472 W KR2015010472 W KR 2015010472W WO 2016053064 A1 WO2016053064 A1 WO 2016053064A1
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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
- H01M10/052—Li-accumulators
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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
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- 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 metal oxide is used as a positive electrode active material of a lithium secondary battery, and lithium metal, a lithium alloy, crystalline or amorphous carbon or a carbon composite material is used as a negative electrode active material.
- the secondary battery may be coated with a positive electrode and a negative electrode active material to a current collector in a suitable thickness and length, or the active material itself in a film form, and then wound or laminated together with a separator as an insulator to manufacture an electrode assembly in a can or a similar container. After putting, it is manufactured by the method of inject
- an electrolyte in a liquid state particularly an ion conductive liquid electrolyte in which salts are dissolved in a non-aqueous organic solvent, has been mainly used.
- liquid electrolyte in this way not only deteriorates the electrode material and volatilizes the organic solvent, but also causes problems in safety due to the combustion caused by an increase in the ambient temperature and the temperature of the battery itself.
- a lithium secondary battery has a problem in that gas is generated inside the battery due to decomposition of a carbonate organic solvent and / or side reaction between the organic solvent and the electrode during charging and discharging, thereby expanding the thickness of the battery. Thus, the amount of gas generated is further increased.
- the gas generated continuously causes an increase in the internal pressure of the battery, which causes the rectangular battery to swell in a specific direction and explodes, or to deform the center of a specific surface of the battery, thereby degrading safety. It causes a local difference in the electrode reaction does not occur the same across the entire electrode surface causes a disadvantage of deterioration of the battery performance.
- 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. Therefore, in order to improve this, a method of thinning the thickness of the gel polymer electrolyte has been proposed.
- a problem in improving battery performance and safety such as a decrease in mechanical strength, a short circuit between the positive electrode and the negative electrode, and a short circuit in the polymer electrolyte.
- the problem to be solved in the present invention is to provide a gel polymer electrolyte comprising a polymer network consisting of an oligomer comprising a urethane, acrylate and siloxane.
- the present invention provides a lithium secondary battery including the gel polymer electrolyte.
- the polymer network is formed by combining an oligomer comprising a unit A derived from a monomer comprising at least one copolymerizable acrylate or an acrylic acid, a unit C including a urethane, and a unit E including a siloxane in a three-dimensional structure.
- a gel polymer electrolyte is provided.
- a gel polymer electrolyte comprising a gel polymer electrolyte comprising a unit A derived from a monomer comprising at least one copolymerizable acrylate or acrylic acid, a unit C comprising urethane, and an oligomer comprising unit E comprising siloxane
- a gel polymer electrolyte comprising a gel polymer electrolyte comprising a unit A derived from a monomer comprising at least one copolymerizable acrylate or acrylic acid, a unit C comprising urethane, and an oligomer comprising unit E comprising siloxane
- the gel polymer electrolyte provides a lithium secondary battery including the gel polymer electrolyte of the present invention.
- various embodiments of the present invention provide a gel polymer electrolyte or a lithium secondary battery as follows.
- polymer network (1) a polymer network; And an electrolyte impregnated on the polymer network, wherein the polymer network comprises unit A derived from monomers comprising at least one copolymerizable acrylate or acrylic acid, unit C comprising urethane, and unit comprising siloxane.
- k is an integer of 1 to 200.
- the unit A is a unit derived from at least one compound selected from the group consisting of hydroxymethyl (meth) acrylate, and hydroxyethyl (meth) acrylate, or a compound represented by the following formula (i)
- R ' is a linear or nonlinear alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted bicycloalkylene group having 6 to 20 carbon atoms, or a substituted or substituted carbon group having 6 to 20 carbon atoms or At least one selected from the group consisting of an unsubstituted arylene group, a substituted or unsubstituted biarylene group having 6 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a naphthalene group and an anthracene group.
- R 1 and R 2 are linear or nonlinear alkylene groups having 1 to 5 carbon atoms
- R 3 and R 4 are each independently one selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, and a phenyl group,
- R 5 to R 10 are each independently one selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and fluorine,
- o is an integer of 0 or 1
- p is 0 or an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- p is 0 or an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- Unit 1 is 1 mol or 2 mol in 1 mol of the first oligomer
- R '' is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted nonlinear alkylene group having 1 to 10 carbon atoms,
- R '' ' is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted nonlinear alkylene group having 1 to 10 carbon atoms,
- n is an integer of 1-30.
- n is 0 or an integer from 1 to 30,
- k is an integer from 1 to 200
- s is 0 or 1.
- the unit A is 1 mol or 2 mol
- the molar ratio of the unit B: unit C: unit D: unit E is 0 to 35: 2 to 201: 0 to 35: 1 to 200 (wherein units B and D are not 0 at the same time);
- k is an integer from 1 to 200
- n is an integer from 1 to 30,
- n 1 to 30
- p is an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- the gel polymer electrolyte is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl meta Acrylate, ethylhexyl acrylate, ethylhexyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetra (1) to (14), further comprising a second oligomer comprising a unit derived from fluoropropyl acrylate, and at least one selected from the group consisting of 2,2,3,3-tetrafluoropropyl methacrylate.
- the gel polymer electrolyte as described in any one of).
- Unit A derived from monomers comprising at least one copolymerizable acrylate or acrylic acid; Unit C comprising urethane; And unit E comprising siloxane.
- (24) comprises oligomers containing units comprising siloxanes
- a gel polymer electrolyte having a Li + ion transfer coefficient of 0.3 or more and a content of unreacted oligomers of 20% or less relative to the total amount of reactive oligomers.
- composition for gel polymer electrolytes in any one of said (1)-(23) containing 1 oligomer.
- k is an integer of 1 to 200.
- the unit A is a unit derived from at least one compound selected from the group consisting of hydroxymethyl (meth) acrylate and hydroxyethyl (meth) acrylate, or a unit represented by the following formula (i)
- R ' is a linear or nonlinear alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted bicycloalkylene group having 6 to 20 carbon atoms, or a substituted or substituted carbon group having 6 to 20 carbon atoms or At least one selected from the group consisting of an unsubstituted arylene group, a substituted or unsubstituted biarylene group having 6 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a naphthalene group and an anthracene group.
- R 1 and R 2 are linear or nonlinear alkylene groups having 1 to 5 carbon atoms
- R 3 and R 4 are each independently one selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, and a phenyl group,
- R 5 to R 10 are each independently one selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and fluorine,
- o is an integer of 0 or 1
- p is 0 or an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- R '' is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted nonlinear alkylene group having 1 to 10 carbon atoms,
- R '' ' is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted nonlinear alkylene group having 1 to 10 carbon atoms,
- n is an integer of 1-30.
- composition for a gel polymer electrolyte according to any one of (25) to (32), wherein the oligomer is represented by at least one selected from the group consisting of the following Chemical Formulas 6a to 6c.
- n is 0 or an integer from 1 to 30,
- k is an integer from 1 to 200
- s is 0 or 1.
- unit A In 1 mol of the oligomer, unit A is 1 mol or 2 mol, and the molar ratio of unit B: unit C: unit D: unit E is 0 to 35: 2 to 201: 0 to 35: 1 to 200 (wherein Unit gel and electrolyte according to any one of (25) to (33), wherein units B and D are not 0 at the same time.
- k is an integer from 1 to 200
- n is an integer from 1 to 30,
- n 1 to 30
- p is an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- composition for gel polymer electrolyte according to any one of (25) to (35), wherein the polymer network further contains inorganic particles on the polymer network.
- composition for gel polymer electrolyte according to any one of (25) to (36), wherein the weight average molecular weight of the oligomer is 1,000 to 100,000.
- the polymerization initiator is benzoyl peroxide, acetyl peroxide, dilauryl peroxide, di-tert- butyl peroxide, t- butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide, hydrogen per Oxides, 2,2'-azobis (2-cyanobutane), 2,2'-azobis (methylbutyronitrile), AIBN (2,2'-Azobis (iso-butyronitrile)) and AMVN (2, 2'-Azobisdimethyl-Valeronitrile)
- the composition for gel polymer electrolytes in any one of said (25)-(37) which is a single substance or mixture of 2 or more types chosen from the group which consists of 2'-Azobisdimethyl-Valeronitrile).
- composition for gel polymer electrolyte according to any one of (25) to (38), wherein the polymerization initiator is contained in an amount of 0.01% by weight to 2% by weight based on the total content of the oligomer.
- the lithium salt may be 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 ( The gel according to any one of (25) to (39), which is any one selected from the group consisting of CF 3 SO 2 ) 3 , LiC 4 BO 8 , LiTFSI, LiFSI, and LiClO 4 , or a mixture of two or more thereof. Polymer electrolyte composition.
- composition for gel polymer electrolyte according to any one of (25) to (41), wherein the electrolyte solvent is a linear carbonate, a cyclic carbonate, or a combination thereof.
- the linear carbonate includes any one or a mixture of two or more selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethylmethyl carbonate, methylpropyl carbonate and ethylpropyl carbonate, wherein the cyclic Carbonates are ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, and halides thereof
- the composition for gel polymer electrolytes in any one of said (25)-(42) containing any 1 or 2 or more types of these selected from the group which consists of these.
- Lithium secondary battery comprising a.
- An electrochromic device comprising a first electrode, a second electrode, an electrochromic material and the gel polymer electrolyte according to any one of (1) to (22).
- the gel polymer electrolyte of the present invention includes a polymer network composed of an oligomer including urethane, acrylate, and siloxane, thereby improving mechanical strength together with ionic conductivity. Therefore, it is possible to manufacture a lithium secondary battery with improved lifetime characteristics and capacity characteristics.
- the gel polymer electrolyte of the present invention has the advantage that it can be used in both aqueous and non-aqueous cathode systems.
- the polymer network comprises a first oligomer comprising unit A derived from a monomer comprising at least one copolymerizable acrylate or acrylic acid, a unit C comprising urethane, and a unit E comprising siloxane in a three-dimensional structure. It provides a gel polymer electrolyte, characterized in that formed.
- the gel polymer electrolyte is not only weak in safety and mechanical properties compared to the solid polymer electrolyte, but also has a disadvantage in that ionic conductivity is lower than that of the liquid electrolyte. Therefore, recently, studies to improve mechanical properties and ionic conductivity using copolymers such as oligomers have been conducted. However, when the monomers are used alone, there is a problem in that deterioration of cycle characteristics and a desired level of mechanical characteristics cannot be obtained. In the case of using the oligomeric compound alone, it is not easy to control the physical properties, it is difficult to form a homogeneous polymer in the battery may be difficult to apply to the recent high capacity and large cells.
- the present invention has been made to solve these problems by providing a gel polymer electrolyte comprising a polymer network formed by oligomer compounds prepared by polymerizing compounds having physical properties that can complement the electrochemical and mechanical properties.
- the present invention provides a gel polymer electrolyte comprising an oligomer in which the ratio of the unit A derived from the monomer containing acrylic acid, the unit C containing urethane, the unit E containing siloxane, and the like is appropriately adjusted. In any situation, such as an aqueous system as well as an aqueous system, it is possible to prevent side reactions from occurring and lower the resistance to improve ion conductivity.
- the first oligomer included in the gel polymer electrolyte of the present invention may be represented by the following Chemical Formula 1.
- k is an integer of 1 to 200.
- the unit A constituting the oligomer is a component that serves to form a gel polymer through a curing reaction in the oligomer, at least one carbon-oxygen single in the molecular structure
- a derived unit derived from a monomer containing a mono- or polyfunctional (meth) acrylate containing a bond or acrylic acid specifically 1 to 20, preferably 1 to 10 acrylate or methacrylate structures It may be a compound containing.
- the unit A constituting the oligomer is a unit derived from at least one compound selected from the group consisting of hydroxymethyl (meth) acrylate, and hydroxyethyl (meth) acrylate as a representative example thereof, or It may include a unit represented by).
- the unit C constituting the oligomer is a component for imparting a function of adjusting the ion transport characteristics, and controlling the mechanical properties and adhesion, specifically, to immobilize the anion of the salt It is a unit structure necessary to form a rigid structure in a molecule so as to secure the flexibility of the polymer.
- the unit C may be represented by the compound of Formula 2a or Formula 2b.
- R ' is a linear or nonlinear alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted bicycloalkylene group having 6 to 20 carbon atoms, or a substituted or substituted carbon group having 6 to 20 carbon atoms or At least one selected from the group consisting of an unsubstituted arylene group, a substituted or unsubstituted biarylene group having 6 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a naphthalene group and an anthracene group.
- R ' may include one selected from the group consisting of the following groups.
- the unit E constituting the oligomer is a component added to control the affinity between the mechanical properties and the separator, specifically, a rigid structural region by a urethane bond in the polymer structure
- the affinity with the polyolefin-based membrane fabric is increased, the resistance can be reduced to implement the effect of improving the ion conductivity more.
- the unit E may be represented by the following formula (3).
- R 1 and R 2 are linear or nonlinear alkylene groups having 1 to 5 carbon atoms
- R 3 and R 4 are each independently one selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, and a phenyl group,
- R 5 to R 10 are each independently one selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, a phenyl group, and fluorine,
- o is an integer of 0 or 1
- p is 0 or an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- the unit E may include a compound selected from the group consisting of the following Chemical Formulas 3a to 3g.
- p is 0 or an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- unit A in one mole of the oligomer, may be 1 mole or 2 moles, and the molar ratio of unit C to unit E may be about 1.005: 1 to 2: 1. .
- the molar ratio of the unit C: E may be 201: 200, that is, 1.005: 1.
- the oligomer may further include at least one or more units selected from the group consisting of a unit B represented by the following formula (4) and a unit D represented by the following formula (5). .
- R '' is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted nonlinear alkylene group having 1 to 10 carbon atoms,
- R '' ' is a substituted or unsubstituted linear alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted nonlinear alkylene group having 1 to 10 carbon atoms,
- n is an integer of 1-30.
- the gel polymer electrolyte of the present invention further includes a unit D derived from the B unit and the oxyalkylene in the oligomer structure, thereby increasing dissociation of the salt in the polymer structure and affinity with the highly polar surface in the battery. You can implement the effect.
- the unit B is a unit for imparting the impregnation ability and the ion transport ability of the solvent, and may include at least one selected from the group consisting of the following groups.
- the unit D is a unit for imparting a function for adjusting the impregnation ability, the electrode affinity, and the ion transfer ability of the solvent, and may include at least one selected from the group consisting of the following groups.
- the oligomer included in the gel polymer electrolyte of the present invention may be represented by at least one selected from the group consisting of the following formulas 6a to 6c.
- n is 0 or an integer from 1 to 30,
- k is an integer from 1 to 200
- s is 0 or 1.
- unit A is 2 mol
- the molar ratio of unit B: unit C: unit D: unit E is 0-35: 2-201: 0-35: 1-200
- the molar ratio of unit D to unit E may be 0 to 35:10 to 100: 0 to 35:20 to 100, and more specifically 0 to 5:10 to 100: 10 to 30:20 to 100. , Units B and D do not go to zero at the same time.
- the oligomer may be at least one selected from the group consisting of the following Chemical Formulas 7a to 7d.
- k is an integer from 1 to 200
- n is an integer from 1 to 30,
- n 1 to 30
- p is an integer from 1 to 400
- r is an integer from 1 to 400
- the molar ratio of p: r is 0: 100 to 80:20.
- the weight average molecular weight of the oligomer for forming the gel polymer electrolyte of the present invention may be about 1,000 to 100,000. When 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 gel polymer electrolyte is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl to further improve mechanical strength and curing effect.
- a second oligomer comprising units derived from at least one selected from the group consisting of 2,2,3,3-tetrafluoropropyl acrylate, and 2,2,3,3-tetrafluoropropyl methacrylate. It may further include.
- the second oligomer is preferably included in less than 50% by weight, specifically 20% by weight based on the total content of the first oligomer. If the content of the second oligomer 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 gel polymer electrolyte of the present invention includes the unit E containing siloxane in the oligomer structure, thereby ensuring excellent mechanical properties of the gel polymer electrolyte and enhancing affinity with the polyolefin-based membrane fabric. Can be.
- the affinity with the membrane fabric is improved, the resistance is reduced to improve the ion transfer characteristics, thereby realizing the effect of improving the ion conductivity more.
- the gel polymer electrolyte of the present invention may include the urethane bond of the unit C, and the unit B and D selectively in the structure, thereby enhancing the effect of further ion transfer properties to realize the effect of improving the ion conductivity, as well as elasticity And by increasing the flexibility and the like can be relieved stress due to volume expansion generated when driving the battery.
- the gel polymer electrolyte of the present invention has improved ion conductivity and does not need to reduce the thickness of the gel polymer electrolyte, sufficient mechanical strength can be ensured and the life characteristics of the secondary battery including the same can be improved. Can be.
- the gel polymer electrolyte of the present invention comprises an oligomer in which the ratio of the unit A derived from the monomer containing acrylic acid, the unit C containing urethane, and the unit E containing siloxane, and the ratio of unit B and unit D are properly adjusted.
- the polymer network may further contain inorganic particles in the range of 10 to 25% by weight based on the total weight of the polymer network.
- the inorganic particles may be impregnated in the polymer network to allow the high viscosity solvent to penetrate well through the pores formed by the void space between the inorganic particles. That is, by including the inorganic particles, it is possible to obtain an effect of further improving the wettability to a high viscosity solvent by affinity between the polar substances and capillary phenomenon.
- inorganic particles having a high dielectric constant and which do not generate an oxidation and / or reduction reaction in an operating voltage range of the lithium secondary battery (for example, 0 to 5V based on Li / Li + ) may be used.
- the inorganic particles are BaTiO 3 , BaTiO 3 , Pb (Zr, Ti) O 3 (PZT), Pb 1 - x La x Zr 1 - y Ti y O 3 (PLZT) having a dielectric constant of 5 or more as a representative example thereof.
- inorganic particles having lithium ion transfer ability that is, lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3 ), Lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 3), 14Li 2 O-9Al 2 O 3 -38TiO 2- (LiAlTiP) such as 39P 2 O 5 x O y series glass (0 ⁇ x ⁇ 4, 0 ⁇ y ⁇ 13), lithium lanthanum titanate (Li x La y TiO 3, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 3), Li 3 .
- lithium phosphate Li 3 PO 4
- lithium titanium phosphate Li x Ti y (PO 4 ) 3 , 0 ⁇ x ⁇ 2, 0
- 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 is 1.0x10 -4 S / cm than in the case of measuring the impedance measurement analysis system at 25 °C temperature, specifically, 1.0x10 -4 S / cm to 2.0x10 -2 S / It may have a Li + ion conductivity of cm.
- the ion conductivity was measured using the Impedance measurement method in the form of a SUS / GPE / SUS cell to form a gel polymer electrolyte film of 13mm thickness.
- 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 may have a Li + ion transfer coefficient of 0.3 or more based on NMR measurement 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 was measured by 19 F diffusion NMR.
- the solvent used was acetone-d 6
- the inner tube (acetone-d 6 ) was used to prevent the sample from mixing with the deuterium solvent to measure the diffusion value in the sample itself.
- 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% 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 of the present invention 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 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 , LiTFSI, LiFSI, and LiClO 4 Or a
- the lithium salt may include 10 to 50% by weight based on the total content of the polymerization initiator and the oligomer.
- a non-aqueous solvent commonly used in a lithium secondary battery electrolyte may be used.
- ether, ester (Acetate, Propionate), amide, linear carbonate or cyclic carbonate, nitrile (aceto Nitrile, SN, and the like) may be used alone or in combination of two or more thereof.
- carbonate compounds which are typically cyclic carbonates, linear carbonates or mixtures thereof may be included.
- cyclic carbonate compound examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene Carbonate, vinylene carbonate, and halides thereof, any one selected from the group consisting of or mixtures of two or more thereof.
- linear carbonate compounds include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC). Any one selected from the group consisting of, or a mixture of two or more thereof may be representatively used, but is not limited thereto.
- 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.
- ester in the electrolyte solvent is methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone And ⁇ -caprolactone, but any one selected from the group consisting of, or a mixture of two or more thereof may be used, but is not limited thereto.
- the electrolyte solvent may improve the performance by adding a conventional additive used in the electrolyte solution.
- VC VEC
- FEC LiPO 2 F 2 , LiODFB, LiBOB, TMSPa, TMSPi, TFEPa, TFEPi
- TFEPi may further include without limitation.
- the metal ions eluted from the positive electrode are precipitated at the negative electrode
- the gel polymer electrolyte of the present invention includes a polymer network formed by the oligomer, thereby combining with the metal ions eluted at the positive electrode to precipitate the metal at the negative electrode.
- I can alleviate it. Therefore, the charge and discharge efficiency of the lithium secondary battery can be improved and good cycle characteristics can be exhibited.
- 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 a high temperature.
- Unit A derived from monomers comprising at least one copolymerizable acrylate or acrylic acid;
- Unit C comprising urethane
- a gel polymer electrolyte comprising unit E comprising siloxane can be provided.
- An oligomer comprising unit E comprising a siloxane
- composition for a gel polymer electrolyte of the present invention comprising an oligomer comprising a unit A derived from a monomer comprising at least one copolymerizable acrylate or acrylic acid, a unit C comprising a urethane, and a unit E comprising a siloxane. can do.
- the oligomer may be included in 0.5% by weight to 20% by weight, more preferably 0.5% by weight to 10% by weight relative to the total weight of the composition for the 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, organic peroxides and hydros such as t-butyl peroxy-2-ethyl-hexanoate, cumyl hydroperoxide, and hydrogen peroxide Peroxides with 2,2'-azobis (2-cyanobutane), 2,2'-azobis (methylbutyronitrile), AIBN (2,2'-Azobis (iso-butyronitrile)) and AMVN (2 And azo compounds such as 2'-Azobisdimethyl-Valeronitrile), but are not limited thereto.
- 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% by weight to 2% by weight based on the total content of the oligomer. If the polymerization initiator is more than 2% 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 the battery performance. Conversely, the polymerization initiator is less than 0.01 part by weight. There is a problem that the gelation is not made well.
- Gel polymer electrolyte composition according to an embodiment of the present invention in addition to the components described above, in order to impart an effect of increasing the efficiency and resistance of the gel reaction, and optionally other additives that can implement such properties known in the art It may contain more.
- the gel polymer electrolyte may be improved by adding a conventional additive used in an electrolyte solution.
- a conventional additive used in an electrolyte solution.
- general additives such as VC, VEC, Propane sultone, SN, 'AdN, ESa, PRS, FEC, LiPO 2 F 2 , LiODFB, LiBOB, TMSPa, TMSPi, TFEPa, TFEPi are applicable.
- 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.
- in-situ polymerization reaction in a lithium secondary battery is added to a predetermined amount of the initiator and the oligomer in an electrolyte solution containing a lithium salt and mixed 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 active material constituting the positive electrode may be applied to a general voltage or a high voltage, and a compound capable of reversibly intercalating / deintercalating lithium may be used.
- a carbon material lithium metal, silicon, tin, or the like, into which lithium ions may be inserted and released, may be used.
- a carbon material may be used, and as the carbon material, both low crystalline carbon and high crystalline carbon may be used.
- Soft crystalline carbon and hard carbon are typical low crystalline carbon, and high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch carbon fiber.
- High temperature calcined carbon such as (mesophase pitch based carbon fiber), meso-carbon microbeads, Mesophase pitches and petroleum or coal tar pitch derived cokes.
- the positive electrode and / or negative electrode may be prepared by mixing and stirring a binder, a solvent, a conductive material and a dispersant, which may be commonly used as necessary, to prepare a slurry, and then applying the same to a current collector and compressing the negative electrode.
- the binder may be polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile, polymethylmethacrylate, Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), Various kinds of binder polymers such as sulfonated EPDM, styrene butyrene rubber (SBR), fluorine rubber, various copolymers and the like may be used.
- PVDF-co-HEP polyvinylidene fluoride-hexafluoropropylene copolymer
- SBR styrene butyrene rubber
- the lithium secondary battery may have a separator between the positive electrode and the negative electrode according to the type.
- a separator a conventional porous polymer film, that is, polyethylene, polypropylene, polyvinylidene fluoride or two or more multilayer films thereof may be used, and a polyethylene / polypropylene two-layer separator and a polyethylene / polypropylene / polyethylene three-layer separator
- a mixed multilayer film such as polypropylene / polyethylene / polypropylene three-layer separator can be used.
- a conventional porous non-woven fabric for example, a non-woven fabric made of glass fibers of high melting point, polyethylene terephthalate fibers and the like can be used, but is not limited thereto.
- 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 , Ir (OH) x, 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.
- inorganic metal oxides such as WO 3 , Ir (OH) x, 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
- 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): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio)
- LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- the oligomer of Formula 7a molecular weight 7,800, unit A is 2 mol, unit B: unit C: unit D: mole ratio of unit E is 4.7: 33.4: 14.3: 47.6) 5% and AIBN as the polymerization initiator 0.5 to the total content of the oligomer
- a composition for gel polymer electrolyte was prepared by adding weight% and 0.5% VC.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio) LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- 5% of the oligomer of Formula 7b molecular weight 8,500, unit A is 2 mol, unit C: unit D: mole ratio of unit E is 30:26:44
- VC 0.5 % was added to prepare a gel polymer electrolyte composition.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio)
- LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- 5% of the oligomer of Chemical Formula 7c molecular weight 8,500, unit A is 1 mol, unit C: unit D: molar ratio of unit E is 30: 26:44
- 0.5 wt% VC 0.5% of the total content of the oligomer as the polymerization initiator was added to prepare a composition for a gel polymer electrolyte.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio)
- LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- the oligomer of Formula 7d molecular weight 8,100, unit A is 2 moles, unit B: unit C: unit D: mole ratio of unit E is 4.7: 33.4: 14.3: 47.6) 5% and AIBN as the polymerization initiator 0.5 to the total content of the oligomer
- a composition for gel polymer electrolyte was prepared by adding 0.5% by weight of VC.
- a gel polymer electrolyte composition was prepared in the same manner as in Example 1, except that 12% of the oligomer of Chemical Formula 7a was included.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio)
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio) LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- the unit C containing urethane and the unit E including siloxane instead of the dipentaerythritol containing only unit A derived from the monomer including acrylate
- a gel polymer electrolyte composition was prepared in the same manner as in Example 1, except that an oligomer made of pentaacrylate (dipentaerythritol pentaacrylate) was used.
- Ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) 2: 3: 5 (volume ratio) LiPF 6 was dissolved in a non-aqueous electrolyte solvent to a concentration of 1 M to prepare an electrolyte solution.
- EMC ethyl methyl carbonate
- DMC dimethyl carbonate
- a unit A derived from a monomer containing acrylate and a unit C including urethane are represented by the following Chemical Formula 8 Except for using the oligomer to prepare a composition for a gel polymer electrolyte in the same manner as in Example 1.
- 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 consisting of the positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and the gel polymer electrolyte composition prepared in Example 1 was injected into the assembled battery. After leaving for 2 days and then heated to 70 °C for 5 hours to prepare a secondary battery containing a gel polymer electrolyte.
- a separator consisting of the positive electrode, the negative electrode, and three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), and the gel polymer electrolyte composition prepared in Example 1 was injected into the assembled battery. After leaving for 2 days and then heated to 70 °C for 5 hours to prepare a secondary battery containing a gel polymer electrolyte.
- a secondary battery including the gel polymer electrolyte was manufactured in the same manner as in Example 7, except that the gel polymer electrolyte composition of Example 2 was injected instead of the gel polymer electrolyte composition of Example 1.
- a secondary battery including the gel polymer electrolyte was manufactured in the same manner as in Example 7, except that the gel polymer electrolyte composition of Example 5 was injected instead of the gel polymer electrolyte composition of Example 1.
- a secondary battery including the gel polymer electrolyte was manufactured in the same manner as in Example 7, except that the gel polymer electrolyte composition of Example 6 was injected instead of the gel polymer electrolyte composition of Example 1.
- a secondary battery including the gel polymer electrolyte was manufactured in the same manner as in Example 7, except that the gel polymer electrolyte composition of Comparative Example 1 was injected instead of the gel polymer electrolyte composition of Example 1.
- a secondary battery including a gel polymer electrolyte was manufactured in the same manner as in Comparative Example 3 except that the gel polymer electrolyte composition of Comparative Example 2 was injected instead of the composition for gel polymer electrolyte of Comparative Example 1.
- the gel polymer electrolyte composition prepared in Examples 1, 2, 5, and 6 and the gel polymer electrolyte composition prepared in Comparative Example 1 were prepared in the form of a film of 13 mm thickness, and then SUS / GPE / SUS cells.
- Li + ion conductivity was measured using Impedance measurement.
- the measuring instrument is Bio Logic's VMP3 model, and the measurement conditions were performed at room temperature (25 °C) under 10,000-0.1Hz and 10mV amplitude conditions. The results are shown in Table 1 below.
- Example 1 8.4mS / cm
- Example 2 8.1mS / cm
- Example 5 6.5mS / cm
- Example 6 4.8mS / cm Comparative
- Example 1 7.0mS / cm
- Example 6 it was found that the ionic conductivity is lower than in Example 1.
- Li + ion migration coefficient Li + ion diffusivity / (Li + ion diffusivity + anion diffusivity)
- Li + ion diffusivity measured by 7 Li diffusion NMR
- Solvent used acetone-d 6 (In this case, the inner tube (acetone-d 6 ) was used to prevent the sample from mixing with 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 is adjusted to be about 2 to 5% of the peak intensity at the lowest gradient power. This section is divided into 16 steps in the same manner as the solution NMR. Different amplitudes were applied.
- Example 6 it can be seen that the Li + ion transfer coefficient is lower than in Example 1.
- the gel polymer electrolyte was extracted with a solvent (acetone). Then, the extracted solvent was analyzed by the NMR measurement of the remaining amount of unreacted oligomer. The results are shown in Table 3 below.
- Example 7 N.D
- Example 8 0.5%
- Example 9 N.D
- Example 10 Comparative Example 3 3.0%
- the content of the unreacted oligomer of the secondary batteries of Examples 7 to 10 is 2% or less, while the content of the unreacted oligomer of the secondary battery of Comparative Example 3 is 3% and the content of the unreacted oligomer is 3%. It is high.
- Capacity maintenance rate at 100th cycle 100th cycle discharge capacity / 1st cycle discharge capacity
- Example 7 1 st cycle discharge capacity 100 th cycle discharge capacity Capacity retention at 100 th cycles (%)
- Example 8 751 mAh 728 mAh 97%
- Example 9 730 mAh 715 mAh 98%
- Example 10 683 mAh 417 mAh 61% Comparative Example 3 720 mAh 117 mAh 16.2%
- Example 5 For each gel polymer electrolyte composition prepared in Example 1 and Comparative Example 2, the surface tension was measured at 25 ° C. using a ring method (a tensiometer K11 model device manufactured by KRUSS). The results are shown in Table 5 below.
- the comparative example 2 of the comparative example including an oligomer containing an acrylate unit and a urethane unit It can be seen that the surface tension is higher than that of the gel polymer electrolyte.
- the affinity with the separator can be improved due to the high surface tension, thereby reducing the resistance and improving the ion conductivity. It can be expected that the improvement of cycle life characteristics can be realized.
- the cell including the gel polymer electrolyte prepared in Example 7 and Comparative Example 4 was decomposed to separate the separator containing the gel polymer electrolyte, and then the separated separator was placed in a chamber at 60 ° C. and 120 ° C. for about 30 minutes. After leaving for a minute, the degree of shrinkage of the membrane before and after the heat treatment was compared. The results (ratios) are shown in Table 6 below.
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Abstract
Description
이온 전도도 | |
실시예 1 | 8.4mS/cm |
실시예 2 | 8.1mS/cm |
실시예 5 | 6.5mS/cm |
실시예 6 | 4.8mS/cm |
비교예 1 | 7.0mS/cm |
젤 폴리머 전해질용 조성물 | Li+ 이온이동계수 |
실시예 1 | 0.435 |
실시예 2 | 0.420 |
실시예 5 | 0.382 |
실시예 6 | 0.310 |
비교예 1 | 0.402 |
이차전지 | 미반응 올리고머 (중량%) |
실시예 7 | N.D |
실시예 8 | 0.5% |
실시예 9 | N.D |
실시예 10 | 2% |
비교예 3 | 3.0% |
1st 사이클 방전 용량 | 100th 사이클 방전 용량 | 100th 사이클에서의 용량 유지율(%) | |
실시예 7 | 754mAh | 739mAh | 98% |
실시예 8 | 751mAh | 728mAh | 97% |
실시예 9 | 730mAh | 715mAh | 98% |
실시예 10 | 683mAh | 417mAh | 61% |
비교예 3 | 720mAh | 117mAh | 16.2% |
표면장력 (mN/m) | |
실시예 1 | 29mN/m |
비교예 2 | 21mN/m |
분리막의 면적 (cm2) | |||
25℃ | 60℃ | 120℃ | |
실시예 7 | 20.52 | 19.76 | 19.38 |
비교예 4 | 20.52 | 14.82 | 11.55 |
Claims (46)
- 폴리머 네트워크; 및상기 폴리머 네트워크 상에 함침되어 있는 전해액을 포함하며,상기 폴리머 네트워크는 적어도 하나 이상의 공중합성 아크릴레이트 또는 아크릴산을 포함하는 단량체로부터 유도된 단위 A, 우레탄을 포함하는 단위 C, 및 실록산을 포함하는 단위 E를 포함하는 제1 올리고머가 3차원 구조로 결합되어 형성된 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 제1 올리고머는 하기 화학식 1로 표시되는 것을 특징으로 하는 젤 폴리머 전해질:[화학식 1]A-[C-E]k-C-A상기 식에서,k는 1 내지 200의 정수이다.
- 청구항 1에 있어서,상기 단위 C는 하기 화학식 2a 또는 화학식 2b로 표시되는 단위를 포함하는 것을 특징으로 하는 젤 폴리머 전해질:[화학식 2a][화학식 2b]상기 식에서,R'은 탄소수 1 내지 10의 선형 또는 비선형 알킬렌기, 탄소수 3 내지 10의 치환 또는 비치환된 사이클로알킬렌기, 탄소수 6 내지 20의 치환 또는 비치환된 바이사이클로알킬렌기, 탄소수 6 내지 20의 치환 또는 비치환된 아릴렌기, 탄소수 6 내지 20의 치환 또는 비치환된 바이아릴렌기, 탄소수 6 내지 20의 치환 또는 비치환된 아릴렌기, 나프탈렌기 및 안트라센기로 이루어진 군으로부터 선택된 적어도 하나이다.
- 청구항 1에 있어서,상기 단위 E는 하기 화학식 3으로 표시되는 단위를 포함하는 것을 특징으로 하는 젤 폴리머 전해질:[화학식 3]상기 식에서,R1 및 R2는 탄소수 1 내지 5의 선형 또는 비선형 알킬렌기이고,R3 및 R4는 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기 및 페닐기로 이루어진 군으로부터 선택된 하나이며,R5 내지 R10는 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기, 페닐기, 및 불소로 이루어진 군으로부터 선택된 하나이고,o는 0 또는 1의 정수이고,p는 0 또는 1 내지 400의 정수이고,r은 1 내지 400의 정수이며,상기 p:r의 몰비는 0:100 내지 80:20이다.
- 청구항 1에 있어서,상기 제1 올리고머 1몰 중에서 단위 A는 1몰 또는 2몰이고,상기 단위 C : 단위 E의 몰비는 1.005:1 내지 2:1인 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 제1 올리고머는 선택적으로 하기 화학식 4로 표시되는 단위 B 및 하기 화학식 5로 표시되는 단위 D로 이루어진 군으로부터 선택된 적어도 하나 이상의 단위를 더 포함하는 것을 특징으로 하는 젤 폴리머 전해질.[화학식 4]*-CO-R''-O-*[화학식 5]*-O-[R'''-O]m-*상기 식에서,R''는 탄소수 1 내지 10의 치환 또는 비치환된 선형의 알킬렌기, 또는 탄소수 1 내지 10의 치환 또는 비치환된 비선형의 알킬렌기이고,R'''는 탄소수 1 내지 10의 치환 또는 비치환된 선형의 알킬렌기, 또는 탄소수 1 내지 10의 치환 또는 비치환된 비선형의 알킬렌기이고,m은 1 내지 30의 정수이다.
- 청구항 9에 있어서,상기 단위 B는 하기 그룹으로부터 이루어진 군으로부터 선택된 적어도 하나의 화합물인 것을 특징으로 하는 젤 폴리머 전해질.*-CO-CH2CH2-O-* (B-i)*-CO-CHCH3CH2-O-* (B-ii)*-CO-CH2CH2CH2CH2 CH2-O-* (B-iii)*-CO-CHCH3CH2CH2-O-* (B-iv)
- 청구항 9에 있어서,상기 단위 D는 하기 그룹으로부터 이루어진 군으로부터 선택된 적어도 하나의 화합물인 것을 특징으로 하는 젤 폴리머 전해질.*-O-CH2CH2-O-* (D-i)*-O-CHCH3CH2-O-* (D-ii)
- 청구항 9에 있어서,상기 제1 올리고머는 하기 화학식 6a 내지 6c로 이루어진 군으로부터 선택된 적어도 하나로 표시되는 것을 특징으로 하는 젤 폴리머 전해질.[화학식 6a][A]s-[B]n-[C-E-]k-C-[B]n-A[화학식 6b][A]s-[C-D-E-D]k-C-A[화학식 6c][A]s-[B]n-[C-D-E-D]k-C-[B]n-A.상기 식에서,n은 0 또는 1 내지 30의 정수이고,k는 1 내지 200의 정수이며,s는 0 또는 1이다.
- 청구항 9에 있어서,상기 제1 올리고머 1몰 중에서 상기 단위 A는 1몰 또는 2몰이고,상기 단위 B : 단위 C : 단위 D : 단위 E의 몰비는 0 내지 35 : 2 내지 201 : 0 내지 35 : 1 내지 200 (이때, 단위 B 및 D는 동시에 0은 아니다)인 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 젤 폴리머 전해질은 메틸 아크릴레이트, 메틸 메타크릴레이트, 에틸 아크릴레이트, 에틸 메타크릴레이트, 프로필 아크릴레이트, 프로필 메타크릴레이트, 부틸 아크릴레이트, 부틸 메타크릴레이트, 헥실 아크릴레이트, 헥실 메타크릴레이트, 에틸헥실 아크릴레이트, 에틸헥실 메타크릴레이트, 2,2,2-트리플루오로에틸 아크릴레이트, 2,2,2-트리플루오로에틸 메타크릴레이트, 2,2,3,3-테트라플루오로프로필 아크릴레이트, 및 2,2,3,3-테트라플루오로프로필 메타크릴레이트로 이루어진 군으로부터 선택된 적어도 하나로부터 유도된 단위를 포함하는 제2 올리고머를 더 포함하는 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 15에 있어서,상기 제2 올리고머는 제1 올리고머의 전체 함량을 기준으로 50중량% 이하로 포함되는 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 폴리머 네트워크는 폴리머 네트워크 상에 무기물 입자를 추가로 함유하는 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 제1 올리고머의 중량평균분자량은 1,000 내지 100,000인 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 젤 폴리머 전해질은 25℃ 온도에서 1.0?10-4S/cm 내지 2.0?10-2S/cm의 Li+ 이온전도도를 가지는 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 젤 폴리머 전해질은 25℃ 온도에서 0.3 이상의 Li+ 이온 이동계수를 가지는 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 젤 폴리머 전해질은 25℃ 온도에서 젤 함량이 1 중량% 이상인 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 1에 있어서,상기 젤 폴리머 전해질은 25℃ 온도에서 반응성 올리고머 전체 투입량 대비 미반응 올리고머의 함량이 20% 이하인 것을 특징으로 하는 젤 폴리머 전해질.
- 적어도 하나 이상의 공중합성 아크릴레이트 또는 아크릴산을 포함하는 단량체로부터 유도된 단위 A;우레탄을 포함하는 단위 C; 및실록산을 포함하는 단위 E를 포함하는 것을 특징으로 하는 젤 폴리머 전해질.
- 실록산을 포함하는 단위를 함유하는 올리고머를 포함하며,25℃ 온도에서 1.0x10-4S/cm 내지 2.0x10-2S/cm의 Li+ 이온전도도와,0.3 이상의 Li+ 이온 이동계수, 및반응성 올리고머 전체 투입량 대비 미반응 올리고머의 함량이 20% 이하인 것을 특징으로 하는 젤 폴리머 전해질.
- 리튬염,전해액 용매,중합개시제, 및적어도 하나 이상의 공중합성 아크릴레이트 또는 아크릴산을 포함하는 단량체로부터 유도된 단위 A, 우레탄을 포함하는 단위 C, 및 실록산을 포함하는 단위 E를 포함하는 제1 올리고머를 포함하는 젤 폴리머 전해질을 포함하는 청구항 1에 기재된 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 제1 올리고머는 젤 폴리머 전해질용 조성물 전체 중량에 대해 0.5 중량% 내지 20 중량%로 포함되는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 제1 올리고머는 하기 화학식 1로 표시되는 것을 특징으로 하는 젤 폴리머 전해질용 조성물:[화학식 1]A-[C-E]k-C-A상기 식에서,k는 1 내지 200의 정수이다.
- 청구항 25에 있어서,상기 단위 C는 하기 화학식 2a 또는 화학식 2b로 표시되는 단위인 것을 특징으로 하는 젤 폴리머 전해질용 조성물:[화학식 2a][화학식 2b]상기 식에서,R'은 탄소수 1 내지 10의 선형 또는 비선형 알킬렌기, 탄소수 3 내지 10의 치환 또는 비치환된 사이클로알킬렌기, 탄소수 6 내지 20의 치환 또는 비치환된 바이사이클로알킬렌기, 탄소수 6 내지 20의 치환 또는 비치환된 아릴렌기, 탄소수 6 내지 20의 치환 또는 비치환된 바이아릴렌기, 탄소수 6 내지 20의 치환 또는 비치환된 아릴렌기, 나프탈렌기 및 안트라센기로 이루어진 군으로부터 선택된 적어도 하나이다.
- 청구항 25에 있어서,상기 단위 E는 하기 화학식 3으로 표시되는 단위인 것을 특징으로 하는 젤 폴리머 전해질용 조성물:[화학식 3]상기 식에서,R1 및 R2는 탄소수 1 내지 5의 선형 또는 비선형 알킬렌기이고,R3 및 R4는 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기 및 페닐기로 이루어진 군으로부터 선택된 하나이며,R5 내지 R10는 각각 독립적으로 수소, 탄소수 1 내지 5의 알킬기, 페닐기, 및 불소로 이루어진 군으로부터 선택된 하나이고,o는 0 또는 1의 정수이고,p는 0 또는 1 내지 400의 정수이고,r은 1 내지 400의 정수이며,상기 p:r의 몰비는 0:100 내지 80:20이다.
- 청구항 25에 있어서,상기 제1 올리고머 1몰 중에서 단위 A는 1몰 또는 2몰이고,상기 단위 C : 단위 E의 몰비는 1.005:1 내지 2:1인 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 제1 올리고머는 선택적으로 하기 화학식 4로 표시되는 단위 B 및 하기 화학식 5로 표시되는 단위 D로 이루어진 군으로부터 선택된 적어도 하나 이상의 단위를 더 포함하는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.[화학식 4]*-CO-R''-O-*[화학식 5]*-O-[R'''-O]m-*상기 식에서,R''는 탄소수 1 내지 10의 치환 또는 비치환된 선형의 알킬렌기, 또는 탄소수 1 내지 10의 치환 또는 비치환된 비선형의 알킬렌기이고,R'''는 탄소수 1 내지 10의 치환 또는 비치환된 선형의 알킬렌기, 또는 탄소수 1 내지 10의 치환 또는 비치환된 비선형의 알킬렌기이고,m은 1 내지 30의 정수이다.
- 청구항 32에 있어서,상기 올리고머는 하기 화학식 6a 내지 6c로 이루어진 군으로부터 선택된 적어도 하나로 표시되는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.[화학식 6a][A]s-[B]n-[C-E-]k-C-[B]n-A[화학식 6b][A]s-[C-D-E-D]k-C-A[화학식 6c][A]s-[B]n-[C-D-E-D]k-C-[B]n-A.상기 식에서,n은 0 또는 1 내지 30의 정수이고,k는 1 내지 200의 정수이며,s는 0 또는 1이다.
- 청구항 32에 있어서,상기 올리고머 1몰 중에서 단위 A는 1몰 또는 2몰이고,단위 B : 단위 C : 단위 D : 단위 E의 몰비는 0 내지 35 : 2 내지 201 : 0 내지 35 : 1 내지 200 (이때, 단위 B 및 D는 동시에 0은 아니다)인 것을 특징으로 하는 젤 폴리머 전해질.
- 청구항 25에 있어서,상기 폴리머 네트워크는 폴리머 네트워크 상에 무기물 입자를 추가로 함유하는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 올리고머의 중량평균분자량은 1,000 내지 100,000인 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 중합개시제는벤조일 퍼옥사이드, 아세틸 퍼옥사이드, 디라우릴 퍼옥사이드, 디-tert-부틸 퍼옥사이드, t-부틸 퍼옥시-2-에틸-헥사노에이트, 큐밀 하이드로퍼옥사이드, 하이드로겐 퍼옥사이드, 2,2'-아조비스(2-시아노부탄), 2,2'-아조비스(메틸부티로니트릴), AIBN(2,2'-Azobis(iso-butyronitrile)) 및 AMVN(2,2'-Azobisdimethyl-Valeronitrile)로 이루어진 군으로부터 선택되는 단일물 또는 2종 이상의 혼합물인 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 중합개시제는 올리고머 전체 함량에 대해 0.01 중량% 내지 2 중량%로 포함되는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 리튬염은 LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiN(C2F5SO2)2, LiN(CF3SO2)2, CF3SO3Li, LiC(CF3SO2)3, LiC4BO8, LiTFSI, LiFSI, 및 LiClO4로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물인 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 리튬염은 상기 중합개시제와 올리고머의 전체 함량에 대해 10 내지 50 중량%를 포함하는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 25에 있어서,상기 전해액 용매는 선형 카보네이트, 환형 카보네이트 또는 이들의 조합인 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 청구항 42에 있어서,상기 선형 카보네이트는 디메틸 카보네이트, 디에틸 카보네이트, 디프로필 카보네이트, 에틸메틸 카보네이트, 메틸프로필 카보네이트 및 에틸프로필 카보네이트로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하고, 상기 환형 카보네이트는 에틸렌 카보네이트, 프로필렌 카보네이트, 1,2-부틸렌 카보네이트, 2,3-부틸렌 카보네이트, 1,2-펜틸렌 카보네이트, 2,3-펜틸렌 카보네이트, 비닐렌 카보네이트, 및 이들의 할로겐화물로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 포함하는 것을 특징으로 하는 젤 폴리머 전해질용 조성물.
- 리튬의 흡장?방출이 가능한 양극과 음극, 및 상기 양극과 음극 사이에 배치되는 폴리머 전해질을 포함하며,상기 폴리머 전해질은 청구항 1 에 기재된 젤 폴리머 전해질을 포함하는 것을 특징으로 하는 리튬 이차전지.
- 청구항 44에 있어서,상기 리튬 이차전지의 충전 전압은 2.5V 내지 5.0V인 것을 특징으로 하는 리튬 이차전지.
- 제1전극, 제2전극, 전기 변색 물질 및청구항 1에 기재된 젤 폴리머 전해질을 포함하는 전기 변색 소자.
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US15/515,547 US10243239B1 (en) | 2014-10-02 | 2015-10-02 | Gel polymer electrolyte and lithium secondary battery comprising the same |
EP15847219.1A EP3203565B1 (en) | 2014-10-02 | 2015-10-02 | Gel polymer electrolyte and lithium secondary battery comprising same |
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CN108886165A (zh) * | 2016-12-08 | 2018-11-23 | 株式会社Lg化学 | 用于锂二次电池的电解质和包括该电解质的锂二次电池 |
CN110603681A (zh) * | 2017-11-13 | 2019-12-20 | 株式会社Lg化学 | 用于凝胶聚合物电解质的组合物、由该组合物制备的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 |
US20200358065A1 (en) * | 2017-10-31 | 2020-11-12 | Lg Chem, Ltd. | Separator having no separator substrate and electrochemical device including the same |
EP3694040A4 (en) * | 2018-01-03 | 2020-12-16 | Lg Chem, Ltd. | COMPOSITION OF POLYMERIC ELECTROLYTE GEL, POLYMERIC ELECTROLYTE GEL PREPARED FROM THE LATTER, AND SECONDARY LITHIUM BATTERY CONTAINING THE SAID COMPOSITION |
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US20210194052A1 (en) * | 2017-11-30 | 2021-06-24 | Lg Chem, Ltd. | Composition for gel polymer electrolyte, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the same |
US20210359342A1 (en) * | 2018-09-21 | 2021-11-18 | Lg Chem, Ltd. | Composition for gel polymer electrolyte and lithium secondary battery including gel polymer electrolyte formed therefrom |
US11316194B2 (en) | 2018-01-03 | 2022-04-26 | Lg Energy Solution, Ltd. | Gel polymer electrolyte composition, gel polymer electrolyte prepared thereby, and lithium secondary battery including the gel polymer electrolyte |
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CN108886165A (zh) * | 2016-12-08 | 2018-11-23 | 株式会社Lg化学 | 用于锂二次电池的电解质和包括该电解质的锂二次电池 |
US20200358065A1 (en) * | 2017-10-31 | 2020-11-12 | Lg Chem, Ltd. | Separator having no separator substrate and electrochemical device including the same |
US11990641B2 (en) * | 2017-10-31 | 2024-05-21 | Lg Energy Solution, Ltd. | Separator having no separator substrate and electrochemical device including the same |
US11411248B2 (en) | 2017-11-13 | 2022-08-09 | Lg Energy Solution, Ltd. | Composition for gel polymer electrolyte including siloxane oligomer, lithium salt, and phosphate or boron-based anion stabilizing additive, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the gel polymer electrolyte |
CN110603681A (zh) * | 2017-11-13 | 2019-12-20 | 株式会社Lg化学 | 用于凝胶聚合物电解质的组合物、由该组合物制备的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 |
US12062756B2 (en) * | 2017-11-30 | 2024-08-13 | Lg Energy Solution, Ltd. | Composition for gel polymer electrolyte, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the same |
US20210194052A1 (en) * | 2017-11-30 | 2021-06-24 | Lg Chem, Ltd. | Composition for gel polymer electrolyte, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the same |
US11581578B2 (en) * | 2017-11-30 | 2023-02-14 | Lg Energy Solution, Ltd. | Composition for gel polymer electrolyte including siloxane oligomer and styrene-based oligomer, gel polymer electrolyte prepared therefrom, and lithium secondary battery including the same |
EP3694040A4 (en) * | 2018-01-03 | 2020-12-16 | Lg Chem, Ltd. | COMPOSITION OF POLYMERIC ELECTROLYTE GEL, POLYMERIC ELECTROLYTE GEL PREPARED FROM THE LATTER, AND SECONDARY LITHIUM BATTERY CONTAINING THE SAID COMPOSITION |
US11316194B2 (en) | 2018-01-03 | 2022-04-26 | Lg Energy Solution, Ltd. | Gel polymer electrolyte composition, gel polymer electrolyte prepared thereby, and lithium secondary battery including the gel polymer electrolyte |
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EP3780235A4 (en) * | 2018-08-16 | 2021-06-02 | Lg Chem, Ltd. | ELECTROLYTE FOR LITHIUM SECONDARY BATTERY |
US20210359342A1 (en) * | 2018-09-21 | 2021-11-18 | Lg Chem, Ltd. | Composition for gel polymer electrolyte and lithium secondary battery including gel polymer electrolyte formed therefrom |
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