Solid polymer electrolyte composite composition, solid polymer electrolyte formed therefrom, and secondary battery comprising same

Abstract

The present invention relates to a solid polymer electrolyte composite composition that, by utilizing an oxide, exhibits improved ionic conductivity and mechanical strength compared to conventional solid polymer electrolytes, thereby enhancing electrochemical properties and stability. The present invention includes a compound having a structure represented by chemical formula 1. [Chemical formula 1]

Description

Solid polymer electrolyte complex composition, solid polymer electrolyte formed therefrom, and secondary battery comprising the same

[0001] The present invention relates to a lithium ion secondary battery and a solid polymer electrolyte used therein.

[0002] Secondary batteries are rechargeable and dischargeable. Lithium-ion secondary batteries, in particular, are widely studied and used due to their superior energy density and output characteristics among various secondary batteries.

[0003] Typically, lithium-ion secondary batteries consist of a positive electrode, a negative electrode, and an electrolyte. The electrolyte is a substance that enables the movement of lithium ions (Li+) between the positive and negative electrodes, and liquid electrolytes are widely used.

[0004] However, liquid electrolytes have inherent risks, such as electrolyte leakage due to deformation or external impact, short circuits caused by damage to the separator, and the risk of overheating or explosion. To address these issues, all-solid-state batteries, which replace liquid electrolytes with solid electrolytes, are gaining attention as next-generation secondary batteries.

[0005] The electrolytes of all-solid-state batteries developed to date can be generally classified into solid electrolytes such as polymer (organic) solid electrolytes, sulfides, oxides, and composite materials, depending on the material.

[0006] In particular, polymer (organic) solid electrolytes have superior advantages over inorganic solid electrolytes in terms of flexibility, lightness, processability, and cost.

[0007] Polymer solid electrolytes were first developed using poly-ethylene oxide (PEO) and alkaline salts, and are currently commonly used in the form of polymer materials such as poly-ethylene oxide (PEO), poly-vinylidene fluoride (PVdF), and poly-acrylonitrile (PAN) and lithium salts.

[0008] However, existing polymer electrolytes have the problem of being easily crystallized and having low ionic conductivity at low temperatures, resulting in limited output characteristics.

[0009] The problem to be solved by the present invention is to provide a solid polymer electrolyte composite composition having improved electrochemical properties and stability by utilizing oxides and having improved ionic conductivity and mechanical strength compared to existing solid polymer electrolytes.

[0010] One aspect of the present invention is a solid polymer electrolyte composite composition comprising a compound having a structure represented by the following chemical formula 1 and an oxide.

[0011] [Chemical Formula 1]

[0012] [Correction pursuant to Rule 91, September 19, 2025]

[0013] In the above chemical formula 1,

[0014] A1 is substituted or unsubstituted C1~C 10 alkylene group, substituted or unsubstituted C5~C 12 Cycloalkylene group, substituted or unsubstituted C6~C 18 Arylene group, substituted or unsubstituted C2~C 18 A heteroarylene group, an alkylene oxide group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group; or a combination of two or more of the above,

[0015] A2 is substituted or unsubstituted C1~C 10 alkylene group, substituted or unsubstituted C5~C 12 Cycloalkylene group, substituted or unsubstituted C6~C 18 Arylene group, substituted or unsubstituted C2~C 18 A heteroarylene group, an alkylene oxide group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group; or a combination of two or more of the above,

[0016] [Correction under Rule 91 19.09.2025] X is C2-C 18 Alkylene oxide group, C1~C 10 alkylene group, C5~C 12 Cycloalkylene group, C6~C 10 Arylene group, C2~C 18 A heteroarylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group, a hydroxy group, a thiol group; or a combination of two or more of the above, or and At least one selected from the group consisting of,

[0017] n is 1-100.

[0018] In the present invention, the compound having a structure represented by the chemical formula 1 may be a compound having one structure selected from the group consisting of the following chemical formulas 1-1 to 1-3.

[0019] [Chemical Formula 1-1]

[0020] [Correction pursuant to Rule 91, September 19, 2025]

[0021] [Chemical Formula 1-2]

[0022] [Correction pursuant to Rule 91, September 19, 2025]

[0023] [Chemical Formula 1-3]

[0024] [Correction pursuant to Rule 91, September 19, 2025]

[0025] In the present invention, the solid polymer electrolyte complex composition may further include a monofunctional methacrylate-based monomer.

[0026] In the present invention, the monofunctional methacrylate-based monomer may be at least one selected from the group consisting of polyethylene glycol methyl ether methacrylate, polyethylene glycol methacrylate, methylene methacrylate, ethylene methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate.

[0027] In the present invention, the weight ratio of the monofunctional methacrylate monomer and the compound having the structure represented by the chemical formula 1 may be 95:5 to 50:50.

[0028] In the present invention, the solid polymer electrolyte complex composition further includes a lithium salt, and the content of the lithium salt may be 10 to 50 parts by weight based on 100 parts by weight of a mixture of a compound having a structure represented by the chemical formula 1 and the methacrylate-based monomer.

[0029] In the present invention, the solid polymer electrolyte complex composition may further include a surfactant or an initiator.

[0030] In the present invention, the content of the oxide may be 10 to 50 parts by weight based on 100 parts by weight of a mixture of a compound having a structure represented by the chemical formula 1 and the methacrylate-based monomer.

[0031] Another aspect of the present invention provides a solid polymer electrolyte formed by curing the above-described solid polymer electrolyte complex composition.

[0032] Another aspect of the present invention provides a secondary battery comprising a positive electrode, a negative electrode, and the aforementioned solid polymer electrolyte.

[0033] The solid polymer electrolyte complex composition according to the present invention contains a compound having a structure represented by chemical formula 1 and an oxide, and can improve ion conductivity and transference number when applied as a solid electrolyte of a secondary battery.

[0034] In addition, the solid polymer electrolyte formed by curing the solid polymer electrolyte complex composition can improve the stability of the secondary battery.

[0035] Hereinafter, the present invention will be described in more detail with reference to exemplary embodiments, examples, etc. so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in various different forms and is not limited to the embodiments, examples, etc. described herein.

[0036]

[0037] In this specification, the phrase "substituted or unsubstituted" means that a substituent is substituted by an arbitrary or specific functional group, and is not substituted. The case of being substituted means that an arbitrary or specific functional group is bonded to one or more carbons of the substituent.

[0038] The functional group substituted here is, for example, alkyl, acyl, cycloalkyl (including dicycloalkyl and tricycloalkyl), haloalkyl, aryl, heteroaryl, heteroalicyclic, hydroxy, alkoxy, azide, amine, ketone, ether, amide, ester, triazole, isocyanate, arylalkyloxy, aryloxy, mercapto, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, O-carboxy, isocyanate, thiocyanate, isothiocyanate, nitro, silyl, trihalomethane sulfonyl, pyrrolidone, pyrrolidine, piperidine, piperazine, morpholine, aldehyde, phosphorus, Sulfur, phosphate, phosphite, sulfate,It may be selected from amino and their derivatives, including disulfide, oxy, and hydrocarbylmono- and di-substituted amino groups. In addition to these, various types of functional groups may be applied.

[0039] The term “alkylene group” as used herein refers to a divalent aliphatic hydrocarbon group. The alkylene group may be, for example, one selected from methylene, ethylene, propylene, butylene, pentylene, and hexylene.

[0040] Additionally, the term “straight-chain alkylene group” used herein means an alkylene group in which all carbons in the alkylene group are secondary carbons, and “branched alkylene group” means an alkylene group in which at least one of the carbons in the alkylene group is a tertiary carbon or a quaternary carbon.

[0041] The term "cycloalkylene group" as used herein refers to a divalent aliphatic cyclic hydrocarbon group, and the positional relationship of the divalent bonding arm is not limited. For example, it can be selected from the group consisting of a 1,2-cycloalkylene group, a 1,3-cycloalkylene group, a 1,4-cycloalkylene group, and a 1,5-cycloalkylene group. Cycloalkylene groups include, for example, 1,2-cyclobutylene, 1,3-cyclobutylene, 1,2-cyclopentylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,2-cycloheptylene, 1,3-cycloheptylene, 1,4-cycloheptylene, 1,2-cyclooctylene, It can be selected from 1,3-cyclooctylene, 1,4-cyclooctylene, and 1,5-cyclooctylene.

[0042] The term “arylene group” as used herein refers to a divalent aromatic substituent. An arylene group is a form of an aryl group with one additional bonding arm.

[0043] As used herein, the term “heteroarylene group” is an aromatic substituent having a divalent shared pi electron system. A heteroarylene group is a heteroaryl group with one additional bonding arm.

[0044] As used herein, the term "heteroalkyl group" means one or more carbon atoms in the carbon chain of an alkyl group are replaced with a heteroatom.

[0045] As used herein, the term "heteroalkylene group" means one or more carbon atoms in the carbon chain of an alkylene group are replaced with a heteroatom.

[0046] As used herein, the term “heteroatom” means an atom other than carbon and hydrogen.

[0047] As used herein, the term "alkyl group" refers to a monovalent aliphatic hydrocarbon group. Alkyl groups include unbranched and branched groups. The alkyl group may be, for example, one or more selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, n-pentyl, and n-hexyl.

[0048] As used herein, "cycloalkyl group" means a monovalent aliphatic cyclic hydrocarbon group. The cycloalkyl group may be selected from the group consisting of, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.

[0049] As used herein, the term "haloalkyl group" means an alkyl group in which one or more hydrogen atoms are replaced with a halogen (F, Cl, Br, I) atom.

[0050] As used herein, the term "amide group" refers to a -C(O)NH- bond. The hydrogen bonded to the nitrogen in the amide bond may be substituted or unsubstituted.

[0051] Additionally, in this specification, the phrase "no substituent" means that the atoms on both sides are directly bonded without the substituent. For example, in a molecule of the form CH3-A-CH3, if the substituent A is not present, the chemical formula of the molecule is CH3-CH3.

[0052]

[0053] Hereinafter, the present invention will be described in detail.

[0054] One aspect of the present invention is a solid polymer electrolyte complex composition comprising a compound having a structure represented by the following chemical formula 1 and an oxide.

[0055] [Chemical Formula 1]

[0056] [Correction pursuant to Rule 91, September 19, 2025]

[0057] In the above chemical formula 1, A1 is substituted or unsubstituted C1~C 10 alkylene group, substituted or unsubstituted C5~C 12 Cycloalkylene group, substituted or unsubstituted C6~C 18 Arylene group, substituted or unsubstituted C2~C 18 A heteroarylene group, an alkylene oxide group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group; or a combination of two or more of the above.

[0058] The above A2 is substituted or unsubstituted C1~C 10 alkylene group, substituted or unsubstituted C5~C 12 Cycloalkylene group, substituted or unsubstituted C6~C 18 Arylene group, substituted or unsubstituted C2~C 18A heteroarylene group, an alkylene oxide group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group; or a combination of two or more of the above.

[0059] The above X is C2-C 18 Alkylene oxide group, C1~C 10 alkylene group, C5~C 12 Cycloalkylene group, C6~C 10 Arylene group, C2~C 18 A heteroarylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group, a hydroxy group, a thiol group; or a combination of two or more of the above, or and At least one species selected from the group consisting of , and n is 1-100.

[0060] Here, when two or more substituents are combined, the two combined substituents can be combined with -O-, -S-, -C(O)O- or -C(O)NH-. In addition, the branched alkylene group and the haloalkylene group are C5~C 18 Cycloalkyl group of C6~C- 18 Aryl group and C3~C 18 It can be substituted with a heteroaryl group. Here, the substituents can be combined in multiple ways. For example, it can be -alkylene-alkylene- or -arylene-arylene-. In addition, two adjacent homogeneous substituents can be the same or not.

[0061] Additionally, the bond between the two bonded substituents can be -O-, -S-. For example, O can be bonded between the two bonded substituents, such as -CH2CH2-O-CH2CH2CH2-.

[0062] [Revised 19.09.2025 by Rule 91] In the present invention, X in chemical formula 1 is preferably and It may be one or more selected from the group consisting of .

[0063] For example, the compound having a structure represented by the above chemical formula 1 may be a compound having one structure selected from the group consisting of the following chemical formulas 1-1 to 1-3.

[0064] [Chemical Formula 1-1]

[0065] [Correction pursuant to Rule 91, September 19, 2025]

[0066] [Chemical Formula 1-2]

[0067] [Correction pursuant to Rule 91, September 19, 2025]

[0068] [Chemical Formula 1-3]

[0069] [Correction pursuant to Rule 91, September 19, 2025]

[0070] Additionally, the weight average molecular weight of the compound represented by Chemical Formula 1-1 may be 2,000 g / mol to 100,000 g / mol, and preferably 4,000 g / mol to 20,000 g / mol.

[0071] If the weight average molecular weight of the compound represented by Chemical Formula 1-1 is less than 2,000 g / mol, there is a problem of reduced electrochemical stability and mechanical strength when manufacturing a battery with a polymer electrolyte, and if it exceeds 100,000 g / mol, there is a problem of reduced ionic conductivity.

[0072] Additionally, the weight average molecular weight of the compound represented by Chemical Formula 1-2 may be 2,000 g / mol to 100,000 g / mol, and preferably 4,000 g / mol to 20,000 g / mol.

[0073] If the weight average molecular weight of the compound represented by Chemical Formula 1-2 is less than 2,000 g / mol, there is a problem of reduced electrochemical stability and mechanical strength when manufacturing a battery with a polymer electrolyte, and if it exceeds 100,000 g / mol, there is a problem of reduced ionic conductivity.

[0074] Additionally, the weight average molecular weight of the compound represented by Chemical Formula 1-3 may be 2,000 g / mol to 100,000 g / mol, and preferably 4,000 g / mol to 20,000 g / mol.

[0075] If the weight average molecular weight of the compound represented by Chemical Formula 1-3 is less than 2,000 g / mol, there is a problem of reduced electrochemical stability and mechanical strength when manufacturing a battery with a polymer electrolyte, and if it exceeds 100,000 g / mol, there is a problem of reduced ionic conductivity.

[0076] In the present invention, the solid polymer electrolyte complex composition may further include a monofunctional methacrylate-based monomer.

[0077] In the present invention, the weight ratio of the monofunctional methacrylate monomer and the compound having the structure represented by the chemical formula 1 may be 95:5 to 50:50, and preferably 95:5 to 80:20.

[0078] In the weight ratio of the monofunctional methacrylate monomer and the compound having the structure represented by the above chemical formula 1, if the weight ratio of the monofunctional methacrylate monomer exceeds 95, there is a problem that mechanical strength is reduced and a film is not formed, and if it is less than 50, there is a problem that ionic conductivity is reduced.

[0079] The monofunctional methacrylate-based monomer may be at least one selected from the group consisting of polyethylene glycol methyl ether methacrylate, polyethylene glycol methacrylate, methylene methacrylate, ethylene methacrylate, glycidyl methacrylate, and hydroxyethyl methacrylate, and preferably polyethylene glycol methyl ether metacrylate.

[0080] When curing a solid polymer electrolyte complex composition, the monofunctional methacrylate monomer undergoes polymerization and crosslinking reactions. Consequently, the cured solid polymer electrolyte forms a three-dimensional network structure, resulting in improved mechanical properties.

[0081] In the present invention, the solid polymer electrolyte composite composition may further include a lithium salt. The lithium salt can be used as an electrolyte salt in a lithium secondary battery and functions as a medium for transferring ions. The lithium salt is a cation, Li + , and contains F as an anion. - , Cl - , Br - , I - , NO3 - , N(CN)2 - , ClO4 - , BF4 - , AlO4 - , AlCl4 - , PF6 - , SbF6 - , AsF6 - , BF2C2O4 - , BC4O8 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , CF3SO3 - ,C4F9SO3 - , CF3CF2SO3 - , (CF3SO2)2N - , (FSO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH - , (SF5)3C - , (CF3SO2)3C - , CF3(CF2)7SO3 - ,CF3CO2 - , CH3CO2 - , SCN - and (CF3CF2SO2)2N- It may include at least one selected from the group consisting of .

[0082] The content of the lithium salt may be 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the mixture of the compound having the structure represented by the chemical formula 1 and the methacrylate-based monomer. If the content of the lithium salt is less than 10 parts by weight, the content of lithium ions may be low, resulting in a decrease in ionic conductivity. If the content of the lithium salt exceeds 50 parts by weight, a large amount of lithium salt that forms ion pairs without being solvated in the polymer matrix will exist. Accordingly, the increase in ionic conductivity is low, and is uneconomical.

[0083] In the present invention, the solid polymer electrolyte complex composition may further include a surfactant, a plasticizer, an oxide, or an initiator.

[0084] The surfactant is intended to facilitate mixing between components, and may be at least one selected from the group consisting of polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether, ZONYL FS-300, and sodium laureth sulfate, and sodium laureth sulfate is preferably used.

[0085] The content of the surfactant may be 0.01 to 10 parts by weight based on 100 parts by weight of the mixture of the compound having the structure represented by the above chemical formula 1 and the above methacrylate-based monomer, and preferably 0.05 to 5 parts by weight, and within the above range, mixing between the components is easy, so that the required ionic conductivity can be achieved.

[0086] In the present invention, the initiator causes a crosslinking reaction. The solid polymer electrolyte complex composition can be cured through polymerization and crosslinking reactions to form a solid electrolyte.

[0087] The initiator may be selected from the group consisting of a radical initiator, a photoinitiator and a thermal initiator, and preferably a photoinitiator and a thermal initiator may be used.

[0088] The initiator may be at least one selected from the group consisting of azobicisobutyronitrile, 1-phenyl-2-hydroxy-2-methylpropan-1-one, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, 1-hydroxychlorohexylphenyl ketone, α-aminoacetophenone, benzoin ether, benzyldimethyl ketal, benzophenone, oxanthone, benzoyl peroxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and bis-acyl phosphine (BAPO). IRGACURE 819 can be used as the bis-acyl phosphine (BAPO).

[0089] The content of the initiator may be 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of a mixture of a compound having a structure represented by Chemical Formula 1 and a methacrylate-based monomer, and the crosslinking reaction may easily proceed within the above range.

[0090] In the present invention, the oxide is used to improve ionic conductivity by reducing the crystallinity of the polymer electrolyte and to increase mechanical strength to improve stability, and the oxide is silica (SiO2), alumina (Al2O3), titania (TiO2), palygorskite, Li7La3Zr2O 12 (LLZO), Li 3x La 2 / 3x TiO3(LLTO), Li 10 GeP2S 12 (LGPS), Li1 . 4Al0 . 4Ti1 .6 (PO4)3(LATP), Ga-doped LLZO, Ta-doped LLZO, Li6 . 75 La3Zr1 . 75 Ta0. 25 O 12 (LLZTO) and Li1 . 5Al0 . 5Ge1 .5 It may be at least one selected from the group consisting of (PO4)3(LAGP), and preferably, gallium-doped lithium lanthanum zirconium oxide (Ga-doped LLZO) may be used.

[0091] The content of the oxide may be 10 to 50 parts by weight, and preferably 15 to 30 parts by weight, based on 100 parts by weight of the mixture of the compound having the structure represented by the chemical formula 1 and the methacrylate-based monomer. If the content of the oxide is less than 10 parts by weight or more than 50 parts by weight based on 100 parts by weight of the mixture of the compound having the structure represented by the chemical formula 1 and the methacrylate-based monomer, ionic conductivity may decrease, and therefore the above range is preferred.

[0092] The solid polymer electrolyte complex composition may further include an organic solvent to control viscosity or improve solubility. The organic solvent may be any of various organic solvents commonly used in solid electrolytes without limitation. For example, the organic solvent may be tetrahydrofuran (THF), 2-methyl tetrahydrofuran, dimethylformamide (DMF), acetonitrile, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dichloromethane, acetone, isopropyl alcohol, methyl ethyl ketone (MEK), etc. However, the present invention is not necessarily limited thereto.

[0093] Another aspect of the present invention is a solid polymer electrolyte formed by curing a solid polymer electrolyte complex composition.

[0094] The cured solid polymer electrolyte is applied as a solid electrolyte for secondary batteries. At this time, the solid polymer electrolyte can exhibit an ionic conductivity value of 0.01 to 0.08 mS / cm at room temperature, preferably an ionic conductivity of 0.03 to 0.07 mS / cm, and more preferably an ionic conductivity of 0.04 to 0.07 mS / cm.

[0095] Curing can be carried out by coating a solid electrolyte composition on a Teflon plate, film, electrode, etc. and then irradiating it with ultraviolet light or heat treating it.

[0096] As a coating method, a coating method such as slot die, gravure coating, spin coating, spray coating, roll coating, casting, screen printing or inkjet printing can be used.

[0097] Another aspect of the present invention is a lithium secondary battery comprising a positive electrode, a negative electrode, and a solid electrolyte.

[0098] The solid electrolyte used in a lithium secondary battery can be the solid electrolyte described above.

[0099] A lithium secondary battery can be manufactured, for example, by applying and curing a solid electrolyte composition on a positive electrode and then laminating a negative electrode.

[0100] The positive electrode includes a positive electrode active material. The positive electrode can be manufactured by coating a positive electrode slurry containing a positive electrode active material, a binder, a conductive agent, a solvent, etc. on a positive electrode current collector, followed by drying and rolling.

[0101] The cathode current collector is not particularly limited, as long as it is conductive and does not induce chemical changes in the lithium secondary battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel with a surface treated with carbon, nickel, titanium, silver, etc. may be used as the cathode current collector.

[0102] In addition, the cathode active material is a compound capable of reversible intercalation and deintercalation of lithium. Specifically, the cathode active material may include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel, or aluminum. The lithium composite metal oxide is a lithium-manganese oxide (e.g., LiMnO2, LiMn2O4, etc.), a lithium-cobalt oxide (e.g., LiCoO2, etc.), a lithium-nickel oxide (e.g., LiNiO2, etc.), a lithium-nickel-manganese oxide (e.g., LiNi1 - Y Mn Y O2 (here, 0 <Y<1), LiMn2 -z Ni z O4 (where 0<Z<2), etc.), lithium-nickel-cobalt oxides (e.g., LiNi1 -Y1 CoY1O2(here, 0 <Y1<1) 등), 리튬-망간-코발트계 산화물(예를 들면, LiCo1 -Y2 Mn Y2 O2 (here, 0 <Y2<1), LiMn2 - z1 Co z1 O4 (wherein, 0<Z1<2) etc.), lithium-nickel-manganese-cobalt oxides (e.g., Li(Ni p Co q Mn r1 )O2(wherein, 0<p<1, 0<q<1, 0<r1<1, p+q+r1=1) or Li(Ni p1 Co q1 Mn r2 )O4 (wherein, 0<p1<2, 0<q1<2, 0<r2<2, p1+q1+r2=2) etc.), or lithium-nickel-cobalt-transition metal (M) oxide (e.g., Li(Ni p2 Co q2 Mn r3 M S2)O2 (wherein, M is selected from the group consisting of Al, Fe, V, Cr, Ti, Ta, Mg, and Mo, and p2, q2, r3, and s2 are atomic fractions of independent elements, respectively, such that 0<p2<1, 0<q2<1, 0<r3<1, 0<s2<1, p2+q2+r3+s2=1).

[0103] In terms of being able to improve the capacity characteristics and stability of the battery, the lithium composite metal oxide may be LiCoO2, LiMnO2, LiNiO2, lithium nickel manganese cobalt oxide (e.g., Li(Ni1 / 3Mn1 / 3Co1 / 3)O2, Li(Ni0.6Mn0.2Co0.2)O2, Li(Ni0.5Mn0.3Co0.2)O2, Li(Ni0.7Mn0.15Co0.15)O2, and Li(Ni0.8Mn0.1Co0.1)O2, or lithium nickel cobalt aluminum oxide (e.g., Li(Ni0.8Co0.15Al0.05)O2, etc.).

[0104] The positive electrode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the solid content in the positive electrode slurry.

[0105] A binder is a component that facilitates bonding between a conductive material, an active material, and a current collector. The binder is added in an amount of 1 to 30 wt% based on the total weight of the solid content in the positive electrode slurry. For example, polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terephthalate monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluoroelastomer, etc. can be used as a binder.

[0106] The conductive material is added in an amount of 1 to 30 wt% based on the total weight of the solids in the positive electrode slurry. The conductive material is not particularly limited as long as it is conductive and does not induce chemical changes in the lithium secondary battery. Examples of conductive materials that can be used include carbon powder, conductive fiber, metal powder, graphite powder, conductive whiskers, conductive metal oxides, and polyphenylene derivatives.

[0107] Carbon powders such as carbon black, acetylene black (or Denka black), Ketjen black, channel black, furnace black, lamp black, or thermal black can be used. Graphite powders such as natural graphite, artificial graphite, or graphite with highly developed crystal structures can be used. Carbon fibers or metal fibers can be used as conductive fibers. Fluorinated carbon, aluminum, or nickel powders can be used as metal powders. Zinc oxide, potassium titanate, etc. can be used as conductive whiskers. Titanium oxide, etc. can be used as conductive metal oxides.

[0108] The positive electrode slurry may include a solvent. The solvent may include an organic solvent such as NMP (Nmethyl-2-pyrrolidone). The solvent may be used in an amount that provides a desirable viscosity when including the positive electrode active material and the binder or conductive material. For example, the solvent may be included so that the solid content of the slurry including the positive electrode active material and the binder or conductive material is 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.

[0109] The negative electrode includes a negative electrode active material. The negative electrode can be manufactured by coating a negative electrode slurry including a negative electrode active material, a binder, a conductive agent, a solvent, etc. on a negative electrode current collector, and then drying and rolling the resulting mixture.

[0110] The negative electrode current collector may have a thickness of 3 to 500 μm. The negative electrode current collector is not particularly limited as long as it has high conductivity and does not cause chemical changes in the lithium secondary battery. For example, the negative electrode current collector may be made of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, etc., or may be made of copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., or may be made of an aluminum-cadmium alloy. In addition, like the positive electrode current collector, the negative electrode current collector may have fine unevenness on its surface to improve bonding strength with the negative electrode active material. The negative electrode collector may be made in the form of a film, sheet, foil, net, porous body, foam, non-woven fabric, etc.

[0111] Additionally, the negative electrode active material is lithium metal, a compound capable of reversibly intercalating and deintercalating lithium ions. The negative electrode active material may be selected from the group consisting of carbon materials, metals or alloys of these metals and lithium, metal composite oxides, materials capable of doping and dedoping lithium, and transition metal oxides.

[0112] As a carbon material, any carbon-based negative electrode active material commonly used in lithium-ion secondary batteries may be used without particular restrictions. For example, crystalline carbon, amorphous carbon, or a mixture thereof may be used as the carbon material. As the crystalline carbon, graphite such as natural graphite or artificial graphite in an amorphous, plate-like, flake-like, spherical, or fibrous form may be used, and as the amorphous carbon, soft carbon (low-temperature calcined carbon), hard carbon, mesophase pitch carbide, calcined coke, etc. may be used.

[0113] Metal complex oxides include PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5, LixFe2O3(0≤x≤1), LixWO2(0≤x≤1), and SnxMe1-xMe'yOz (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, elements of group 1, 2, and 3 of the periodic table, halogens; 0 <x≤1; 1≤y≤3; 1≤z≤8) 로 이루어진 군에서 선택되는 것이 사용될 수 있다.

[0114] Si, SiOx(0) as a material capable of doping and dedoping lithium <x≤2), Si-Y 합금(Y는 알칼리 금속, 알칼리토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si은 아님), Sn, SnO2, Sn-Y(Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이 금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 등이 사용될 수 있고, 이들 중 적어도 하나와 SiO2를 혼합하여 사용될 수 있다. 원소 Y로 Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ge, P, As, Sb, Bi, S, Se, Te, Po 및 이들의 조합으로 이루어진 군에서 선택된 원소가 사용될 수 있다.

[0115] Transition metal oxides that can be used include lithium-containing titanium composite oxide (LTO), vanadium oxide, and lithium vanadium oxide.

[0116] The negative electrode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the solid content in the negative electrode slurry.

[0117] A binder is a component that facilitates bonding between the conductive material, active material, and current collector. The binder is added in an amount of 1 to 30 wt% based on the total weight of the solid content in the negative electrode slurry. For example, polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, and fluoroelastomer can be used as the binder.

[0118] A conductive agent is a component that further enhances the conductivity of the negative electrode active material and can be added in an amount of 1 to 20 wt% based on the total weight of the solid content in the negative electrode slurry. The conductive agent may be the same as or different from the conductive agent used in the manufacture of the positive electrode. For example, the conductive agent may include carbon powder, conductive fiber, metal powder, graphite powder, conductive whiskers, conductive metal oxides, and polyphenylene derivatives.

[0119] Carbon powders such as carbon black, acetylene black (or Denka black), Ketjen black, channel black, furnace black, lamp black, or thermal black can be used. Graphite powders such as natural graphite, artificial graphite, or graphite with highly developed crystal structures can be used. Carbon fibers or metal fibers can be used as conductive fibers. Fluorinated carbon, aluminum, or nickel powders can be used as metal powders. Zinc oxide, potassium titanate, etc. can be used as conductive whiskers. Titanium oxide, etc. can be used as conductive metal oxides.

[0120] The negative active material slurry may further include a solvent. The solvent may be water or an organic solvent such as NMP or alcohol, and may be used in an amount that provides a desirable viscosity when including the negative active material and a binder or conductive agent. For example, the solvent may be included so that the solids concentration in the slurry including the negative active material and the binder or conductive agent is 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.

[0121] A lithium secondary battery including a positive electrode, a negative electrode, and a solid electrolyte as described above can exhibit excellent lithium ion mobility and excellent ion conductivity without significantly reducing the output of the lithium secondary battery even at low temperatures because the solid electrolyte is suppressed from crystallizing at low temperatures.

[0122] In addition, a lithium secondary battery according to one aspect of the present invention can be usefully used in portable devices such as mobile phones, laptop computers, and digital cameras, and electric vehicles such as hybrid electric vehicles (HEVs).

[0123] Hereinafter, the present invention will be described in more detail by way of preferred embodiments thereof.

[0124]

[0125] Synthesis Example 1

[0126] In a reactor, 1,4-Butanediol diglycidyl ether and 2,2′-Thiodiethanethiol are added in a 2:1 molar ratio and tetrahydrofuran is used as a solvent to make a 40 wt% solution, then cooled to 0℃. Lithium hydroxide is added in an amount of 1 part by weight per 100 parts by weight of 2,2′-Thiodiethanethiol, and the mixture is reacted for 4 hours while maintaining 0℃. Then, 65 parts by weight of 1,4-Butanediol diglycidyl ether is additionally added per 100 parts by weight of 2,2′-Thiodiethanethiol. After that, acetic acid is added in an amount of 3 parts by weight per 1 part by weight of lithium hydroxide, neutralized, and the filtered solution is washed and precipitated three or more times with ether, and dried in a vacuum oven to obtain a composite. A 10 wt% first solution is prepared using ethyleneglycol dimethacrylate and tetrahydrofuran as a solvent. 2 wt parts of 1,8-Diazabicyclo 5.4.0 undec-7-ene is added to the above compound in an amount of 100 wt parts per compound, and a 30 wt% solution prepared using tetrahydrofuran as a solvent is added dropwise, reacted at room temperature for 2 hours, washed and precipitated at least three times with ether, and freeze-dried at -60°C and 40 mbar for 12 hours to obtain a compound.

[0127]

[0128] Synthesis Example 2

[0129] A 7 wt% first solution is prepared using Tetrahydrofuran as a solvent for Carbonyl diimidazole. A 50 wt% second solution is prepared using Tetrahydrofuran as a solvent for the compound prepared in Synthesis Example 1, and the solution is added dropwise to the first solution. At this time, the amount of Carbonyl diimidazole is 3 parts by weight based on 1 part by weight of the compound prepared in Synthesis Example 1. After adding the solution dropwise, it is reacted at room temperature for 24 hours, and then 4-(Hydroxymethyl)-1,3-dioxolan-2-one is added at a ratio of 1 part by weight to 4 parts by weight of Carbonyl diimidazole. After reacting at room temperature for 20 hours, the mixture is washed and precipitated at least three times with ether and methanol, and freeze-dried at -60°C and 40 mbar for 12 hours to obtain a compound of the following chemical formula 1-1, and the weight average molecular weight of the following chemical formula 1-1 is 5,880 g / mol.

[0130] [Chemical Formula 1-1]

[0131] [Correction pursuant to Rule 91, September 19, 2025]

[0132]

[0133] Synthesis Example 3

[0134] A 7 wt% first solution is prepared using Tetrahydrofuran as a solvent for Carbonyl diimidazole. A 50 wt% second solution is prepared using Tetrahydrofuran as a solvent for the composite prepared in Synthesis Example 1, and the solution is added dropwise to the first solution. At this time, the amount of Carbonyl diimidazole is 2.4 parts by weight based on 1 part by weight of the composite prepared in Synthesis Example 1. After adding the solution dropwise, it is reacted at room temperature for 24 hours, and then 4 parts by weight of ethylene cyanohydrin is added based on 1 part by weight of Carbonyl diimidazole. After reacting at room temperature for 20 hours, washing and precipitation are performed three or more times with ether and methanol, and freeze-drying is performed at -60°C and 40 mbar for 12 hours to obtain a composite of the following chemical formula 1-2, and the weight average molecular weight of the following chemical formula 1-2 is 6,350 g / mol.

[0135] [Chemical Formula 1-2]

[0136] [Correction pursuant to Rule 91, September 19, 2025]

[0137]

[0138] Synthesis Example 4

[0139] A 20 wt% first solution was prepared using Tetrahydrofuran as a solvent for the compound prepared in Synthesis Example 1. A 20 wt% second solution was prepared using Tetrahydrofuran as a solvent for 1,3-propanesultone, and the solution was added dropwise to the first solution. At this time, the amount of 1,3-propanesultone was 3 parts by weight based on 1 part by weight of the compound prepared in Synthesis Example 1. After the solution was added dropwise, it was reacted at room temperature for 20 hours, and then washed and precipitated three or more times with ether and methanol, and freeze-dried at -60°C and 40 mbar for 12 hours to obtain a compound of the following chemical formula 1-3. The weight average molecular weight of the following chemical formula 1-3 was 5,200 g / mol.

[0140] [Chemical Formula 1-3]

[0141] [Correction pursuant to Rule 91, September 19, 2025]

[0142]

[0143] Example 1

[0144] A solid electrolyte composition was prepared using the composite prepared in Synthesis Example 2 as the first monomer, polyethylene glycol methyl ether metacrylate as the second monomer, LiTFSI as the lithium salt, sodium laureth sulfate as the additive (surfactant), and Ga-doped LLZO as the oxide.

[0145] Specifically, a mixture was prepared by mixing the first monomer and the second monomer at a weight ratio of 15:85. Thereafter, 30 parts by weight and 1 part by weight of a lithium salt and an additive were added, respectively, based on 100 parts by weight of the mixture. Thereafter, irgacure 819 as a photoinitiator and Azobisisobutyronitrile as a thermal initiator were each added at 0.5 parts by weight based on 100 parts by weight of the mixture, and 20 parts by weight of an oxide was added based on 100 parts by weight of the mixture, thereby preparing a solid electrolyte composition.

[0146] The manufactured solid electrolyte composition was applied onto a glass plate, irradiated with UV light at a wavelength of 365 nm for 30 minutes, heated to 90°C, and dried for more than 12 hours to produce a solid electrolyte film with a thickness of approximately 150 μm, which was then peeled off from the glass plate. The manufactured solid electrolyte film was laminated between stainless steel and lithium metal according to the electrochemical characteristics, and then a 2032 coin cell was manufactured.

[0147]

[0148] Examples 2 to 9 and Comparative Examples 1 to 4

[0149] A 2032 coin cell was manufactured using the same method as Example 1 using the components and contents shown in Table 1 below.

[0150]

[0151] Comparative Example 5

[0152] A solid electrolyte composition was prepared using polyethylene oxide (PEO) with a weight average molecular weight of 600,000 g / mol as a polymer for solid electrolyte, LiTFSI as a lithium salt, sodium laureth sulfate as an additive (surfactant), and acetonitrile as a solvent.

[0153] Specifically, 30 parts by weight, 1 part by weight, and 900 parts by weight of lithium salt, additive, and solvent were added, respectively, relative to 100 parts by weight of PEO.

[0154] The manufactured solid electrolyte composition was applied onto a glass plate, heated to 70°C in a vacuum oven, and dried for more than 12 hours to produce a solid electrolyte membrane with a thickness of approximately 150 μm, which was then peeled off from the Teflon. The manufactured solid electrolyte membrane was laminated between stainless steel and lithium metal according to electrochemical characteristics, and a 2032 coin cell was manufactured.

[0155]

[0156] Synthesis Example Mixing ratio (weight parts) Oxide type 1st monomer system 2nd monomer Lithium salt Additive Initiator Oxide Example 1 Synthesis Example 2 1585 30 1120 Ga-doped LLZO Example 2 Synthesis Example 3 1585 30 1120 Ga-doped LLZO Example 3 Synthesis Example 4 1585 30 1120 Ga-doped LLZO Example 4 Synthesis Example 2 595 30 1120 Ga-doped LLZO Example 5 Synthesis Example 2 2080 30 1120 Ga-doped LLZO Example 6 Synthesis Example 2 1585 30 1110 Ga-doped LLZO Example 7 Synthesis Example 2 1585 30 1130 Ga-doped LLZO Example 8 Synthesis Example 21585301120LATPExample 9Synthesis Example 21585301120LAGPComparative Example 1Synthesis Example 2199301120Ga-doped LLZOComparative Example 2Synthesis Example 26040301120Ga-doped LLZOComparative Example 3Synthesis Example 2158530115Ga-doped LLZOComparative Example 4Synthesis Example 21585301160Ga-doped LLZOComparative Example 5PEO100301---

[0157]

[0158] Exam example

[0159] <Molecular weight measurement method>

[0160] The method for measuring the molecular weight of the composite manufactured in the synthetic example is as follows.

[0161] The device used was Agilent's 1260 Infinity II Isocratic Pump (G7110B), 1260 Infinity II Autosampler (G7129A), Multicolumn Thermostat (G7116A), and 1260 Infinity II RI Detector (G7162A). The measurement conditions were Injection: 100 ㎕, Flow: 1 ml / min, and Column & Detector Temperature: 40℃.

[0162] The sample was used as a mobile phase with THF at a concentration of 0.02 g / 5 ml (4,000 ppm), and the columns used were HR 0.5: Mw 0~1,000, 60 Å, HR 1: Mw 100~5,000, 120 Å, HR 2: Mw 500~20,000, 500 Å, HR 4E: Mw 50~100,000, Mixture, and the polystyrene standards were Standard A: MP 95400, 31400, 9000, 2980, 486, Standard B: MP 68900, 18200, 6480, 1260, 340 (KE 8128 “n=0”), Standard C: MP 55100, 13900, 3950, 891, 94 (Phenol) was used.

[0163]

[0164] The ionic conductivity, transference number, and ESW (electrochemical stability window) of the coin cells manufactured in the examples and comparative examples were measured and are shown in Table 2 below.

[0165]

[0166] <Method for measuring ionic conductivity>

[0167] The ionic conductivity of the polymer solid electrolyte was calculated using the following mathematical equation 1 after measuring the impedance at temperatures from room temperature to 80 ℃. The coin cells manufactured according to the examples and comparative examples were brought into contact with the substrate, and an AC voltage was applied through the electrodes on both sides of the coin cell. At this time, the measurement frequency was set to an amplitude range of 7.0 MHz to 0.1 Hz as the applied condition, and the impedance was measured using VMP3 from BioLogic. The resistance of the bulk electrolyte was obtained from the intersection of the semicircle or straight line of the measured impedance trace with the real side, and the ionic conductivity of the polymer solid electrolyte membrane was calculated from the area and thickness of the sample.

[0168] [Mathematical Formula 1]

[0169]

[0170] σ: ionic conductivity (S / cm)

[0171] R: Intersection of the impedance trace and the real axis

[0172] A: Area of ​​the solid electrolyte membrane

[0173] t: Thickness of the solid electrolyte membrane

[0174]

[0175] <Transference Number 측정 방법>

[0176] The mobility of lithium cations was measured for coin cells manufactured in the examples and comparative examples. The measurement was performed using an Ivium n-Stat electrochemical analyzer. After applying a voltage of 10 mV, the changes in current and impedance were measured, and the difference was used to calculate the Transference Number (TN) using the following mathematical formula 2.

[0177]

[0178] [Equation 2]

[0179] TN = Iss(V-I0R0) / I0(V-IssRss)

[0180] I0: Initial current

[0181] Iss: Current after polarization

[0182] R0: Resistance before polarization

[0183] Rss: Resistance after polarization

[0184]

[0185] <ESW(Electrochemical stability window) 측정방법>

[0186] ESW was measured using the coin cells manufactured in the examples and comparative examples. ESW (Electrochemical stability window) was measured using linear sweep voltammetry (LSV) up to 6 V at a scan rate of 5 mV / s.

[0187]

[0188] Classification Ionic Conductivity (mS / cm) @ 25℃Transference number ESW (V) Example 10.0480.665.9 Example 20.0300.586.0 Example 30.0350.606.2 Example 40.0350.615.8 Example 50.0430.655.9 Example 60.0420.666.0 Example 70.0400.656.3 Example 80.0380.606.1 Example 90.0350.626.0 Comparative Example 1 Film Formation X Film Formation X Film Formation X Comparative Example 20.0250.605.7 Comparative Example 30.0350.655.8 Comparative Example 40.0320.586.3Comparative example 50.0050.254.0

[0189]

[0190] Referring to Table 2, it can be confirmed that when the content ratio of the first monomer and the second monomer is 5:95 to 20:80 (Examples 1 and 4 to 7), film formation was easy, but when the content ratio of the first monomer and the second monomer is 1:99 (Comparative Example 1), film formation was not performed. In addition, it can be confirmed that when the content ratio of the first monomer and the second monomer is 60:40 (Comparative Example 2), the ionic conductivity value is lower than when the content ratio of the first monomer and the second monomer is 5:95 to 20:80 (Examples 1 to 7).

[0191] In addition, it can be confirmed that the ionic conductivity value is higher when the content of the oxide is 10 to 30 parts by weight relative to 100 parts by weight of the total of the first monomer and the second monomer (Examples 1, 6, and 7), 5 parts by weight (Comparative Example 3), and 60 parts by weight (Comparative Example 4).

[0192] In addition, it can be confirmed that when the first monomer and the second monomer are used, both the ionic conductivity and the transfer number are higher than when PEO is used (Comparative Example 5).

[0193]

[0194] The present invention includes a compound and an oxide having a structure represented by Chemical Formula 1, and can improve ionic conductivity and Transference Number when applied as a solid electrolyte of a secondary battery.

Claims

1. [Revised on September 19, 2025, pursuant to Article 91 of the Rules] A solid polymer electrolyte complex composition comprising a compound having a structure represented by the following chemical formula 1 and an oxide. [Chemical formula 1] In the above chemical formula 1, A1 is substituted or unsubstituted C1~C 10 alkylene group, substituted or unsubstituted C5~C 12 Cycloalkylene group, substituted or unsubstituted C6~C 18 Arylene group, substituted or unsubstituted C2~C 18 A heteroarylene group, an alkylene oxide group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group; or a combination of two or more of the above, and A2 is a substituted or unsubstituted C1~C 10 alkylene group, substituted or unsubstituted C5~C 12 Cycloalkylene group, substituted or unsubstituted C6~C 18 Arylene group, substituted or unsubstituted C2~C 18 A heteroarylene group, an alkylene oxide group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group; or a combination of two or more of the above, and X is C2-C 18 Alkylene oxide group, C1~C 10 alkylene group, C5~C 12 Cycloalkylene group, C6~C 10 Arylene group, C2~C 18 A heteroarylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted thio ether group, a hydroxy group, a thiol group; or a combination of two or more of the above, or and At least one selected from the group consisting of , and n is 1-100.

2. [Revised on 19.09.2025 by Article 91 of the Rules] In paragraph 1, the compound having the structure represented by the chemical formula 1 is a solid polymer electrolyte complex composition having one structure selected from the group consisting of the following chemical formulas 1-1 to 1-3. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] 3. In paragraph 1, A solid polymer electrolyte complex composition, wherein the solid polymer electrolyte complex composition further comprises a monofunctional methacrylate-based monomer.

4. In paragraph 3, A solid polymer electrolyte complex composition, wherein the above monofunctional methacrylate-based monomer is at least one selected from the group consisting of polyethylene glycol methyl ether methacrylate (Polyethylene glycol methyl ether MA), polyethylene glycol methacrylate (Polyethylene glycol MA), methylene methacrylate (Methyl MA), ethylene methacrylate (Ethyl MA), glycidyl methacrylate (Glycidyl MA), and hydroxyethyl methacrylate (Hydroxyethyl MA).

5. In paragraph 3, A solid polymer electrolyte complex composition in which the weight ratio of the above monofunctional methacrylate monomer and the compound having a structure represented by the above chemical formula 1 is 95:5 to 50:

50.

6. In paragraph 3, The above solid polymer electrolyte complex composition further comprises a lithium salt, A solid polymer electrolyte complex composition in which the content of the lithium salt is 10 to 50 parts by weight based on 100 parts by weight of a mixture of a compound having a structure represented by the chemical formula 1 and the methacrylate-based monomer.

7. In paragraph 6, The solid polymer electrolyte complex composition further comprises a surfactant or an initiator.

8. In paragraph 1, The content of the above oxide is 10 to 50 parts by weight based on 100 parts by weight of a mixture of a compound having a structure represented by the above chemical formula 1 and the above methacrylate-based monomer, a solid polymer electrolyte complex composition.

9. A solid polymer electrolyte formed by curing a solid polymer electrolyte complex composition according to any one of claims 1 to 8.

10. A secondary battery comprising a positive electrode, a negative electrode, and a solid polymer electrolyte of claim 9.

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