Composite polymer electrolyte, method for manufacturing same, and all-solid-state battery comprising same

Abstract

According to the present invention, a composite polymer electrolyte having excellent ionic conductivity as well as mechanical strength, and a method for manufacturing same can be provided. In addition, according to the present invention, the composite polymer electrolyte is particularly applied to an all-solid-state battery using lithium metal or a lithium alloy as a negative electrode, thereby suppressing the generation of lithium dendrites and improving lifespan characteristics.

Description

Composite polymer electrolyte, method for producing the same, and all-solid-state battery comprising the same

[0001] This application claims the benefit of priority to Republic of Korea Patent Application No. 2024-0002097, filed January 5, 2024, the entire disclosure of which is incorporated herein by reference. The present invention relates to a single-ion conductive composite polymer electrolyte, a method for preparing the same, and an all-solid-state battery comprising the same.

[0002] Organic liquid electrolytes commonly used in lithium-ion secondary batteries have problems such as flammability, corrosiveness, thermal instability, high-voltage instability, and leakage, and are problematic because they can cause fire or explosion when the battery behaves abnormally.

[0003] To solve these problems, research has been conducted to replace the organic liquid electrolyte with a more stable form, and a polymer electrolyte has been proposed as one alternative.

[0004] Polymer electrolytes are a type of solid electrolyte. They offer superior stability compared to liquid electrolytes, eliminating the risk of electrolyte leakage or flammable vaporization during abnormal behavior. Furthermore, because they are leak-free, they can be used to create thin, lightweight, and flexible batteries that replace rigid external packaging. Furthermore, they are attracting attention for their numerous advantages, including high energy density, low volatility, and low reactivity.

[0005] However, polymer electrolytes have weak mechanical strength and low ionic conductivity, making it difficult to implement high-performance all-solid-state batteries. Recently, attempts have been made to use lithium metal as the anode to improve energy density. However, this approach poses challenges, such as reduced battery life due to the formation of lithium dendrites.

[0006] The purpose of the present invention is to provide a composite polymer electrolyte having excellent mechanical strength as well as ionic conductivity and a method for producing the same.

[0007] The present invention also aims to apply the composite polymer electrolyte as described above to an all-solid-state battery using lithium metal or a lithium alloy as a negative electrode, thereby suppressing the occurrence of lithium dendrites and improving life characteristics.

[0008] One aspect of the present invention relates to a composite polymer electrolyte comprising: a single-ion conductive polymer polymerized from a mixed solution containing a single-ion conductive monomer of the following chemical formula 1 and a cross-linking agent; a cyclic carbonate; and inorganic particles; characterized in that the molar ratio between the cyclic carbonate and lithium ions contained in the single-ion conductive polymer is 5 or more:

[0009] [Chemical Formula 1]

[0010]

[0011] [Chemical Formula 2]

[0012]

[0013] In the above equation, Q1 is C 6-12 An arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 is an alkyl group, and Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It is an alkyl group.

[0014] In one embodiment, the single ion conductive monomer of the above chemical formula 1 may be characterized by being at least one selected from the group consisting of the following chemical formulas A to E:

[0015] [Chemical Formula A]

[0016]

[0017] [Chemical Formula B]

[0018]

[0019] [Chemical Formula C]

[0020]

[0021] [Chemical Formula D]

[0022]

[0023] [Chemical Formula E]

[0024]

[0025] In one embodiment, the inorganic particles are selected from the group consisting of lithium lanthanum zirconium tantalum oxide (LLZTO), lithium lanthanum zirconium oxide (LLZO), lithium lanthanum tantalum oxide (LLTaO), lithium lanthanum titanate (LLT), lithium phosphorous oxynitride (LiPON), lithium orthosilicate (Li4SiO4), lithium borate (Li3BO3), lithium aluminum germanium phosphate (LAGP), and lithium aluminum titanium phosphate (LAGP). The lithium ion battery may be characterized by at least one active inorganic particle selected from the group consisting of lithium lanthanum zirconium niobium oxide (LATP), lithium lanthanum zirconium niobium oxide (LLZ-Nb), and lithium orthosilicate-lithium phosphate composite (Li4SiO4-Li3PO4), or at least one inactive inorganic particle selected from the group consisting of zinc oxide (ZnO), silicon dioxide (SiO2), aluminum oxide (Al2O3), and titanium dioxide (TiO2).

[0026] In one embodiment, the particle size of the active inorganic particles may be 1.5 μm or less, and the particle size of the inactive inorganic particles may be 500 nm or less.

[0027] In one embodiment, the crosslinking agent is selected from the group consisting of polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polyethylene glycol monoethyl ether acrylate (PEGMEA), polyethylene glycol monomethacrylate (PEGMEMA), pentaerythritol triacrylate (PETA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), and ethoxylated trimethylolpropane. It may be characterized by being at least one selected from the group consisting of triacrylate (Ethoxylated Trimethylolpropane Triacrylate; ETPTA).

[0028] In one embodiment, the crosslinking agent may be characterized by having a number average molecular weight (Mn) of 100 to 10,000 g / mol.

[0029] In one embodiment, the cyclic carbonate may be characterized in that it is at least one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), and γ-butyrolactone.

[0030] In one embodiment, the composite polymer electrolyte of the present invention may be characterized by containing 40 wt% or less of the single ion conductive polymer.

[0031] In one embodiment, the composite polymer electrolyte of the present invention may be characterized by containing 100 to 1000 parts by weight of the inorganic particles relative to 100 parts by weight of the single-ion conductive polymer.

[0032] In one embodiment, the composite polymer electrolyte of the present invention may be characterized by containing 100 to 1000 parts by weight of the cyclic carbonate relative to 100 parts by weight of the single-ion conductive polymer.

[0033] In one embodiment, the composite polymer electrolyte of the present invention has an ionic conductivity of 1.0 X 10 at 25°C. -4 It can be characterized by being greater than S / cm.

[0034] Another aspect of the present invention relates to a method for producing a composite polymer electrolyte, comprising the steps of: preparing a mixed solution containing a single-ion conductive monomer of the following chemical formula 1, inorganic particles, and a cross-linking agent (step S1); heating the mixed solution at a high temperature to polymerize a single-ion conductive polymer and forming a film containing the single-ion conductive polymer (step S2); and impregnating the film with a cyclic carbonate (step S3); characterized in that the molar ratio of the cyclic carbonate to lithium ions contained in the single-ion conductive polymer is 5 or more:

[0035] [Chemical Formula 1]

[0036]

[0037] [Chemical Formula 2]

[0038]

[0039] In the above equation, Q1 is C 6-12An arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 is an alkyl group, and Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It is an alkyl group.

[0040] In one embodiment, the S2 step may be characterized in that it is performed at a temperature of 40 to 100° C. under vacuum conditions for 12 to 24 hours.

[0041] Another aspect of the present invention relates to an all-solid-state battery comprising a positive electrode, a solid electrolyte membrane, and a negative electrode, wherein the solid electrolyte membrane comprises a composite polymer electrolyte, wherein the composite polymer electrolyte comprises a single-ion conductive polymer polymerized from a mixed solution comprising a single-ion conductive monomer of the following chemical formula 1 and a cross-linking agent; a cyclic carbonate; and inorganic particles; and wherein the molar ratio between the cyclic carbonate and lithium ions contained in the single-ion conductive polymer is 5 or more:

[0042] [Chemical Formula 1]

[0043]

[0044] [Chemical Formula 2]

[0045]

[0046] In the above equation, Q1 is C 6-12 An arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 is an alkyl group, and Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It is an alkyl group.

[0047] In one embodiment, the all-solid-state battery of the present invention may be characterized by using lithium metal or a lithium alloy as a negative electrode.

[0048] According to the present invention, a composite polymer electrolyte having excellent mechanical strength as well as ionic conductivity and a method for producing the same can be provided.

[0049] According to the present invention, the composite polymer electrolyte as described above can be applied to an all-solid-state battery using lithium metal or a lithium alloy as a negative electrode, in particular, to suppress lithium dendrite generation and improve life characteristics.

[0050] Terms or words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0051] Accordingly, the configuration of the embodiments described in this specification is only one of the most preferred embodiments of the present invention and does not represent all of the technical ideas of the present invention, so it should be understood that various equivalents and modified examples that can replace them may exist at the time of filing this application.

[0052] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0053] When a part in this specification is said to “comprise” a certain component, this does not exclude other components unless specifically stated to the contrary, but rather means that other components may be included. Thus, for example, a composition comprising compound A may include compounds other than A. However, the term “comprise” also encompasses, as a specific embodiment thereof, the more restrictive meanings of “consisting essentially / essentially of” and “consisting of,” so that, for example, “a composition comprising compound A” may also consist (essentially / essentially) of compound A.

[0054] In this connection, it should be understood that terms such as “have” or “have” as used herein are intended to specify the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0055] When it is said in this specification that any layer is located “on” or “between” any other layer, this includes not only cases where any layer is in contact with any other layer, but also cases where another layer or material, etc., exists between the two layers.

[0056] Where an amount, concentration, or other value or parameter is given herein as a range, a preferred range, or an enumeration of an upper preferred value and a lower preferred value, this should be understood to specifically disclose any range that can be formed by any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the range is separately disclosed. Where a range of numerical values ​​is recited herein, unless otherwise stated, e.g., there is no limiting term such as greater than, less than, etc., the range is intended to include the endpoint values ​​and all integers and fractions within the range. The scope of the present invention is not intended to be limited to the specific values ​​recited when defining a range.

[0057] Among the properties mentioned in this specification, if the measurement temperature affects the property, the property is measured at room temperature unless otherwise specified. The term "room temperature" refers to the natural temperature without heating or cooling, and may mean, for example, any temperature within the range of about 10°C to 30°C, or about 23°C or about 25°C. In addition, unless otherwise specified, the unit of temperature in this specification is ℃.

[0058] In addition, among the properties mentioned in this specification, if the measurement pressure affects the property, the property is measured at normal pressure, i.e., atmospheric pressure (approximately 1 atm), unless otherwise specified.

[0059] The first aspect of the present invention relates to a composite polymer electrolyte.

[0060] The composite polymer electrolyte of the present invention may include, for example, a single-ion conductive polymer polymerized from a mixed solution containing a single-ion conductive monomer of the following chemical formula 1 and a cross-linking agent; a cyclic carbonate; and / or inorganic particles:

[0061] [Chemical Formula 1]

[0062]

[0063] [Chemical Formula 2]

[0064]

[0065] In the above equation, Q1 is C 6-12 It may be an arylene group or a functional group represented by chemical formula 2, wherein n may be an integer from 1 to 10, and R1 is hydrogen or C 1-3 It can be an alkyl group, and Q2 is a halogen group or C substituted with a halogen group. 1-3 It may be an alkyl group, and Q3 may be =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It may be an alkyl group.

[0066] The term “arylene group” as used herein refers to a functional group derived primarily from benzene or a related aromatic structure. Examples of such arylene groups include, but are not limited to, a phenylene group, a biphenylene group, a terphenylene group, a quaterphenylene group, a naphthalenylene group, an anthracenylene group, a phenanthrenylene group, a pyrenylene group, or a benzopyrenylene group, but are not intended to limit the scope of the present invention.

[0067] In this specification, the term “alkyl group” by itself or as part of another substituent, unless otherwise stated, refers to a group having the indicated number of carbon atoms (i.e., C 1-10 It means a straight or branched chain monovalent hydrocarbon having 1 to 10 carbons.

[0068] Examples of the above alkyl group include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, an n-heptyl group, a 1-methylhexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, Examples thereof include a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an octyl group, an n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, an n-nonyl group, a 2,2-dimethylheptyl group, a 1-ethyl-propyl group, a 1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl group, a 4-methylhexyl group, and a 5-methylhexyl group, but these are non-limiting examples and the scope of the present invention is not limited thereto.

[0069] As used herein, the term “halogen” includes, but is not limited to, fluoro, chloro, bromo, or iodo.

[0070] The above Q1 is for example C 6-12 It may be an arylene group or a functional group represented by the above chemical formula 2. In another example, the above Q1 is C 6-10 Arylene group, C 6-8 When it is an arylene group or a functional group represented by the above chemical formula 2, n may be 1 or more, 2 or more, or 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less. In terms of improving polymerization stability and mechanical strength, the above Q1 may preferably be a phenylene group or a functional group represented by the chemical formula 2 where n=3.

[0071] The above R1 is, for example, hydrogen or C 1-3 It may be an alkyl group. In terms of improving polymerization reactivity, the R1 may preferably be a hydrogen or methyl group.

[0072] The above Q2 is, for example, a halogen group or a C substituted with a halogen group. 1-3 It may be an alkyl group. In terms of improving ionic conductivity, the above Q2 may preferably be fluorine or -CF3.

[0073] The above Q3 may be, for example, =O or =NS(O)2-R2. In terms of improving ionic conductivity, the above Q3 may preferably be =O or =NS(O)2-CF3.

[0074] The single ion conductive monomer of the above chemical formula 1 may be characterized by being, for example, at least one selected from the group consisting of the following chemical formulas A to E:

[0075] [Chemical Formula A]

[0076]

[0077] [Chemical Formula B]

[0078]

[0079] [Chemical Formula C]

[0080]

[0081] [Chemical Formula D]

[0082]

[0083] [Chemical Formula E]

[0084] .

[0085] The composite polymer electrolyte of the present invention has a high transference rate (transference numbers, t) by synthesizing a single-ion conductive polymer using the single-ion conductive monomer as described above, thereby restricting the movement of anions. Li+) can suppress lithium dendrites by reducing the ion concentration gradient.

[0086] The crosslinking agent is, for example, polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polyethylene glycol monoethyl ether acrylate (PEGMEA), polyethylene glycol monomethacrylate (PEGMEMA), pentaerythritol triacrylate (PETA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), and ethoxylated trimethylolpropane. It may be characterized by at least one selected from the group consisting of triacrylate (Ethoxylated Trimethylolpropane Triacrylate; ETPTA). From the viewpoint of easy polymerization reaction with a single ion conductive monomer, improvement of ion conductivity, and control of various physical properties, it may be characterized by the crosslinking agent being polyethylene glycol diacrylate (PEGDA).

[0087] The crosslinking agent may be characterized by, for example, a number average molecular weight (Mn) of 100 to 10,000 g / mol. In other examples, the crosslinking agent may have a number average molecular weight (Mn) of 200 g / mol or more, 300 g / mol or more, 400 g / mol or more, or 500 g / mol or more, or 9,000 g / mol or less, 8,000 g / mol or less, 7,000 g / mol or less, 6,000 g / mol or less, 5,000 g / mol or less, 4,000 g / mol or less, 3,000 g / mol or less, 2,000 g / mol or less, or 1,000 g / mol or less. The present invention can provide a composite polymer electrolyte having excellent ionic conductivity and mechanical strength by introducing a crosslinking agent having the above-described number average molecular weight (Mn).

[0088] The composite polymer electrolyte of the present invention may be characterized by including a single-ion conductive polymer polymerized from a mixed solution containing, for example, a single-ion conductive monomer of the above-described chemical formula 1 and a cross-linking agent. The mixed solution may further include a solvent as described in the second aspect described below, but the solvent may be evaporated during the polymerization process and not be included in the single-ion conductive polymer, or even if included, may be included in an amount of 1 wt% or less, 0.1 wt% or less, 0.01 wt% or less, or 0.001 wt% or less.

[0089] The composite polymer electrolyte of the present invention may include, for example, a carbonate, and the carbonate may be characterized as being a cyclic carbonate. The carbonate may be cyclic or chain-shaped, but when a cyclic carbonate is applied to the composite polymer electrolyte of the present invention, compared to when a chain-shaped carbonate is applied, better bonding with lithium ions can be achieved, and as a result, better ionic conductivity can be exhibited.

[0090] The above cyclic carbonate may be characterized by being at least one selected from the group consisting of, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), and γ-butyrolactone.

[0091] The composite polymer electrolyte of the present invention may be characterized, for example, by having a molar ratio of cyclic carbonate to lithium ions contained in a single-ion conductive polymer of 5 or more. In the present specification, the molar ratio of cyclic carbonate to lithium ions contained in the single-ion conductive polymer may be a molar ratio based on the input amount or a value measured for the final manufactured composite polymer electrolyte. In the prior art, even when carbonate is introduced, the carbonate evaporates during the manufacturing process of the polymer electrolyte, making it difficult to control the molar ratio as described above in the final manufactured composite polymer electrolyte, and there was no motivation to control it. The inventors of the present invention have developed a method for manufacturing a composite polymer electrolyte, which will be described later, in which a film formed by polymerizing a single-ion conductive polymer is impregnated with a cyclic carbonate, thereby assembling a battery, thereby enabling the manufacture of a composite polymer electrolyte without evaporation of the carbonate. As a result, the molar ratio of cyclic carbonate to lithium ions contained in the single-ion conductive polymer could be controlled to 5 or more in the final manufactured composite polymer electrolyte. As a result, it is possible to provide a composite polymer electrolyte that has excellent mechanical strength and excellent ionic conductivity, making it suitable for use as a solid electrolyte in itself, and can be applied to an all-solid-state battery using lithium metal or a lithium alloy as an anode, thereby contributing to suppressing lithium dendrite generation and improving life characteristics and performance. In another example, the composite polymer electrolyte of the present invention may be controlled so that the molar ratio between the cyclic carbonate to the lithium ion contained in the single ion conductive polymer is 5.2 or more, 5.4 or more, 5.6 or more, 5.8 or more, 6.0 or more, 6.2 or more, 6.4 or more, 6.6 or more, 6.8 or more, 7.0 or more, 7.2 or more, 7.4 or more, or 7.6 or more, or 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less.

[0092] The composite polymer electrolyte of the present invention may include, for example, inorganic particles. The inorganic particles include, for example, LLZTO(Li 6.75 La3Zr 1.75 Ta 0.25 O 12 , Li 6.5 La3Zr 1.5 Ta 0.5 O 12 , Li7La3Zr 2-x Ta x O 12 ), LLZO(Li7La3Zr2O 12 ), LLTaO(Li5La3Ta2O 12 ), LLT(Li 0.33 La 0.55 TiO3), LiPON(Li3PO4), Li4SiO4, Li3BO3, LAGP(Li 1.5 Al 0.5 Ge 1.5 P3O 12 ), LATP(Li 1.3 Al 0.3 Ti 1.7 P3O 12 ), LLZ-Nb(Li7La3Zr 2-x Nb x O 12 ) and at least one active inorganic particle selected from the group consisting of Li4SiO4-Li3PO4, or at least one inactive inorganic particle selected from the group consisting of ZnO, SiO2, Al2O3, and TiO2. From a manufacturing cost perspective, using inactive inorganic particles may be advantageous compared to using active inorganic particles.

[0093] The above active inorganic particles may have, for example, a particle size of 1.5 μm or less. In the present specification, the particle size may be measured by a particle size analyzer (Particle Size Analyzer using Laser Diffraction, Mastersizer 3000, Malvern Pnalytical) and may mean the maximum, average and / or minimum particle size. In other examples, the above active inorganic particles may have a particle size of 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, or 1.0 μm or less, or 0.1 μm or more, 0.5 μm or more, or 0.8 μm or more. By controlling the particle size of the active inorganic particles as described above, sedimentation due to particle agglomeration can be suppressed and excellent dispersibility can be achieved.

[0094] The above-described inert inorganic particles may have, for example, a particle size of 500 nm or less. In other examples, the above-described inert inorganic particles may be characterized by a particle size of 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, or 100 nm or less, or 10 nm or more, 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, or 150 nm or more, or 1000 nm or less, 800 nm or less, 600 nm or less, or 400 nm or less. By controlling the particle size of the inert inorganic particles as described above, sedimentation due to particle agglomeration can be suppressed and excellent dispersibility can be achieved.

[0095] The composite polymer electrolyte of the present invention can have better ionic conductivity and mechanical strength by controlling the weight ratio of each material as follows.

[0096] The composite polymer electrolyte of the present invention may be characterized by, for example, containing 40 wt% or less of the single-ion conductive polymer. In other examples, the composite polymer electrolyte of the present invention may be characterized by containing 35 wt% or less, 30 wt% or less, or 25 wt% or less of the single-ion conductive polymer, or 1 wt% or more, 5 wt% or more, or 10 wt% or more of the single-ion conductive polymer. The composite polymer electrolyte of the present invention may further improve ionic conductivity and mechanical strength by containing the single-ion conductive polymer in the above weight range.

[0097] The composite polymer electrolyte of the present invention may be characterized by, for example, containing 60 to 90 parts by weight of the single-ion conductive monomer of the above chemical formula 1 relative to 100 parts by weight of the single-ion conductive polymer. In another example, the composite polymer electrolyte of the present invention may be characterized by containing 65 parts by weight or more, 70 parts by weight or more, or 75 parts by weight or more, or 85 parts by weight or less, or 80 parts by weight or less, of the single-ion conductive monomer of the above chemical formula 1 relative to 100 parts by weight of the single-ion conductive polymer.

[0098] The composite polymer electrolyte of the present invention may be characterized by, for example, containing 100 to 1000 parts by weight of the inorganic particles relative to 100 parts by weight of the single-ion conductive polymer. In another example, the composite polymer electrolyte of the present invention may be characterized by containing 110 parts by weight or more, 120 parts by weight or more, 130 parts by weight or more, 140 parts by weight or more, or 150 parts by weight or more of the inorganic particles relative to 100 parts by weight of the single-ion conductive polymer, or 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, 600 parts by weight or less, 500 parts by weight or less, or 400 parts by weight or less.

[0099] The composite polymer electrolyte of the present invention may be characterized by, for example, containing 100 to 1000 parts by weight of the cyclic carbonate relative to 100 parts by weight of the single-ion conductive polymer. In another example, the composite polymer electrolyte of the present invention may be characterized by containing 110 parts by weight or more, 120 parts by weight or more, 130 parts by weight or more, 140 parts by weight or more, 150 parts by weight or more, or 160 parts by weight or more, or 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, 600 parts by weight or less, 500 parts by weight or less, or 400 parts by weight or less of the cyclic carbonate relative to 100 parts by weight of the single-ion conductive polymer.

[0100] The composite polymer electrolyte of the present invention may be characterized by further including, for example, other additives. Examples of the other additives include lithium salts (LiTFSI, LiClO4, LiPF6, etc.), but as long as the purpose of the present invention is not hindered, additives commonly used in polymer electrolytes may be used without limitation.

[0101] The composite polymer electrolyte of the present invention has, for example, an ionic conductivity of 1.0 × 10 at 25°C through a combination of the above-described components. -4 S / cm It may be ideal. The above 25°C ionic conductivity may be measured in a manner according to the evaluation example described below. The 25°C ionic conductivity of the composite polymer electrolyte of the present invention is, in another example, 1.2 × 10 -4 S / cm Above, 1.4× 10 -4 S / cm Above, 1.6 × 10 -4 S / cm Above, 1.8 × 10 -4 S / cm Above, 2.0 × 10 -4 S / cm Above, 2.2 × 10 -4 S / cm Above, 2.4 × 10 -4 S / cm Above, 2.6 × 10 -4 S / cm Above, 2.8 × 10 -4 S / cm Above, 3.0 × 10 -4 S / cm Above, 3.5 × 10 -4 S / cm Above, 4.0 × 10 -4 S / cm Above, 4.5 × 10 -4 S / cm Above, 5.0 × 10 -4 S / cm Above, 5.5 × 10 -4 S / cm Above, 6.0 × 10 -4 S / cm Above, 6.5 × 10 -4 S / cm Above, 7.0 × 10 -4 S / cm Above, 7.5 × 10 -4 S / cm Ideal or 8.0 × 10 -4 S / cm or 20.0 × 10 -4 S / cm Below, 15.0 × 10 -4 S / cm Below, 10.0 × 10 -4 S / cm Below, 9.0 × 10 -4 S / cm Below, 8.0 × 10 -4 S / cm Below, 7.0 × 10 -4 S / cm Below, 6.0 × 10 -4 S / cm Below, 5.0 × 10 -4 S / cm Below, 4.0 × 10 -4 S / cm or less than or equal to 3.0 × 10 -4S / cm It could be as follows:

[0102] The second aspect of the present invention relates to a method for producing a composite polymer electrolyte.

[0103] Matters relating to the first aspect of the present invention may be equally applied to matters relating to the second aspect, unless specifically stated otherwise.

[0104] The method for producing a composite polymer electrolyte of the present invention may include, for example, a step (S1) of producing a mixed solution containing a single-ion conductive monomer of the following chemical formula 1, inorganic particles, and a cross-linking agent; a step (S2) of heating the mixed solution at a high temperature to polymerize a single-ion conductive polymer and form a film containing the single-ion conductive polymer; and a step (S3) of impregnating the film with a cyclic carbonate, and may be characterized in that the molar ratio of the cyclic carbonate to lithium ions contained in the single-ion conductive polymer is 5 or more:

[0105] [Chemical Formula 1]

[0106]

[0107] [Chemical Formula 2]

[0108]

[0109] In the above equation, Q1 is C 6-12 An arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 is an alkyl group, and Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It may be an alkyl group.

[0110] The solvent of the above step S1 may be, for example, alcohols, acetonitrile, ethers, or mixtures thereof. Examples of the alcohols include methanol, ethanol, butanol, and the like, and examples of the ethers include, but are not limited to, dimethyl ether, diethyl ether, methyl tert-butyl ether, and the like.

[0111] The mixed solution of the above step S1 can be prepared, for example, through a step of dissolving the single ion conductive monomer in a solvent (step S1-1); a step of adding inorganic particles to the solvent and stirring (step S1-2); and a step of adding a cross-linking agent to the solvent and stirring to prepare a mixed solution (step S1-3).

[0112] The stirring in step S1-2 may be characterized by being performed, for example, at room temperature for 15 to 21 hours. In another example, the stirring in step S1-2 may be performed at room temperature for 16 hours or more, 17 hours or more, or 20 hours or less, or 19 hours or less.

[0113] The stirring in step S1-3 may be performed, for example, at room temperature for 1 to 30 minutes. In other examples, the stirring in step S1-3 may be characterized by being performed at room temperature for 3 minutes or more, 5 minutes or more, 7 minutes or more, or 9 minutes or more, or 25 minutes or less, 20 minutes or less, or 15 minutes or less.

[0114] The above step S2 may be characterized in that it is performed for 12 to 24 hours at a temperature of 40 to 100° C. under vacuum conditions, for example. The temperature of the step S2 may be, in other examples, 45° C. or higher, 50° C. or higher, or 55° C. or higher, or 95° C. or lower, 90° C. or lower, 85° C. or lower, 80° C. or lower, 75° C. or lower, 70° C. or lower, or 65° C. or lower. The performing time of the step S2 may be, in other examples, 14 hours or higher, 16 hours or higher, or 17 hours or higher, or 22 hours or lower, 20 hours or lower, or 19 hours or lower.

[0115] The method for producing the composite polymer electrolyte of the present invention may further include, for example, a step of liquefying the cyclic carbonate. However, this can be performed if the cyclic carbonate is in a solid state at room temperature, and if it is in a liquid state, it can be used directly without the liquefaction step.

[0116] The third aspect of the present invention relates to an all-solid-state battery.

[0117] Matters relating to the first and / or second aspects of the present invention may be equally applied to matters relating to the third aspect unless specifically stated otherwise.

[0118] The all-solid-state battery of the present invention may include, for example, a positive electrode, a solid electrolyte membrane, and a negative electrode, wherein the solid electrolyte membrane includes a composite polymer electrolyte, and the composite polymer electrolyte includes a single-ion conductive polymer polymerized from a mixed solution containing the single-ion conductive monomer of the above chemical formula 1 and a cross-linking agent; a cyclic carbonate; and inorganic particles; and may be characterized in that the molar ratio between the cyclic carbonate and lithium ions included in the single-ion conductive polymer is 5 or more.

[0119] In this specification, the matters relating to each of the positive and negative electrodes are described below as examples to facilitate understanding, but are not limited thereto, and the matters relating to the positive and negative electrodes applied to known all-solid-state batteries can be equally applied.

[0120] The above positive electrode includes, for example, a positive electrode current collector and a positive electrode active material layer, and the positive electrode active material layer may include a positive electrode active material, a binder, a conductive material, and / or a solid electrolyte.

[0121] The positive electrode current collector is not particularly limited as long as it is conductive and does not cause a chemical change in the battery, and may be, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel surface-treated with carbon, nickel, titanium, silver, etc. In addition, the positive electrode current collector may be formed with fine irregularities on the surface to strengthen the bonding strength with the positive electrode active material layer, and may be used in various forms such as a film, sheet, foil, net, porous body, foam, or non-woven fabric.

[0122] The above-described positive electrode active material reversibly intercalates and deintercalates lithium ions. The positive electrode active material may be, but is not limited to, lithium transition metal oxides such as lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganate, lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, and any material used as a positive electrode active material in the art may be used. The positive electrode active materials may be used alone or in combination of two or more.

[0123] The above lithium transition metal oxide is, for example, Li a A 1-b B b D2 (in the above formula, 0.90≤a≤1, and 0≤b≤0.5); Li a Ni 1-b-c Co b B c O 2-α F2 (in the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0 <α<2); Li a Ni 1-b-c Mn b B c D α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0≤α≤2); Li a Ni 1-b-c Co b B c D α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); Li a E 1-b B b O 2-c D c (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05); LiE 2-b B b O 4-c D c (In the above formula, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b B c O 2-α F α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a CoG b O2 (in the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a MnG b O2 (in the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a Mn2G bO4 (in the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a Ni 1-b-c Mn b B c O 2-α F α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni 1-b-c Mn b B c O 2-α F2 (in the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni b E c G d O2 (in the above formula, 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1); Li a Ni b Co c Mn d G e O2 (in the above formula, 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0 ≤d≤0.5, 0.001≤e≤0.1); Li a NiG b O2 (in the above formula, 0.90≤a≤1, 0.001≤b≤0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiIO2; LiNiVO4; Li (3- f) J2(PO4)3(0≤f≤2); Li (3-f)Fe2(PO4)3(0≤f≤2); It may be a compound represented by any one of the chemical formulas of LiFePO4. In this compound, A is Ni, Co, Mn, or a combination thereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; F is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; I is Cr, V, Fe, Sc, Y, or a combination thereof; J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof. A compound having a coating layer added to the surface of this compound may be used as the positive electrode active material, or a mixture of the above-mentioned compound and the compound having a coating layer added may be used. The coating layer added to the surface of such compounds may contain, for example, a lithium ion conductive oxide. The lithium ion conductive oxide may be, for example, LiNbO3, Li4Ti5O. 12 , Li3PO4, etc., but are not limited thereto. The compound forming the coating layer may be amorphous or crystalline. The method for forming the coating layer may include, for example, spray coating, dipping, etc., but may be selected without limitation within a range that does not adversely affect the properties of the positive electrode active material.

[0124] When the above-mentioned cathode active material is a ternary lithium transition metal oxide such as NCA or NCM and contains nickel (Ni), it may be possible to increase the capacity density of the all-solid-state battery and reduce metal dissolution of the cathode active material in a charged state. Accordingly, the cycle characteristics of the all-solid-state battery in a charged state may be improved.

[0125] The shape of the above-mentioned positive electrode active material may be, for example, a spherical particle shape, such as an elliptical sphere. The particle size of the positive electrode active material is not particularly limited and may be within the range applicable to positive electrode active materials of conventional all-solid-state secondary batteries. The content of the positive electrode active material is also not particularly limited and may be within the range applicable to positive electrodes of conventional all-solid-state secondary batteries.

[0126] The binder may be, for example, an aqueous binder, an organic binder, or a combination thereof. The binder may be, for example, a polymer including polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinylidene fluoride, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene, fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or a combination thereof. The aqueous binder may be, for example, styrene butadiene rubber, carboxymethyl cellulose, or a combination thereof. As the organic binder, for example, polytetrafluoroethylene, polyvinylidene fluoride, or a combination thereof may be used, but is not limited thereto, and any known binder may be used without limitation as long as it does not impede the purpose of the present invention.

[0127] The conductive material may be, for example, graphite, carbon black, acetylene black, Ketzen black, carbon fiber, carbon nanotube, or metal powder, but is not limited thereto, and any conductive material that can be introduced into an all-solid-state battery may be used without limitation as long as it does not hinder the purpose of the present invention.

[0128] The solid electrolyte included in the above-described positive electrode active material layer may be, for example, an organic, inorganic, or composite electrolyte. The organic electrolyte is a polymer electrolyte, and any polymer electrolyte applicable to an all-solid-state battery may be exemplified without limitation, and may also include a composite polymer electrolyte according to the present invention. The inorganic electrolyte may be a sulfide-based, oxide-based, or halide-based solid electrolyte, but any inorganic electrolyte applicable to an all-solid-state battery may be exemplified without limitation. The composite electrolyte may mean including a nanoparticle filler and a polymer, and any composite electrolyte applicable to an all-solid-state battery may be exemplified without limitation.

[0129] In addition to the above-mentioned positive electrode active material layer, the positive electrode active material layer may further include additives such as fillers, coating agents, dispersants, and ion conductive assistants, and these additives may be used without limitation as long as they are known materials generally used in electrodes of all-solid-state batteries.

[0130] The above-described solid electrolyte membrane may include, for example, a composite polymer electrolyte having the characteristics described above. The all-solid-state battery of the present invention may have excellent lifespan characteristics and performance, etc. by including the composite polymer electrolyte as described above in the solid electrolyte membrane.

[0131] The above solid electrolyte membrane may further include, for example, a binder. As the binder, the binder included in the above-described positive electrode active material layer may be exemplified.

[0132] The thickness of the above solid electrolyte membrane is not particularly limited, but may typically be within the range of 0.1 ㎛ to 500 ㎛.

[0133] The above negative electrode includes, for example, a negative electrode active material layer, and the negative electrode active material layer may include a negative electrode active material, a binder, a conductive material, and / or a solid electrolyte.

[0134] The above negative active material is, for example, carbon such as non-graphitizable carbon, graphite carbon, etc.; Lix Fe2O3(0≤x≤1), Li x WO2(0≤x≤1), Sn x Me 1-x Me' y O z (Me: Mn, Fe, Pb, Ge; Me'; Al, B, P, Si, elements of group 1, group 2, group 3 of the periodic table, halogen; 0≤x≤1; 1≤y≤3; 1≤z≤8) and other metal composite oxides; lithium metal; lithium alloy; lithium-indium alloy; silicon-based alloy; tin-based alloy; indium; indium-based alloy; metal oxides such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, and Bi2O5; conductive polymers such as polyacetylene; Li-Co-Ni-based materials; titanium oxide; lithium titanium oxide; and the like. One or more selected from the group consisting of:

[0135] The solid electrolyte, conductive material, and / or binder included in the above-described negative electrode active material layer may be one of the types included in the above-described positive electrode or solid electrolyte membrane, but is not limited thereto, and any solid electrolyte, conductive material, and / or binder used in the relevant technical field may be used. The solid electrolyte, conductive material, and / or binder included in the negative electrode active material layer may be the same as or different from the solid electrolyte, conductive material, and / or binder included in the positive electrode active material layer, solid electrolyte membrane, etc.

[0136] The above-mentioned negative active material layer may also further include, for example, other additives. These additives may be used without limitation as long as they are known materials generally used in electrodes of all-solid-state batteries.

[0137] The all-solid-state battery of the present invention can use lithium metal or a lithium alloy as an anode, particularly from the viewpoint of improving energy density. When lithium metal or a lithium alloy is used as an anode, there are problems in that lithium dendrites are generated and the life characteristics of the battery are reduced due to the formation of an uneven interface with the solid electrolyte and high reactivity. The present invention can solve these problems, and thus provide an all-solid-state battery in which energy density, lifespan, performance, etc. are all improved, by making the solid electrolyte membrane include the composite polymer electrolyte as described above and / or the solid electrolyte included in the anode or cathode include the composite polymer electrolyte as described above.

[0138] The above-described negative electrode may further include, for example, a negative electrode current collector. The negative electrode current collector may be a known metal that can be used as a current collector of an all-solid-state battery. The negative electrode current collector may be, for example, a material that does not form an alloy or compound with lithium. The negative electrode current collector may be, for example, selected from the group consisting of copper, nickel, aluminum, vanadium, gold, platinum, magnesium, iron, titanium, cobalt, chromium, zinc, germanium, indium, and stainless steel, but is not limited thereto. Any material used as an electrode current collector in the relevant technical field may be used as long as it does not impede the purpose of the present invention. The negative electrode current collector may be composed of one type of the above-described metal, or may be composed of an alloy or a coating material of two or more types of metals. The negative electrode current collector may be used in various forms, for example, a film, a sheet, a foil, a net, a porous body, a foam, a non-woven fabric, etc.

[0139] Hereinafter, the present invention will be described in detail by way of examples to specifically illustrate the disclosure of the present invention and its intended functions and effects, as described above. However, these examples may be modified in various ways, and the scope of this specification is not construed as being limited to these examples. It is emphasized that these examples are provided to represent the present invention and to provide a more concrete explanation to those skilled in the art.

[0140] Example 1.

[0141] A composite polymer electrolyte was manufactured in the following manner so that the weight ratio of the single-ion conductive monomer, cross-linker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 13:4:52:31.

[0142] First, LiSTFSI ((trifluoromethane)sulfonamide lithium styrene) as a single-ion conductive monomer was dissolved in acetonitrile solvent at a concentration of 10 wt%, and then LLZTO with an average particle diameter of 1 μm as an inorganic particle was added and stirred at room temperature for 18 hours using a magnetic bar. Next, PEGDA with Mn=575 g / mol as a cross-linking agent was added to the solution, stirred at room temperature for 10 minutes, and then the prepared mixed solution was applied to a substrate. After that, a polymer structure was formed through a cross-linking reaction and a solvent drying process was performed in a vacuum oven at 60°C for 18 hours to obtain a film. Then, EC (ethylene carbonate), which was liquefied by briefly placing it in an oven at 35 to 40°C as a cyclic carbonate, was impregnated into the film to obtain a composite polymer electrolyte. At this time, Li contained in the single-ion conductive monomer of the prepared composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 8.5.

[0143] Example 2.

[0144] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 11:3:45:41. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 13.2.

[0145] Example 3.

[0146] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 10:3:38:49. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 18.9.

[0147] Example 4.

[0148] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that ZnO with an average particle diameter of 50 nm was used instead of LLZTO with an average particle diameter of 1 μm as an inorganic particle, and that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was set to 12:4:54:30. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 8.9.

[0149] Example 5.

[0150] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that SiO2 with an average particle diameter of 200 nm was used instead of LLZTO with an average particle diameter of 1 μm as an inorganic particle, and that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was set to 18:6:37:39. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 7.7.

[0151] Example 6.

[0152] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 15:4.5:59.5:21. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 5.2.

[0153] Example 7.

[0154] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that PC (Propylene carbonate) was introduced instead of EC as a cyclic carbonate, and the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was set to 13:4:52:31. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 7.4.

[0155] Example 8.

[0156] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that ZnO with an average particle diameter of 50 nm was used instead of LLZTO with an average particle diameter of 1 μm as an inorganic particle, and that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 14.2:4.3:61.2:20.3. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 5.2.

[0157] Example 9.

[0158] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that SiO2 with an average particle diameter of 200 nm was used instead of LLZTO with an average particle diameter of 1 μm as an inorganic particle, and that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 21:6.5:43:29.5. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 5.

[0159] Comparative Example 1.

[0160] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that the weight ratio of the single-ion conductive monomer, cross-linker, and inorganic particles included in the manufactured composite polymer electrolyte was 19:6:75 without introducing a cyclic carbonate. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 0.

[0161] Comparative Example 2.

[0162] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that EMC (Ethyl methyl carbonate) was introduced as a chain-type carbonate instead of a cyclic carbonate, and the weight ratio of the single-ion conductive monomer, cross-linker, inorganic particles, and chain-type carbonate included in the manufactured composite polymer electrolyte was set to 13:4:54:29. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the chain carbonate to the mole number of the ion was 6.6.

[0163] Comparative Example 3.

[0164] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that PC (Propylene carbonate) was introduced instead of EC as a cyclic carbonate, and the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was set to 17:5:67:11. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 2.

[0165] Comparative Example 4.

[0166] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that SiO2 with an average particle diameter of 200 nm was used instead of LLZTO with an average particle diameter of 1 μm as an inorganic particle, and the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was set to 27.5:8:55:9.5. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 1.2.

[0167] Comparative Example 5.

[0168] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that SiO2 with an average particle diameter of 200 nm was used instead of LLZTO with an average particle diameter of 1 μm as an inorganic particle, and that the weight ratio of the single-ion conductive monomer, crosslinker, inorganic particles, and cyclic carbonate included in the manufactured composite polymer electrolyte was 24:7:48.5:20.5. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 3.1.

[0169] Comparative Example 6.

[0170] A composite polymer electrolyte was obtained in the same manner as in Example 1, except that the weight ratio of the single-ion conductive monomer, crosslinker, and cyclic carbonate included in the manufactured composite polymer electrolyte was 51.3:15.4:33.3 without introducing inorganic particles. At this time, Li included in the single-ion conductive monomer of the manufactured composite polymer electrolyte The ratio of the mole number of the cyclic carbonate to the mole number of the ion was 2.4.

[0171] Evaluation example. Ionic conductivity

[0172] In order to measure the ionic conductivity of the composite polymer electrolyte, the composite polymer electrolyte was formed on the lower plate of a 2032 type coin cell, and then a 1.6 cm diameter SUS disc was used as a blocking electrode to manufacture a coin cell with a SUS / composite polymer electrolyte / SUS symmetrical structure. Using an electrochemical impedance spectrometer (EIS, VM3, Bio Logic Science Instrument), the resistance was measured at 25°C with an amplitude of 10 mV and a scan range of 1 Hz to 0.1 MHz, and then the ionic conductivity of the composite polymer electrolyte was calculated using the following equation 1.

[0173] [Formula 1]

[0174]

[0175] In the above formula 1, σ i is the ionic conductivity (S cm) of the composite polymer electrolyte. -1 ), R is the resistance (Ω) of the composite polymer electrolyte measured by the electrochemical impedance spectrometer, L is the thickness (cm) of the composite polymer electrolyte, and A is the measured area (cm) of the composite polymer electrolyte. 2 ) means.

[0176] As a result, the ionic conductivity of the composite polymer electrolytes of the examples and comparative examples was confirmed as shown in Table 1 below.

[0177]

Claims

1. A single-ion conductive polymer polymerized from a mixed solution containing a single-ion conductive monomer of the following chemical formula 1 and a cross-linking agent; a cyclic carbonate; and inorganic particles; A composite polymer electrolyte characterized in that the molar ratio between the cyclic carbonate and the lithium ion contained in the single ion conductive polymer is 5 or more: [Chemical Formula 1] [Chemical formula 2] In the above formula, Q1 is C 6-12 is an arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, R1 is hydrogen or C 1-3 is an alkyl group, Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It is an alkyl group.

2. In the first paragraph, a composite polymer electrolyte characterized in that the single ion conductive monomer of the chemical formula 1 is at least one selected from the group consisting of the following chemical formulas A to E: [Chemical Formula A] [Chemical Formula B] [Chemical Formula C] [Chemical Formula D] [Chemical formula E] 3. In the first paragraph, the inorganic particles are lithium lanthanum zirconium tantalum oxide (LLZTO), lithium lanthanum zirconium oxide (LLZO), lithium lanthanum tantalum oxide (LLTaO), lithium lanthanum titanate (LLT), lithium phosphorous oxynitride (LiPON), lithium orthosilicate (Li4SiO4), lithium borate (Li3BO3), lithium aluminum germanium phosphate (LAGP), lithium aluminum titanium phosphate (LiAlO). A composite polymer electrolyte, characterized in that the active inorganic particle is at least one selected from the group consisting of lithium phosphate (LATP), lithium lanthanum zirconium niobium oxide (LLZ-Nb), and lithium orthosilicate-lithium phosphate composite (Li4SiO4-Li3PO4), or at least one inactive inorganic particle is selected from the group consisting of zinc oxide (ZnO), silicon dioxide (SiO2), aluminum oxide (Al2O3), and titanium dioxide (TiO2).

4. A composite polymer electrolyte according to claim 3, characterized in that the particle size of the active inorganic particles is 1.5 ㎛ or less, and the particle size of the inactive inorganic particles is 500 nm or less.

5. In the first paragraph, the crosslinking agent is polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polyethylene glycol monoethyl ether acrylate (PEGMEA), polyethylene glycol monomethacrylate (PEGMEMA), pentaerythritol triacrylate (PETA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), and ethoxylated trimethylolpropane. A composite polymer electrolyte characterized by comprising at least one selected from the group consisting of triacrylate (Ethoxylated Trimethylolpropane Triacrylate; ETPTA).

6. A composite polymer electrolyte according to claim 5, characterized in that the cross-linking agent has a number average molecular weight (Mn) of 100 to 10,000 g / mol.

7. A composite polymer electrolyte according to claim 1, characterized in that the cyclic carbonate is at least one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), and γ-butyrolactone.

8. A composite polymer electrolyte according to claim 1, characterized in that it contains 40 wt% or less of the single ion conductive polymer.

9. A composite polymer electrolyte characterized in that the inorganic particles in the first paragraph are contained in an amount of 100 to 1,000 parts by weight per 100 parts by weight of the single ion conductive polymer.

10. A composite polymer electrolyte characterized in that the cyclic carbonate of claim 1 is contained in an amount of 100 to 1,000 parts by weight per 100 parts by weight of the single ion conductive polymer.

11. In the first paragraph, the ionic conductivity at 25°C is 1.0 X 10 -4 A composite polymer electrolyte characterized by having a S / cm or greater.

12. A step of preparing a mixed solution containing a single ion conductive monomer of the following chemical formula 1, inorganic particles, and a cross-linking agent (step S1); A step of heating the above mixed solution at a high temperature to polymerize a single ion conductive polymer and form a film including the single ion conductive polymer (step S2); and A step of impregnating the above film with a cyclic carbonate (step S3); A method for producing a composite polymer electrolyte, characterized in that the molar ratio of the cyclic carbonate to lithium ions contained in the single ion conductive polymer is 5 or more: [Chemical Formula 1] [Chemical formula 2] In the above formula, Q1 is C 6-12 is an arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, R1 is hydrogen or C 1-3 is an alkyl group, Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It is an alkyl group.

13. A method for producing a composite polymer electrolyte, characterized in that in the 12th paragraph, the S2 step is performed at a temperature of 40 to 100° C. under vacuum conditions for 12 to 24 hours.

14. Containing a positive electrode, a solid electrolyte membrane and a negative electrode, The above solid electrolyte membrane comprises a composite polymer electrolyte, The above composite polymer electrolyte comprises a single ion conductive polymer polymerized from a mixed solution containing a single ion conductive monomer of the following chemical formula 1 and a cross-linking agent; a cyclic carbonate; and inorganic particles; An all-solid-state battery characterized in that the molar ratio between the cyclic carbonate and the lithium ion contained in the single ion conductive polymer is 5 or more: [Chemical Formula 1] [Chemical formula 2] In the above formula, Q1 is C 6-12 is an arylene group or a functional group represented by chemical formula 2, wherein n is an integer from 1 to 10, R1 is hydrogen or C 1-3 is an alkyl group, Q2 is a halogen group or C substituted with a halogen group. 1-3 is an alkyl group, Q3 is =O or =NS(O)2-R2, wherein R2 is a halogen group or C substituted with a halogen group. 1-3 It is an alkyl group.

15. An all-solid-state battery according to claim 14, characterized in that lithium metal or a lithium alloy is used as a negative electrode.

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