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

Abstract

According to the present invention, a composite polymer electrolyte and a method for producing the same can be provided, which are excellent not only in mechanical strength but also in ionic conductivity. Furthermore, according to the present invention, such a composite polymer electrolyte can be applied in particular to all-solid-state batteries that use lithium metal or lithium alloy as the negative electrode, suppressing the generation of lithium dendrites and improving lifespan characteristics.

Description

[Technical Field]

[0001] This application claims priority under Korean Patent Application No. 2024-0002097 dated January 5, 2024, and all content disclosed in the documents of the said Korean Patent Application is incorporated herein by reference. The present invention relates to a monoionic conductive composite polymer electrolyte, a method for producing the same, and an all-solid-state battery comprising the same. [Background technology]

[0002] Organic liquid electrolytes, which have been commonly used in lithium-ion secondary batteries, have problems such as flammability, corrosiveness, thermal instability, high-voltage instability, and leakage, and can induce ignition or explosion when the battery behaves abnormally, thus posing a problem.

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

[0004] Polymer electrolytes are a type of solid electrolyte that offers superior stability compared to liquid electrolytes because they are free from the risks of electrolyte leakage or flammability in the event of abnormal behavior. Furthermore, because they do not leak, they can be used to create thin, lightweight, and flexible batteries that do not require rigid external packaging. They also possess several advantages, including high energy density, low volatility, and low reactivity, making them a subject of considerable interest.

[0005] However, polymer electrolytes have low mechanical strength and low ionic conductivity, making it difficult to realize all-solid-state batteries with superior performance. In particular, there have recently been attempts to use lithium metal as the negative electrode to improve energy density, but when lithium metal is used as the negative electrode, problems such as a decrease in lifespan due to the generation of lithium dendrites arise. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] The present invention aims to provide a composite polymer electrolyte and a method for producing the same, which are excellent not only in mechanical strength but also in ionic conductivity.

[0007] The present invention also aims to apply the above-mentioned composite polymer electrolyte to all-solid-state batteries, particularly those using lithium metal or lithium alloy as the negative electrode, in order to suppress the generation of lithium dendrites and improve lifespan characteristics. [Means for solving the problem]

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

[0009] [Chemical formula 1] [ka]

[0010] [Chemical formula 2] [ka]

[0011] In the above formula, Q1 is C 6-12 It is an allylene group or a functional group represented by chemical formula 2, where n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 It is an alkyl group, and Q2 is a halogen group or a C substituted with a halogen group. 1-3 It is an alkyl group, where Q3 is =O or =NS(O)2-R2, and R2 is a halogen group or a C substituted with a halogen group. 1-3 It is an alkyl group.

[0012] In one embodiment, the monoionic conductive monomer of chemical formula 1 may be characterized by being one or more selected from the group consisting of the following chemical formulas A to E:

[0013] [Chemical formula A] [ka]

[0014] [Chemical formula B] [ka]

[0015] [Chemical formula C] [ka]

[0016] [Chemical formula D] [ka]

[0017] [Chemical formula E] [ka]

[0018] In one embodiment, 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 phosphate oxynitride (LiPON), lithium orthosilicate (Li4SiO4), lithium borate (Li3BO3), lithium aluminum germanium phosphate (LAGP), and lithium aluminum titanium phosphate (Lithium Aluminum Titanium The particles may be characterized by being one or more active inorganic particles selected from the group consisting of Phosphate (LATP), Lithium Lanthanum Zirconium Niobium Oxide (LLZ-Nb), and Lithium Orthosilicate-Lithium Phosphate Composite (Li4SiO4-Li3PO4), or by being one or more inactive inorganic particles selected from the group consisting of Zinc oxide (ZnO), Silicon Dioxide (SiO2), Aluminum Oxide (Al2O3), and Titanium Dioxide (TiO2).

[0019] 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.

[0020] In one embodiment, the crosslinking binder may be characterized by being one or more 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 triacrylate (ETPTA).

[0021] In one embodiment, the number-average molecular weight (Mn) of the crosslinking binder may be characterized as being between 100 g / mol and 10,000 g / mol.

[0022] In one embodiment, the cyclic carbonate may be characterized by being one or more selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), and γ-butyrolactone.

[0023] In one embodiment, the composite polymer electrolyte of the present invention may be characterized by containing 40% by weight or less of the monoionic conductive polymer.

[0024] 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 with respect to 100 parts by weight of the monoionic conductive polymer.

[0025] 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 per 100 parts by weight of the monoionic conductive polymer.

[0026] In one embodiment, the composite polymer electrolyte of the present invention has an ionic conductivity of 1.0 × 10⁻¹⁰ at 25°C. -4 It can be characterized by being S / cm or higher.

[0027] Another aspect of the present invention relates to a method for producing a composite polymer electrolyte, comprising the steps of: producing a mixed solution containing a monoionic conductive monomer of the following chemical formula 1, inorganic particles, and a crosslinking binder (S1 step); heating the mixed solution to a high temperature to polymerize a monoionic conductive polymer and form a film containing the monoionic conductive polymer (S2 step); and impregnating the film with a cyclic carbonate (S3 step); wherein the molar ratio of the cyclic carbonate to the lithium ions contained in the monoionic conductive polymer is 5 or more.

[0028] [Chemical formula 1] [ka]

[0029] [Chemical formula 2] [ka]

[0030] In the above formula, Q1 is C 6-12an arylene group or a functional group represented by Chemical Formula 2, where n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 an alkyl group, Q2 is a halogen group or a C 1-3 alkyl group substituted with a halogen group, Q3 is =O or =N-S(O)2-R2, and R2 is a halogen group or a C 1-3 alkyl group substituted with a halogen group.

[0031] In one embodiment, the S2 step may be characterized in that it is performed at a temperature of 40°C to 100°C for 12 hours to 24 hours under vacuum conditions.

[0032] Still another aspect of the present invention relates to a all-solid-state battery including 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 including a single-ion conductive monomer of the following Chemical Formula 1 and a crosslinking agent; a cyclic carbonate; and inorganic particles, and a molar ratio of the cyclic carbonate to lithium ions contained in the single-ion conductive polymer is 5 or more:

[0033] [Chemical Formula 1] [Chemical Formula 2]

[0034] [Chemical Formula 2] [Chemical Formula 1]

[0035] In the above formula, Q1 is a C 6-12 arylene group or a functional group represented by Chemical Formula 2, where n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 an alkyl group, Q2 is a halogen group or a C 1-3 alkyl group substituted with a halogen group, Q3 is =O or =N-S(O)2-R2, and R2 is a halogen group or a C1-3 It is an alkyl group.

[0036] In one embodiment, the all-solid-state battery of the present invention may be characterized by using lithium metal or a lithium alloy as the negative electrode. [Effects of the Invention]

[0037] According to the present invention, it is possible to provide a composite polymer electrolyte that is excellent not only in mechanical strength but also in ionic conductivity, as well as a method for producing the same.

[0038] According to the present invention, since the composite polymer electrolyte described above is applied in particular to all-solid-state batteries that use lithium metal or lithium alloy as the negative electrode, the generation of lithium dendrites can be suppressed and the lifespan characteristics can be improved. [Modes for carrying out the invention]

[0039] The terms and words used in this specification and in the claims should not be interpreted in a manner limited to their ordinary or dictionary meanings, but rather in a manner consistent with the technical idea of ​​the present invention, based on the principle that inventors can appropriately define the concepts of terms in order to best describe their invention.

[0040] Therefore, the configurations of the embodiments described herein represent only one of the most preferred embodiments of the present invention and do not represent the entire technical concept of the invention. It should be understood that, at the time of filing, there may be a variety of equivalents and modifications that can be substituted for these.

[0041] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0042] In this specification, when a part is said to "contain" a component, this means, unless otherwise stated, that it may contain other components rather than excluding them. For example, a composition containing compound A may contain other compounds other than A. However, the term "contains" also encompasses, in its particular embodiment, the more restrictive meanings of "essentially / essentially composed of" and "composed of," for example, a "composition containing compound A" may also be (essentially / essentially) composed of compound A.

[0043] In this regard, as described herein, terms such as “equipped with” or “possess” are intended to specify the presence of implemented features, figures, stages, components, or combinations thereof, and should be understood not to preemptively exclude the possibility of the presence or addition of one or more different features, figures, stages, components, or combinations thereof.

[0044] In this specification, when any layer is said to be located "on top of" or "between" any other layer, this includes not only cases where any layer is in contact with any other layer, but also cases where there are other layers or materials between the two layers.

[0045] In this specification, where a quantity, concentration, or other value or parameter is given by listing a range, preferred range, preferred upper limit, and preferred lower limit, it should be understood that this specifically discloses all ranges that can be formed by any pair of any upper range limits or preferred values ​​and any lower range limits or preferred values, regardless of whether the range is disclosed separately. Where a range of a number is referred to herein, unless otherwise stated, and without limiting terms such as greater than or less than, the range is intended to include its endpoint and all integers and fractions within that range. The scope of the invention is intended not to be limited to specific values ​​referred to when defining a range.

[0046] In this specification, if the measurement temperature affects the physical properties mentioned, those properties are measured at room temperature unless otherwise specified. The term "room temperature" refers to the natural temperature without heating or deheating, and may mean, for example, any temperature within the range of approximately 10°C to 30°C, or approximately 23°C or 25°C. Furthermore, unless otherwise specified, the unit of temperature in this specification is °C.

[0047] Furthermore, in the case of any physical properties mentioned herein where the measurement pressure affects the property in question, unless otherwise specified, the physical properties are measured at normal pressure, i.e., atmospheric pressure (approximately 1 atmosphere).

[0048] The first aspect of this invention relates to composite polymer electrolytes.

[0049] The composite polymer electrolyte of the present invention may include, for example, a monoionic conductive polymer polymerized from a mixed solution containing a monoionic conductive monomer of the following chemical formula 1 and a crosslinking binder; a cyclic carbonate; and / or inorganic particles:

[0050] [Chemical formula 1] [ka]

[0051] [Chemical formula 2] [ka]

[0052] In the above formula, Q1 is C 6-12 It can be an allylene group or a functional group represented by chemical formula 2, in which case n can 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 a C substituted with a halogen group. 1-3 It can be an alkyl group, Q3 can be =O or =NS(O)2-R2, and R2 is a halogen group or C substituted with a halogen group. 1-3It can be an alkyl group.

[0053] In this specification, the term "arylene group" refers to a functional group derived primarily from benzene or related aromatic structures. Examples of such arylene groups include, but are not limited to, phenylene, biphenylene, terphenylene, quarterphenylene, naphthalenylene, anthracenylene, phenantrenylene, phenylene, or benzopyrenylene groups.

[0054] In this specification, the term "alkyl group" refers to itself or part of other substituents, and unless otherwise specified, to the number of carbon atoms indicated (i.e., C 1-10 A monovalent hydrocarbon is a straight-chain or branched-chain hydrocarbon having one to ten carbon atoms.

[0055] Examples of the alkyl groups mentioned above include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1-ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, Examples of cyclohexyl groups include cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group, isohexyl group, 2-methylpentyl group, 4-methylhexyl group, and 5-methylhexyl group, but these are non-limiting examples and do not limit the scope of the present invention.

[0056] In this specification, the term "halogen" includes, but is not limited to, fluoro, chloro, bromo, or iodine, for example.

[0057] The aforementioned Q1 is, for example, C 6-12 It may be an allylene group or a functional group represented by the above chemical formula 2. In other examples, Q1 is C 6-10 Allylene group, C 6-8 When n is an allylene group or a functional group represented by chemical formula 2, n may be 1 or more, 2 or more, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less. In terms of polymerization stability and improved mechanical strength, Q1 is preferably a phenylene group or a functional group represented by chemical formula 2 with n=3.

[0058] R1 is, for example, hydrogen or C 1-3 It may be an alkyl group. In terms of improving polymerization reactivity, R1 may preferably be a hydrogen or methyl group.

[0059] 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, Q2 may preferably be fluorine or -CF3.

[0060] Q3 can be, for example, =O or =NS(O)2-R2. In terms of improving ionic conductivity, Q3 is preferably =O or =NS(O)2-CF3.

[0061] The monoionic conductive monomer of chemical formula 1 may be characterized by being, for example, one or more selected from the group consisting of the following chemical formulas A to E:

[0062] [Chemical formula A] [ka]

[0063] [Chemical formula B] [ka]

[0064] [Chemical formula C] [ka]

[0065] [Chemical formula D] [ka]

[0066] [Chemical formula E] [ka]

[0067] The composite polymer electrolyte of the present invention achieves a high transport efficiency (transference numbers, t) by synthesizing a monoion-conducting polymer using the monoion-conducting monomers described above, thereby restricting the movement of anions. Li+ It has a value of ) and can suppress lithium dendrites by reducing the ion concentration gradient.

[0068] The crosslinking binder may be characterized by being one or more selected from the group consisting of, 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 triacrylate (ETPTA). From the viewpoint of easy polymerization reaction with monoionic conductive monomers, improvement of ionic conductivity, and control of diverse physical properties, the crosslinking binder may preferably be characterized by polyethylene glycol diacrylate (PEGDA).

[0069] The crosslinking binder may be characterized, for example, by having a number-average molecular weight (Mn) of 100 g / mol to 10,000 g / mol. In other examples, the crosslinking binder 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. By introducing a crosslinking binder having such a number-average molecular weight (Mn), the present invention can provide a composite polymer electrolyte with excellent ionic conductivity and mechanical strength.

[0070] The composite polymer electrolyte of the present invention may be characterized by comprising a monoionic conductive polymer polymerized from a mixed solution containing, for example, a monoionic conductive monomer of chemical formula 1 and a crosslinking binder as described above. The mixed solution may further contain a solvent as described in the second aspect described later, but during the polymerization process, the solvent evaporates and is not contained in the monoionic conductive polymer, or if it is contained, it may be in an amount of 1% by weight or less, 0.1% by weight or less, 0.01% by weight or less, or 0.001% by weight or less.

[0071] The composite polymer electrolyte of the present invention may, for example, include a carbonate, and the carbonate may be characterized by being a cyclic carbonate. The carbonate may be cyclic or linear, but when a cyclic carbonate is applied to the composite polymer electrolyte of the present invention, better bonding with lithium ions can be achieved compared to when a linear carbonate is applied, and as a result, superior ionic conductivity can be observed.

[0072] The cyclic carbonate may be characterized by being one or more selected from the group consisting of, for example, ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), and γ-butyrolactone.

[0073] 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 monoionic conductive polymer of 5 or more. In this specification, the molar ratio of cyclic carbonate to lithium ions contained in the monoionic conductive polymer may be a molar ratio based on the amount added, or a value measured for the final manufactured composite polymer electrolyte. In the prior art, even if carbonate is introduced, it is difficult to control the above-mentioned molar ratio in the final manufactured composite polymer electrolyte because the carbonate evaporates during the manufacturing process of the polymer electrolyte, and there was no motivation to try to control it. The inventors have found that by impregnating a film formed by polymerizing a monoionic conductive polymer with cyclic carbonate and assembling a battery, as described later for the manufacturing method of composite polymer electrolytes, it is possible to manufacture a composite polymer electrolyte without evaporation of carbonate, and therefore, even in the final manufactured composite polymer electrolyte, it was possible to control the molar ratio of cyclic carbonate to lithium ions contained in the monoionic conductive polymer to 5 or more. As a result, a composite polymer electrolyte can be provided that has excellent mechanical strength while also having excellent ionic conductivity, making it suitable for use as a solid electrolyte on its own. In particular, it can be applied to all-solid-state batteries that use lithium metal or lithium alloy as the negative electrode, which can suppress the generation of lithium dendrites and contribute to improving lifespan characteristics and performance. In other examples, the composite polymer electrolyte of the present invention can be controlled so that the molar ratio of the cyclic carbonate to lithium ions contained in the monoionic 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.

[0074] The composite polymer electrolyte of the present invention may include, for example, inorganic particles. The inorganic particles may be, for example, LLZTO(Li 6.75 La3Zr 1.75 Ta 0.25 O 12 Li6.5 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 The particles may be characterized by being one or more active inorganic particles selected from the group consisting of ), and Li4SiO4-Li3PO4, or one or more inactive inorganic particles selected from the group consisting of ZnO, SiO2, Al2O3, and TiO2. From the standpoint of manufacturing costs, using inactive inorganic particles may be more advantageous than using active inorganic particles.

[0075] The active inorganic particles may, for example, have a particle size of 1.5 μm or less. In this specification, particle size may be measured by a particle size analyzer (Particle Size Analyzer using Laser Diffraction, Mastersizer 3000, Malvern Panalytical), and may refer to the maximum, average, and / or minimum particle size. In other examples, the 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 aggregation can be suppressed, and excellent dispersibility can be achieved.

[0076] The inactive inorganic particles may, for example, have a particle size of 500 nm or less. In other examples, the inactive inorganic particles may be characterized by having 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 inactive inorganic particles as described above, sedimentation due to particle aggregation can be suppressed, and excellent dispersibility can be achieved.

[0077] The composite polymer electrolyte of the present invention can have superior ionic conductivity and mechanical strength by controlling the weight ratio of each material as follows.

[0078] The composite polymer electrolyte of the present invention may be characterized by containing, for example, 40% by weight or less of the monoionic conductive polymer. In other examples, the composite polymer electrolyte of the present invention may be characterized by containing 35% by weight or less, 30% by weight or less, or 25% by weight or less of the monoionic conductive polymer, or by containing 1% by weight or more, 5% by weight or more, or 10% by weight or more. By containing the monoionic conductive polymer in the weight ranges described above, the ionic conductivity and mechanical strength of the composite polymer electrolyte of the present invention can be further improved.

[0079] The composite polymer electrolyte of the present invention may be characterized by containing, for example, 60 to 90 parts by weight of the monoionic conductive monomer of chemical formula 1 per 100 parts by weight of the monoionic conductive polymer. In other examples, 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, per 100 parts by weight of the monoionic conductive monomer of chemical formula 1 per 100 parts by weight of the monoionic conductive polymer.

[0080] The composite polymer electrolyte of the present invention may be characterized by containing, for example, 100 to 1000 parts by weight of the inorganic particles per 100 parts by weight of the monoionic conductive polymer. In other examples, 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, 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, per 100 parts by weight of the monoionic conductive polymer.

[0081] The composite polymer electrolyte of the present invention may be characterized by containing, for example, 100 to 1000 parts by weight of the cyclic carbonate per 100 parts by weight of the monoionic conductive polymer. In other examples, 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, per 100 parts by weight of the monoionic conductive polymer.

[0082] The composite polymer electrolyte of the present invention may further contain, for example, other additives. Examples of such other additives include lithium salts (LiTFSI, LiClO4, LiPF6, etc.), but are not limited thereto, as long as they do not hinder the objective of the present invention, and additives commonly used in polymer electrolytes may be used.

[0083] The composite polymer electrolyte of the present invention, through the combination of the above-described configurations, for example, has an ionic conductivity of 1.0 × 10 at 25°C. -4 It may be greater than S / cm. The ionic conductivity at 25°C may be measured by the method described in the evaluation example below. In other examples, the ionic conductivity of the composite polymer electrolyte of the present invention at 25°C is 1.2 × 10⁻⁶. -4 S / cm or more, 1.4×10 -4 S / cm or more, 1.6×10-4 S / cm or more, 1.8×10 -4 S / cm or more, 2.0×10 -4 S / cm or more, 2.2×10 -4 S / cm or more, 2.4×10 -4 S / cm or more, 2.6×10 -4 S / cm or more, 2.8×10 -4 S / cm or more, 3.0×10 -4 S / cm or more, 3.5×10 -4 S / cm or more, 4.0×10 -4 S / cm or more, 4.5×10 -4 S / cm or more, 5.0×10 -4 S / cm or more, 5.5×10 -4 S / cm or more, 6.0×10 -4 S / cm or more, 6.5×10 -4 S / cm or more, 7.0×10 -4 S / cm or more, 7.5×10 -4 S / cm or larger, or 8.0 × 10 -4 Is it S / cm or more, or 20.0 × 10 -4 S / cm or less, 15.0×10 -4 S / cm or less, 10.0×10 -4 S / cm or less, 9.0×10 -4 S / cm or less, 8.0×10 -4 S / cm or less, 7.0×10 -4 S / cm or less, 6.0×10 -4 S / cm or less, 5.0×10 -4 S / cm or less, 4.0×10 -4 S / cm or less, or 3.0 × 10 -4 It may be less than S / cm.

[0084] A second aspect of the present invention relates to a method for producing a composite polymer electrolyte.

[0085] Unless otherwise specified, the matters relating to the first aspect of the present invention may be applied identically to the matters relating to the second aspect.

[0086] The present invention provides a method for producing a composite polymer electrolyte, which may include, for example, the steps of: producing a mixed solution containing a monoionic conductive monomer of the following chemical formula 1, inorganic particles, and a crosslinking binder (S1 step); heating the mixed solution to a high temperature to polymerize the monoionic conductive polymer and form a film containing the monoionic conductive polymer (S2 step); and impregnating the film with a cyclic carbonate (S3 step), characterized in that the molar ratio of the cyclic carbonate to the lithium ions contained in the monoionic conductive polymer is 5 or more.

[0087] [Chemical formula 1] [ka]

[0088] [Chemical formula 2] [ka]

[0089] In the above formula, Q1 is C 6-12 It is an allylene group or a functional group represented by chemical formula 2, where n is an integer from 1 to 10, and R1 is hydrogen or C 1-3 It is an alkyl group, and Q2 is a halogen group or a C substituted with a halogen group. 1-3 It is an alkyl group, where Q3 is =O or =NS(O)2-R2, and R2 is a halogen group or a C substituted with a halogen group. 1-3 It can be an alkyl group.

[0090] The solvent in step S1 can be, for example, alcohols, acetonitrile, ethers, or mixtures thereof. Examples of alcohols include methanol, ethanol, and butanol, and examples of ethers include dimethyl ether, diethyl ether, and methyl tert-butyl ether, but are not limited thereto.

[0091] The mixed solution in step S1 can be produced, for example, through the steps of: dissolving the monoionic conductive monomer in a solvent (step S1-1); further adding inorganic particles to the solvent and stirring (step S1-2); and further adding a crosslinking binder to the solvent and stirring to produce a mixed solution (step S1-3).

[0092] The stirring in step S1-2 may be characterized by being carried out, for example, at room temperature for 15 to 21 hours. In other examples, the stirring in step S1-2 may be carried out at room temperature for 16 hours or more or 17 hours or more, or for 20 hours or less or 19 hours or less.

[0093] The stirring in stages S1-3 may be carried out, for example, at room temperature for 1 minute to 30 minutes. In other examples, the stirring in stages S1-3 may be characterized by being carried out at room temperature for 3 minutes or more, 5 minutes or more, 7 minutes or more, or 9 minutes or more, or for 25 minutes or less, 20 minutes or less, or 15 minutes or less.

[0094] The S2 stage may be characterized by being carried out, for example, under vacuum conditions at a temperature of 40°C to 100°C for 12 to 24 hours. The temperature of the S2 stage may, in other examples, be 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 duration of the S2 stage may, in other examples, be 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.

[0095] 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 done when the cyclic carbonate is in a solid phase at room temperature, and if it is in a liquid state, it can be used immediately without the liquefaction step.

[0096] A third aspect of the present invention relates to all-solid-state batteries.

[0097] The matters relating to the first and / or second aspects of the present invention may be applied identically to the matters relating to the third aspect, unless otherwise specified.

[0098] 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 contains a composite polymer electrolyte, and the composite polymer electrolyte contains a monoionic conductive polymer polymerized from a mixed solution containing a monoionic conductive monomer of chemical formula 1 and a crosslinking binder; a cyclic carbonate; and inorganic particles, and the molar ratio of the cyclic carbonate to lithium ions contained in the monoionic conductive polymer is 5 or more.

[0099] In this specification, the matters relating to the positive and negative electrodes are described below as examples for the sake of ease of understanding, but are not limited thereto; the matters relating to the positive and negative electrodes of known solid-state batteries may also apply.

[0100] The positive electrode may include, for example, a positive electrode current collector and a positive electrode active material layer, the positive electrode active material layer may include a positive electrode active material, a binder, a conductive material, and / or a solid electrolyte.

[0101] The positive electrode current collector is not particularly limited as long as it is conductive without inducing chemical changes in the battery, and may be, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel with a surface treatment of carbon, nickel, titanium, silver, etc. Furthermore, fine irregularities can be formed on the surface to strengthen the bonding force with the positive electrode active material layer, and it can be used in a variety of forms such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.

[0102] The positive electrode active material reversibly intercalates and deintercalates lithium ions. Examples of the positive electrode active material include, but are 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, and vanadium oxide. Any material that can be used as a positive electrode active material in the relevant technical field is possible. The positive electrode active material can be used alone or in combination of two or more kinds.

[0103] The 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-cD c (In the above formula, 0.90 ≤ a ≤ 1, 0 ≤ b ≤ 0.5, and 0 ≤ c ≤ 0.05); LiE 2-b B b O 4-c D c (In the above formula, 0 ≤ b ≤ 0.5 and 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, and 0 < α < 2); Li a CoG b O2 (In the above formula, 0.90 ≤ a ≤ 1 and 0.001 ≤ b ≤ 0.1); Li a MnG b O2 (In the above formula, 0.90 ≤ a ≤ 1 and 0.001 ≤ b ≤ 0.1); Li a Mn2G b O4 (In the above formula, 0.90 ≤ a ≤ 1 and 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, and 0 < α < 2); Li a Ni 1-b-c Mn b B c O 2-α F2(In the above equation, 0.90≦a≦1, 0≦b≦0.5, 0≦c≦0.05, and 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 bO2 (In the above formula, 0.90 ≤ a ≤ 1 and 0.001 ≤ b ≤ 0.1); QO2; QS2; LiQS2; V2O5; LiV2O5; LiIO2; LiNiVO4; Li (3-f) J2(PO4)3(0≦f≦2);Li (3-f) The compound may be represented by one of the following chemical formulas: Fe2(PO4)3 (0≦f≦2);LiFePO4. In such a compound, A is Ni, Co, Mn, or a combination thereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements, 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 is V, Cr, Mn, Co, Ni, Cu, or a combination thereof. As the positive electrode active material, a compound with a coating layer attached to its surface may be used, or a mixture of the aforementioned compound and the compound with the coating layer attached may be used. The coating layer added to the surface of such a compound may contain, for example, a lithium-ion conductive oxide. The lithium-ion conductive oxide may be, for example, LiNbO3, Li4Ti5O 12 Examples include, but are not limited to, Li3PO4. The compound forming such a coating layer may be amorphous or crystalline. Methods for forming the coating layer may include, for example, spray coating or immersion, but can be selected without limitation as long as they do not adversely affect the physical properties of the positive electrode active material.

[0104] If the positive electrode active material includes nickel (Ni) as a ternary lithium transition metal oxide such as NCA or NCM, it may be possible to increase the capacity density of the all-solid-state battery and reduce the metal leaching of the positive electrode active material in the charged state. This may improve the cycle characteristics of the all-solid-state battery in the charged state.

[0105] The shape of the positive electrode active material may be, for example, a perfect sphere, an ellipsoid, or some other particle shape. The particle size of the positive electrode active material is not particularly limited and should be within a range applicable to the positive electrode active material of conventional all-solid-state secondary batteries. The content of the positive electrode active material in the positive electrode is also not particularly limited and should be within a range applicable to the positive electrode of conventional all-solid-state secondary batteries.

[0106] The binder may be, for example, an aqueous binder, an organic binder, or a combination thereof. The binder may be, for example, polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinylidene fluoride, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene, fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or a combination thereof. For the aqueous binder, for example, styrene-butadiene rubber, carboxymethylcellulose, or a combination thereof can be used. For the organic binder, for example, polytetrafluoroethylene, polyvinylidene fluoride, or a combination thereof can be used, but is not limited thereto, and known binders can be used without limitation as long as they do not hinder the purpose of the present invention.

[0107] The conductive material may be, for example, graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanotubes, or metal powder, but is not limited thereto. Any conductive material that can be introduced into an all-solid-state battery can be used without limitation, as long as it does not hinder the purpose of the present invention.

[0108] The solid electrolyte contained in the 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 all-solid-state batteries may be exemplified without limitation, and the composite polymer electrolyte according to the present invention may also be included. The inorganic electrolyte may be a sulfide, oxide, or halide solid electrolyte, but any inorganic electrolyte applicable to all-solid-state batteries may be exemplified without limitation. The composite electrolyte may mean a composite electrolyte containing nanoparticle fillers and polymers, and any composite electrolyte applicable to all-solid-state batteries may be exemplified without limitation.

[0109] The positive electrode active material layer may further contain additives such as fillers, coating agents, dispersants, and ion conductivity enhancers, and these additives can be used without limitation as long as they are known materials commonly used in electrodes for all-solid-state batteries.

[0110] The solid electrolyte membrane may, for example, include a composite polymer electrolyte having the characteristics described above. The all-solid-state battery of the present invention includes such a composite polymer electrolyte in the solid electrolyte membrane and may have excellent lifespan characteristics and performance.

[0111] The solid electrolyte membrane may further contain, for example, a binder. An example of such a binder is the binder contained in the positive electrode active material layer described above.

[0112] The thickness of the solid electrolyte membrane is not particularly limited, but is usually in the range of 0.1 μm to 500 μm.

[0113] The negative electrode may include, for example, a negative electrode active material layer, the negative electrode active material layer may include a negative electrode active material, a binder, a conductive material, and / or a solid electrolyte.

[0114] The negative electrode active material is, for example, carbon such as non-graphitizable carbon or graphite-based carbon; Li x Fe2O3 (0 ≤ x ≤ 1), Li x WO2(0≦x≦1), Sn xMe 1-x Me' y O z One or more of the following can be used: metal composite oxides such as (Me: Mn, Fe, Pb, Ge; Me'; Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogens; 0≦x≦1; 1≦y≦3; 1≦z≦8); lithium metal; lithium alloys; lithium-indium alloys; silicon alloys; tin alloys; indium; indium alloys; 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 materials; titanium oxides; lithium titanium oxides; etc.

[0115] The solid electrolyte, conductive material, and / or binder contained in the negative electrode active material layer may be one of the types contained in the positive electrode or solid electrolyte membrane described above, but is not limited to these; any solid electrolyte, conductive material, and / or binder used in the art may be used. The solid electrolyte, conductive material, and / or binder contained in the negative electrode active material layer may be the same as or different from the solid electrolyte and / or binder contained in the positive electrode active material layer, solid electrolyte membrane, etc.

[0116] The negative electrode active material layer may further include, for example, other additives. These additives can be any known material commonly used in electrodes for all-solid-state batteries, without limitation.

[0117] The all-solid-state battery of the present invention can use lithium metal or a lithium alloy as the negative electrode, particularly from the viewpoint of improving energy density. However, when lithium metal or a lithium alloy is used as the negative electrode, there is a problem in that lithium dendrites are generated due to the formation of an uneven interface with the solid electrolyte and high reactivity, which reduces the battery's lifespan characteristics. In particular, the present invention can solve this problem in such an all-solid-state battery using lithium as the negative electrode by having the solid electrolyte membrane contain the aforementioned composite polymer electrolyte, and / or by having the solid electrolyte contained in the negative or positive electrode contain the aforementioned composite polymer electrolyte. This makes it possible to provide an all-solid-state battery in which energy density, lifespan, performance, and other aspects can all be improved.

[0118] The negative electrode may further include, for example, a negative electrode current collector. The negative electrode current collector can be a known metal usable as a current collector in all-solid-state batteries. The negative electrode current collector can be, for example, a material that does not form alloys or compounds with lithium. The negative electrode current collector can 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 art can be used as long as it does not hinder the purpose of the present invention. The negative electrode current collector may be composed of one of the aforementioned metals, or an alloy or coating material of two or more metals. The negative electrode current collector can be used in a variety of forms, such as films, sheets, foils, nets, porous materials, foams, and nonwoven fabrics.

[0119] In the following, the present invention will be described in detail with reference to examples in order to specifically illustrate the disclosures of the present invention as described above and the intended functions and effects of the present invention. However, the examples may be modified into several different forms, and the scope of this specification should not be construed as being limited to these examples alone. It should be emphasized that the examples are provided to illustrate the present invention in more detail to those skilled in the art.

[0120] Example 1. The composite polymer electrolyte was manufactured using the following method, such that the weight ratio of monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 13:4:52:31.

[0121] First, LiSTFSI ((trifluoromethane)sulfonamide lithium styrene) was dissolved in acetonitrile solvent at a concentration of 10% by weight as a monoionic conductive monomer. Then, LLZTO with an average particle size of 1 μm was added as inorganic particles, and the mixture was stirred for an additional 18 hours at room temperature using a magnetic bar. Subsequently, PEGDA with Mn = 575 g / mol was added to the solution as a crosslinking binder, and the mixture was stirred for an additional 10 minutes at room temperature. The prepared mixed solution was then applied to a substrate. After that, a film was obtained by forming a polymer structure through a crosslinking reaction and performing a solvent drying process in a 60°C vacuum oven for 18 hours. Subsequently, EC (ethylene carbonate), which had been liquefied by instantaneous immersion in an oven at 35°C or 40°C, was impregnated into the film as a cyclic carbonate to obtain a composite polymer electrolyte. At this time, the ratio of the number of moles of cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the prepared composite polymer electrolyte was 8.5.

[0122] Example 2. A composite polymer electrolyte was obtained using the same method as in Example 1, except that the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was set to 11:3:45:41. At this time, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 13.2.

[0123] Example 3. A composite polymer electrolyte was obtained using the same method as in Example 1, except that the weight ratio of the monoionic conductive monomer, crosslinking agent, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was set to 10:3:38:49. At this time, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 18.9.

[0124] Example 4. A composite polymer electrolyte was obtained using the same method as in Example 1, except that ZnO with an average particle size of 50 nm was used as the inorganic particle instead of LLZTO with an average particle size of 1 μm, and the weight ratio of monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 12:4:54:30. At this time, the ratio of the number of moles of cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 8.9.

[0125] Example 5. A composite polymer electrolyte was obtained using the same method as in Example 1, except that SiO2 with an average particle size of 200 nm was used as the inorganic particle instead of LLZTO with an average particle size of 1 μm, and the weight ratio of monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 18:6:37:39. At this time, the ratio of the number of moles of cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 7.7.

[0126] Example 6. A composite polymer electrolyte was obtained using the same method as in Example 1, except that the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 15:4.5:59.5:21. At this time, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 5.2.

[0127] Example 7. A composite polymer electrolyte was obtained using the same method as in Example 1, except that PC (propylene carbonate) was introduced as the cyclic carbonate instead of EC, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate in the manufactured composite polymer electrolyte was set to 13:4:52:31. At this time, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 7.4.

[0128] Example 8. A composite polymer electrolyte was obtained using the same method as in Example 1, except that ZnO with an average particle size of 50 nm was used as the inorganic particle instead of LLZTO with an average particle size of 1 μm, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 14.2:4.3:61.2:20.3. At this time, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 5.2.

[0129] Example 9. A composite polymer electrolyte was obtained using the same method as in Example 1, except that SiO2 with an average particle size of 200 nm was used as the inorganic particle instead of LLZTO with an average particle size of 1 μm, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 21:6.5:43:29.5. At this time, the ratio of the number of moles of cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 5.

[0130] Comparative Example 1. A composite polymer electrolyte was obtained using the same method as in Example 1, except that a cyclic carbonate was not introduced and the weight ratio of the monoionic conductive monomer, crosslinking binder, and inorganic particles in the manufactured composite polymer electrolyte was 19:6:75. In this case, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 0.

[0131] Comparative Example 2. A composite polymer electrolyte was obtained using the same method as in Example 1, except that ethyl methyl carbonate (EMC) was introduced as a linear carbonate instead of a cyclic carbonate, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and linear carbonate in the manufactured composite polymer electrolyte was set to 13:4:54:29. At this time, the ratio of the number of moles of the linear carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 6.6.

[0132] Comparative Example 3. A composite polymer electrolyte was obtained using the same method as in Example 1, except that PC (propylene carbonate) was introduced as the cyclic carbonate instead of EC, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate in the manufactured composite polymer electrolyte was set to 17:5:67:11. In this case, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 2.

[0133] Comparative Example 4. A composite polymer electrolyte was obtained using the same method as in Example 1, except that SiO2 with an average particle size of 200 nm was used as the inorganic particle instead of LLZTO with an average particle size of 1 μm, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 27.5:8:55:9.5. At this time, the ratio of the number of moles of cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 1.2.

[0134] Comparative Example 5. A composite polymer electrolyte was obtained using the same method as in Example 1, except that SiO2 with an average particle size of 200 nm was used as the inorganic particle instead of LLZTO with an average particle size of 1 μm, and the weight ratio of the monoionic conductive monomer, crosslinking binder, inorganic particles, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 24:7:48.5:20.5. At this time, the ratio of the number of moles of cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 3.1.

[0135] Comparative Example 6. A composite polymer electrolyte was obtained using the same method as in Example 1, except that inorganic particles were not introduced and the weight ratio of the monoionic conductive monomer, crosslinking binder, and cyclic carbonate contained in the manufactured composite polymer electrolyte was 51.3:15.4:33.3. In this case, the ratio of the number of moles of the cyclic carbonate to the number of moles of Li ions contained in the monoionic conductive monomer of the manufactured composite polymer electrolyte was 2.4.

[0136] Evaluation example: Ionic conductivity 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. A 1.6 cm diameter SUS disc was then used as a blocking electrode to fabricate a coin cell with a symmetrical structure of SUS / composite polymer electrolyte / SUS. 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. The ionic conductivity of the composite polymer electrolyte was then calculated using Equation 1 below.

[0137] [Formula 1]

number

[0138] In the above formula 1, σ i This is the ionic conductivity (Scm) of the composite polymer electrolyte. -1 ) where R is the resistance (Ω) of the composite polymer electrolyte measured with the electrochemical impedance spectrometer, L is the thickness (cm) of the composite polymer electrolyte, and A is the measurement area (cm) of the composite polymer electrolyte. 2 ) means.

[0139] 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.

[0140] Table 1

Claims

1. The material comprises a monoionic conductive polymer polymerized from a mixed solution containing a monoionic conductive monomer of the following chemical formula 1 and a crosslinking binder, a cyclic carbonate, and inorganic particles. A composite polymer electrolyte characterized in that the molar ratio of the cyclic carbonate to the lithium ions contained in the monoionic conductive polymer is 5 or more: [Chemical formula 1] 【Chemistry 1】 [Chemical formula 2] 【Chemistry 2】 In the above formula, Q １ is C ６－１２ It is an allylene group or a functional group represented by chemical formula 2, in which case n is an integer from 1 to 10. R １ is hydrogen or C １－３ It is an alkyl group, Q ２ C is a halogen group or a C substituted with a halogen group. １－３ It is an alkyl group, Q ３ is =O or =N-S(O) ２ -R ２ wherein said R ２ is a halogen group or a C １－３ alkyl group substituted with a halogen group.

2. The composite polymer electrolyte according to claim 1, characterized in that the monoionic conductive monomer of chemical formula 1 is one or more selected from the group consisting of the following chemical formulas A to E: [Chemical formula A] 【Transformation 3】 [Chemical formula B] 【Chemistry 4】 [Chemical formula C] 【Transformation 5】 [Chemical formula D] 【Transformation 6】 [Chemical formula E] 【Transformation 7】

3. 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-phosphorus-oxynitride (LiPON), lithium orthosilicate (Lithium Orthosilicate;Li ４ SiO ４ ), Lithium borate (Lithium Borate; Li ３ BO ３ ), lithium-aluminum-germanium-phosphate (LAGP), lithium-aluminum-titanium-phosphate (LAATP), lithium-lanthanum-zirconium-niobium oxide (LLZ-Nb), and lithium orthosilicate-lithium phosphate composite (Li ４ SiO ４ -Li ３ PO ４ One or more active inorganic particles selected from the group consisting of ) or zinc oxide (ZnO), silicon dioxide (SiO2) ２ ), aluminum oxide (Al ２ O ３ ), and titanium dioxide (TiO2). ２ The composite polymer electrolyte according to claim 1, characterized in that it is one or more inactive inorganic particles selected from the group consisting of ).

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

5. The aforementioned crosslinking binders are polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polyethylene glycol monoethyl ether acrylate (PEGMEA), polyethylene glycol monomethacrylate (PEGMEMA), pentaerythritol triacrylate (PETA), and 1,6-hexanediol diacrylate (1,6-Hexanediol The composite polymer electrolyte according to claim 1, characterized in that it is one or more selected from the group consisting of Diacrylate (HDDA), Trimethylolpropane Triacrylate (TMPTA), Trimethylolpropane Trimethacrylate (TMPTMA), and Ethoxylated Trimethylolpropane Triacrylate (ETPTA).

6. The composite polymer electrolyte according to claim 5, characterized in that the number average molecular weight (Mn) of the crosslinking binder is 100 g / mol to 10,000 g / mol.

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

8. The composite polymer electrolyte according to claim 1, characterized in that it contains 40% by weight or less of the monoionic conductive polymer.

9. The composite polymer electrolyte according to claim 1, characterized in that the inorganic particles are present in an amount of 100 to 1000 parts by weight per 100 parts by weight of monoionic conductive polymer.

10. The composite polymer electrolyte according to claim 1, characterized in that the cyclic carbonate is contained in an amount of 100 to 1000 parts by weight per 100 parts by weight of the monoionic conductive polymer.

11. The ionic conductivity at 25°C is 1.0 × 10⁻⁶. －４ The composite polymer electrolyte according to claim 1, characterized in that it is S / cm or higher.

12. The process involves a step (S1) of producing a mixed solution containing a monoionic conductive monomer of the following chemical formula 1, inorganic particles, and a crosslinking binder, The steps include heating the mixed solution at a high temperature to polymerize the monoionic conductive polymer and form a film containing the monoionic conductive polymer (step S2), The step includes impregnating the film with an annular carbonate (step S3), A method for producing a composite polymer electrolyte, characterized in that the molar ratio of the cyclic carbonate to the lithium ions contained in the monoionic conductive polymer is 5 or more: [Chemical formula 1] 【Transformation 8】 [Chemical formula 2] 【Chemistry 9】 In the above formula, Q １ is C ６－１２ It is an allylene group or a functional group represented by chemical formula 2, in which case n is an integer from 1 to 10. R １ is hydrogen or C １－３ It is an alkyl group, Q ２ C is a halogen group or a C substituted with a halogen group. １－３ It is an alkyl group, Q ３ is = O or = N-S(O) ２ -R ２ And the R ２ C is a halogen group or a C substituted with a halogen group. １－３ It is an alkyl group.

13. The method for producing a composite polymer electrolyte according to claim 12, characterized in that the S2 step is carried out under vacuum conditions at a temperature of 40°C to 100°C for 12 to 24 hours.

14. It comprises a positive electrode, a solid electrolyte membrane, and a negative electrode. The solid electrolyte membrane contains a composite polymer electrolyte, The aforementioned composite polymer electrolyte comprises a monoionic conductive polymer polymerized from a mixed solution containing a monoionic conductive monomer of the following chemical formula 1 and a crosslinking binder, a cyclic carbonate, and inorganic particles. A solid-state battery characterized in that the molar ratio of the cyclic carbonate to the lithium ions contained in the monoionic conductive polymer is 5 or more: [Chemical formula 1] 【Chemistry 10】 [Chemical formula 2] 【Chemistry 11】 In the above formula, Q １ is C ６－１２ It is an allylene group or a functional group represented by chemical formula 2, in which case n is an integer from 1 to 10. R １ is hydrogen or C １－３ It is an alkyl group, Q ２ C is a halogen group or a C substituted with a halogen group. １－３ It is an alkyl group, Q ３ is = O or = N-S(O) ２ -R ２ And the R ２ C is a halogen group or a C substituted with a halogen group. １－３ It is an alkyl group.

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

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