Method for manufacturing an all-solid-state battery including a solid-liquid hybrid electrolyte membrane, and solid-liquid hybrid electrolyte membrane

Abstract

To provide a method for manufacturing an all-solid-state battery without any separate step of injecting a liquid electrolyte to an electrode assembly after manufacturing the electrode assembly, or by injecting merely a small amount of a liquid electrolyte to an electrode assembly.SOLUTION: The present invention relates to a solid-liquid hybrid electrolyte membrane including a predetermined amount of a liquid electrolyte in a porous structure formed by solid polymer particles, and a method for manufacturing an all-solid-state battery including the same. According to an embodiment of the present invention, it is possible to manufacture a battery even without any separate step of injecting an electrolyte. According to one embodiment of the present invention, since the solid-state battery includes a liquid electrolyte, it is possible to ensure improved ion conductivity compared to conventional solid electrolyte batteries.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for manufacturing an all-solid-state battery including a solid-liquid hybrid electrolyte membrane and a solid-liquid hybrid electrolyte membrane.

[0002] This application claims priority based on Korean Patent Application No. 10-2020-0004979 filed on January 14, 2020.

Background Art

[0003] As the use of vehicles, computers, and mobile terminals increases, the importance of lithium secondary batteries is increasing. In particular, the development of lithium secondary batteries that are lightweight and have a high energy density is required.

[0004] Such a lithium secondary battery can be manufactured by injecting a liquid electrolyte after interposing a separator between a positive electrode and a negative electrode, or by interposing a solid electrolyte membrane between the positive electrode and the negative electrode.

[0005] However, a lithium ion battery using a liquid electrolyte has a structure in which the negative electrode and the positive electrode are partitioned by a separator. Therefore, if the separator is damaged due to deformation or external impact, a short circuit may occur, leading to risks such as overheating or explosion.

[0006] On the other hand, a lithium secondary battery using a solid electrolyte has advantages in that the safety of the battery is increased, leakage of the electrolyte can be prevented, the reliability of the battery is improved, and it is easy to manufacture a thin battery. However, even when using a solid electrolyte, there is still a need to develop a solid electrolyte membrane having a high energy density and improved processability. In addition, in the case of a solid electrolyte, there is a problem in that the performance deteriorates due to low ionic conductivity, and there is a technical problem to be solved in that it is much thicker than a conventional porous polyolefin-based separator and the energy density is lost.

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention is for solving the above-described technical problems, and relates to a method for manufacturing an all-solid-state battery without a separate step of injecting a liquid electrolyte after manufacturing an electrode assembly, or by injecting only a small amount of the liquid electrolyte.

[0008] Also, conventionally, due to the liquid electrolyte injection step performed after manufacturing the electrode assembly, time was required for the liquid electrolyte to impregnate the electrode, but the liquid electrolyte according to the present invention can shorten the time for impregnating the inside of the electrode.

[0009] Also, by minimizing the amount of the liquid electrolyte, there is little risk of liquid leakage even when an external impact is applied to the battery.

[0010] Also, it is possible to provide an ionic conductivity significantly improved compared to the ionic conductivity of conventional all-solid-state batteries.

[0011] Also, it is an object to provide a solid-phase - liquid-phase hybrid electrolyte membrane having improved mechanical strength despite being a thin film compared to currently commercially available solid electrolyte membranes.

[0012] Also, it is an object to provide a solid-phase - liquid-phase hybrid electrolyte membrane that can be formed into a thinner film compared to currently commercially available solid electrolyte membranes and has an improved energy density per weight compared to the thickness.

[0013] On the other hand, other objects and advantages of the present invention will be understood from the following description. Also, the objects and advantages of the present invention can be realized by means, methods, or combinations thereof shown in the claims.

Means for Solving the Problems

[0014] One aspect of the present invention provides a method for manufacturing an all-solid-state battery according to the following embodiments.

[0015] The first embodiment of the present invention relates to a method for manufacturing an all-solid-state battery, The method is, (S1) Containing a plurality of solid polymer particles and a liquid electrolyte, including a porous structure in which the solid polymer particles are filled and in contact with each other, and a pore structure is formed between the solid polymer particles, wherein the liquid electrolyte surrounds a portion where the solid polymer particles are in surface contact with each other or the surface of the solid polymer particles, preparing a solid-liquid hybrid electrolyte membrane in which the content of the liquid electrolyte is 30 to 40% by weight based on 100% by weight of the total content of the solid-liquid hybrid electrolyte membrane; (S2) manufacturing an electrode assembly by interposing the solid-liquid hybrid electrolyte membrane between electrodes; (S3) pressurizing the electrode assembly, and providing a method for manufacturing an all-solid-state battery, wherein the ratio (B / A) of the thickness (B) of the solid-liquid hybrid electrolyte membrane after pressurizing the electrode assembly to the thickness (A) of the solid-liquid hybrid electrolyte membrane before pressurizing the electrode assembly is 86 to 92%.

[0016] In a second embodiment of the present invention, in the first embodiment, the step (S1) includes: (S11) preparing a composition in which a large number of polymer particles are dispersed in a solvent; (S12) applying and drying the composition on a substrate to form a pre-porous structure; (S13) pressurizing the product of (S12) to form the porous structure; and (S14) impregnating the porous structure with a liquid electrolyte to manufacture a solid-liquid hybrid electrolyte membrane. At this time, the content of the liquid electrolyte is 30 to 40% by weight based on the total content of the solid-liquid hybrid electrolyte membrane, and a method for manufacturing an all-solid-state battery is provided.

[0017] In a third embodiment of the present invention, in the first or second embodiment, the step (S3) is a step in which, by pressurizing the electrode assembly, the liquid electrolyte in the solid-liquid hybrid electrolyte membrane is discharged and impregnated into the electrode, and a method for manufacturing an all-solid-state battery is provided.

[0018] A fourth embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the first to third embodiments, wherein the solid polymer particles are an engineering plastic resin.

[0019] A fifth embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the first to fourth embodiments, wherein the solid polymer particles are any one or two or more of polyphenylene sulfide, polyether ether ketone, polyimide, polyamideimide, liquid crystal polymer, polyetherimide, polysulfone, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyoxymethylene, polycarbonate, polypropylene, polyethylene, and polymethyl methacrylate.

[0020] A sixth embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the first to fifth embodiments, wherein the solid-phase - liquid-phase hybrid electrolyte membrane does not contain a binder polymer.

[0021] A seventh embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the first to sixth embodiments, further including an electrolyte injection step.

[0022] An eighth embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the first to seventh embodiments, wherein the content of the liquid electrolyte is 31 to 36% by weight based on the total content of the solid polymer particles.

[0023] A ninth embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the second to eighth embodiments, wherein the impregnation in the step (S14) is performed by any one of dip coating, spray coating, and drop coating.

[0024] A tenth embodiment of the present invention provides a method for manufacturing an all-solid-state battery, in any one of the first to ninth embodiments, wherein the solid-phase - liquid-phase hybrid electrolyte membrane further includes a porous polymer substrate or a non-woven fabric substrate.

[0025] Another aspect of the present invention provides a solid-liquid hybrid electrolyte membrane according to the following embodiments.

[0026] The 11th embodiment of the present invention relates to an electrolyte membrane, which includes a large number of solid polymer particles and a liquid electrolyte, and the solid polymer particles are filled and in contact with each other. It includes a porous structure in which a pore structure is formed between the solid polymer particles. The liquid electrolyte surrounds the portion where the solid polymer particles are in surface contact or the surface of the solid polymer particles. The content of the liquid electrolyte is 30 to 40% by weight based on 100% by weight of the total content of the solid-liquid hybrid electrolyte membrane. The ionic conductivity of the solid-liquid hybrid electrolyte membrane is 1×10 -5 ~1×10 -1 S / cm, and provides a solid-liquid hybrid electrolyte membrane.

[0027] The 12th embodiment of the present invention provides a solid-liquid hybrid electrolyte membrane which further includes a porous polymer substrate or a non-woven fabric substrate in the 11th embodiment.

Advantages of the Invention

[0028] According to one aspect of the present invention, after manufacturing an electrode assembly, it is possible to provide an all-solid battery with an ionic conductivity equal to or similar to the previous one without injecting a small amount of liquid electrolyte or without injecting liquid electrolyte. In addition, conventionally, it was necessary to perform a liquid electrolyte injection process so that the liquid electrolyte was impregnated into the electrode for a certain time, but the liquid electrolyte according to the present invention can shorten the time for impregnating the inside of the electrode. This is advantageous in terms of the process.

[0029] Further, according to one aspect of the present invention, by using compressible particulate polymers, a solid-liquid hybrid electrolyte membrane with improved mechanical strength can be provided. Furthermore, since no solid electrolyte is used, a solid-liquid hybrid electrolyte membrane that can be deformed by external pressure can be provided. Also, since the polymer particles are physically bonded, it is advantageous for the formation of porosity and pore channels.

[0030] According to one aspect of the present invention, since no binder polymer is used, a solid-liquid hybrid electrolyte membrane with low resistance can be provided.

[0031] On the other hand, according to one aspect of the present invention, by containing a small amount of liquid electrolyte, not only can leakage be prevented, but also improved ionic conductivity can be ensured compared to conventional solid electrolyte batteries.

[0032] Also, compared to currently commercial solid electrolyte membranes, a solid-liquid hybrid electrolyte membrane that can be formed into a thin film and has an improved energy density per weight compared to the thickness can be provided.

[0033] The drawings attached to this specification illustrate desirable embodiments of the present invention and serve to further understand the technical idea of the present invention together with the content of the invention. Therefore, the present invention should not be construed as being limited only to the matters described in the drawings. On the other hand, the shape, size, scale, or ratio of elements in the drawings attached to this specification may be exaggerated for more clear explanation.

Brief Description of the Drawings

[0034]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0035] Hereinafter, embodiments of the present invention will be described in detail. Prior to this, terms and words used in this specification and the claims should not be construed as being limited to their ordinary or dictionary meanings. The inventor himself must interpret them in accordance with the meaning and concept corresponding to the technical idea of the present invention in accordance with the principle that he can appropriately define the concept of the terms in order to explain the invention in the best way. Therefore, it should be understood that the configurations shown in the embodiments described in this specification are merely the most desirable embodiments of the present invention and do not represent all of the technical ideas of the present invention. Therefore, there may be various equivalents and modifications that can replace them at the time of this application.

[0036] Throughout this specification, when a certain part "includes" other components, unless otherwise specified, it means that it may further include other components rather than excluding other components. Also, terms such as "about" and "substantially" used throughout this specification are used to mean the numerical value or a meaning close to that numerical value when manufacturing and material tolerances inherent in the mentioned meaning are presented, and are used to prevent unscrupulous infringers from misusing the disclosure in which exact or absolute numerical values are mentioned to assist in the understanding of this application.

[0037] Throughout this specification, the description of "A and / or B" means "A, B, or all of these".

[0038] Specific terms in the detailed description are used for convenience and are not restrictive. Words such as "right", "left", "upper surface", and "lower surface" indicate directions in the reference drawings. The words "inside" and "outside" indicate the directions towards and away from the geometric center of the specified device, system, and its members, respectively. Words such as "front", "rear", "above", "below", and their related words and phrases indicate positions and orientations in the reference drawings and are not restrictive. Such terms include the above words, their derivatives, and words with similar meanings.

[0039] The present invention relates to a solid-liquid hybrid electrolyte membrane and a method for manufacturing an all-solid-state battery including the same. A method for manufacturing an all-solid-state battery according to an embodiment of the present invention includes a solid-liquid hybrid electrolyte membrane in which a liquid electrolyte is sufficiently impregnated between pore structures formed by a large number of solid polymer particles. When the solid-liquid hybrid electrolyte membrane sufficiently impregnated with the liquid electrolyte is interposed as a separation layer and pressed, the liquid electrolyte contained in the solid-liquid hybrid electrolyte membrane is discharged and impregnated into the electrode. As a result, after assembling the electrode assembly, there is no need for a separate electrolyte injection step or only a small amount of liquid electrolyte is injected, so there is no leakage, and the ionic conductivity is equivalent to or similar to that of a conventional all-solid-state battery, and an all-solid-state battery having a uniform ionic conductivity can be manufactured.

[0040] FIG. 1 is a diagram schematically showing the structure of a solid-liquid hybrid electrolyte membrane and an all-solid-state battery including the same according to an embodiment of the present invention. FIG. 2 is a diagram schematically showing a method for manufacturing an all-solid-state battery according to an embodiment of the present invention. Hereinafter, the present invention will be described in more detail with reference to the drawings.

[0041] Referring to FIG. 1, an all-solid-state battery 100 according to an embodiment of the present invention includes a positive electrode 10, a negative electrode 20, and a solid-liquid hybrid electrolyte membrane (30) interposed between the positive electrode and the negative electrode.

[0042] At this time, the solid-liquid hybrid electrolyte membrane 30 includes a large number of solid polymer particles 31 and a predetermined amount of liquid electrolyte 32.

[0043] The solid polymer particles are solid at room temperature and are polymer substances having low solubility in an electrolyte solution.

[0044] On the other hand, in the present invention, it is desirable that the solid polymer particles are surrounded by a liquid electrolyte and have low solubility in the liquid electrolyte. Further, it is desirable that the polymer has excellent chemical resistance.

[0045] Specifically, when the solid polymer particles are impregnated with a liquid electrolyte, for example, ethylene carbonate:ethyl methyl carbonate = 30:70 (volume %), they have a solubility of less than 30%. More specifically, they may have a solubility of less than 20%, less than 15%, or less than 10%. As a result, the solid polymer particles can exist in a solid state even when dispersed in a solvent.

[0046] Specifically, the solid polymer particles can be an engineering plastic resin.

[0047] At this time, the engineering plastic resin can include any one or two or more of polyphenylene sulfide, polyether ether ketone, polyimide, polyamideimide, liquid crystal polymer, polyetherimide, polysulfone, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyoxymethylene, polycarbonate, polypropylene, polyethylene, and polymethyl methacrylate. At this time, the engineering plastic resin can have a molecular weight of 100,000 Da to 10,000,000 Da.

[0048] Unlike general commercial inorganic particles, the solid polymer particles have compressibility. As a result, a lithium secondary battery with an increased energy density per thickness and specific gravity can be provided. Also, by using solid polymer particles instead of a conventional solid electrolyte, a deformable solid-liquid hybrid electrolyte membrane can be provided. Since such solid polymer particles have ductility, they can be physically or chemically connected by pressure or heat. As a result, the solid-liquid hybrid electrolyte membrane according to an embodiment of the present invention does not require a separate binder polymer. That is, the solid-liquid hybrid electrolyte membrane does not contain a binder polymer. As a result, a solid-liquid hybrid electrolyte membrane with reduced resistance can be provided.

[0049] In a specific embodiment of the present invention, the average particle size of the solid polymer particles can be 100 nm to 10 μm, 200 nm to 5 μm, or 500 nm to 2 μm. By controlling the particle size within the above numerical range, pores of an appropriate size are formed, short circuits do not occur, and the liquid electrolyte can be sufficiently impregnated.

[0050] The solid polymer particles are filled and in contact with each other, and a pore structure is formed between the solid polymer particles.

[0051] At this time, the solid polymer particles can be filled by external pressure and come into contact with each other. For example, the external pressure can be uniaxial pressing, roll pressing, cold isostatic pressing (CIP), hot isostatic pressing (HIP), etc. However, it is not limited to these, and physical or chemical methods that can adhere the solid polymer particles can be used.

[0052] At this time, the solid polymer particles plastically deform beyond the physical elastic region of the particles by the above-described external pressure, and the contact surface between the particles increases compared to before pressurization, or the volume changes to form a new contact surface, or the adhesive force of the adhesive surface between the particles due to plastic deformation increases to form a predetermined structure. For example, the solid polymer particles can be pelletized.

[0053] The liquid electrolyte exists at the portion where the solid polymer particles are in surface contact with each other, or surrounds the surface of the solid polymer particles. In other words, the liquid electrolyte covers the surface of the solid polymer particles. The presence of such a liquid electrolyte can provide a solid-liquid hybrid electrolyte membrane with high ionic conductivity.

[0054] In one embodiment of the present invention, the liquid electrolyte exists in a predetermined amount. The liquid electrolyte is impregnated in the porous structure 33 formed by the solid polymer particles.

[0055] Thereafter, as will be described later, after interposing a porous composite electrolyte membrane impregnated with the liquid electrolyte between the positive electrode and the negative electrode, through a pressurization process, the impregnated liquid electrolyte is discharged into the electrodes. Thereby, according to one embodiment of the present invention, after assembling the electrode assembly, without a separate electrolyte injection process or by injecting only a small amount of liquid electrolyte, it is possible to provide an all-solid-state battery having an ion conductivity equivalent to or similar to that of the conventional one.

[0056] The content of the liquid electrolyte therefor is 30 to 40% by weight based on 100% by weight of the total content of the solid-liquid hybrid electrolyte membrane. Specifically, the content of the liquid electrolyte can be 30% by weight or more, 31% by weight or more, 32% by weight or more, or 33% by weight or more with respect to the total content of the solid-liquid hybrid electrolyte membrane. Also, the content of the liquid electrolyte can be 40% by weight or less, 39% by weight or less, 38% by weight or less, or 37% by weight or less with respect to the total content of the solid polymer particles. That is, since the solid-liquid hybrid electrolyte membrane according to one embodiment of the present invention has a liquid electrolyte with the above content, when interposed between the positive electrode and the negative electrode hereafter, it can exhibit the effect of having high ion conductivity and desired mechanical strength. If the content range of the liquid electrolyte is less than 30% by weight, the desired ion conductivity cannot be achieved, and if it exceeds 40% by weight, it is difficult to manufacture a porous structure using solid polymer particles, and even if it is manufactured, the strength is reduced due to the electrolyte and it is difficult to maintain the porous structure.

[0057] On the other hand, in one embodiment of the present invention, even if the liquid electrolyte exists in a predetermined amount, it provides a solid-liquid hybrid electrolyte membrane with high ion conductivity. This is because the liquid electrolyte is uniformly dispersed and present on the surface of the solid polymer particles or at the portion in surface contact. In one embodiment of the present invention, in order to uniformly impregnate the liquid electrolyte in this way, dip coating, spray coating, drop coating, or the like can be used.

[0058] In a specific embodiment of the present invention, the liquid electrolyte does not dissolve the solid polymer particles and has excellent chemical resistance and electrochemical resistance.

[0059] For example, the liquid electrolyte is a salt having a structure such as A + B - , where A + is an ion composed of an alkali metal cation such as Li + , Na + , K + or a combination thereof, and B - is PF6 - , BF4 - , Cl - , Br - , I - , ClO4 - , AsF6 - , CH3CO2 - , CF3SO3 - , N(CF3SO2)2 - , C(CF2SO2)3 - or an anion composed of a combination thereof. The salt dissolved or dissociated in an organic solvent such as an ether-based, carbonate-based, or nitrile-based solvent can be used, but is not limited thereto.

[0060] For example, the ether-based organic solvent can include dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether, ethyl propyl ether, 1,2-dimethoxyethane, or a mixture of two or more thereof.

[0061] For example, the carbonate-based organic solvent can include propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), or a mixture of two or more thereof.

[0062] For example, the nitrile-based organic solvent can include acetonitrile, succinonitrile, or a mixture of two or more of these.

[0063] In addition, it can include an organic solvent composed of dimethyl sulfoxide, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, or a mixture thereof, but is not limited thereto.

[0064] In a solid-phase - liquid-phase hybrid electrolyte membrane according to an embodiment of the present invention, the porosity of the porous structure itself is larger than the porosity of the solid-phase - liquid-phase hybrid electrolyte membrane.

[0065] Specifically, the porosity of the porous structure itself can be 1 to 90% by volume, 5 to 80% by volume, 10 to 70% by volume, or 20 to 50% by volume.

[0066] The porosity of the solid-phase - liquid-phase hybrid electrolyte membrane is smaller than the porosity of the porous structure itself, and specifically, it can be 0 to 80% by volume, 5 to 60% by volume, 10 to 30% by volume, or 15 to 20% by volume.

[0067] Also, in a solid-phase - liquid-phase hybrid electrolyte membrane according to an embodiment of the present invention, the ionic conductivity of the solid-phase - liquid-phase hybrid electrolyte membrane is greater than the ionic conductivity of the porous structure itself.

[0068] Also, the ionic conductivity of a solid-phase - liquid-phase hybrid electrolyte membrane according to an embodiment of the present invention is greater than the ionic conductivity of the porous structure itself, and is 1×10 -5 ~1×10 -1 S / cm, 1×10 -4 ~1×10 -2 S / cm, or 1×10 -4 ~5×10 -3 S / cm.

[0069] Thus, the solid-phase / liquid-phase hybrid electrolyte membrane according to one embodiment of the present invention can exhibit a higher ionic conductivity compared to the porous structure itself, even though its porosity is smaller than that of the porous structure.

[0070] On the other hand, in the present invention, the porosity and pore size of the porous structure itself and the electrolyte membrane can be adjusted by controlling the average particle size of the solid polymer particles used or the pressure conditions during production. For example, it can be adjusted by adjusting the roll gap of a roll press, controlling the production temperature, or controlling the content or particle size of the solid polymer particles.

[0071] In a specific embodiment of the present invention, the thickness of the porous structure can be 10 μm to 500 μm, 20 μm to 300 μm, or 30 μm to 100 μm. In one embodiment of the present invention, by using a thin porous structure such as 10 to 50 μm, it is advantageous in terms of energy density when manufacturing a lithium secondary battery later.

[0072] In a specific embodiment of the present invention, the thickness of the solid-phase / liquid-phase hybrid electrolyte membrane can be 10 μm to 500 μm, 20 μm to 300 μm, or 30 μm to 100 μm. In one embodiment of the present invention, a thin film-like separation membrane such as 10 to 50 μm can be provided, which is advantageous in terms of energy density when manufacturing a lithium secondary battery later.

[0073] In a specific embodiment of the present invention, the solid-phase / liquid-phase hybrid electrolyte membrane can further include a porous polymer substrate or a non-woven fabric substrate. In particular, since the content of the liquid electrolyte to be impregnated is large in the solid-phase / liquid-phase hybrid electrolyte membrane according to one embodiment of the present invention, forming it on the above-mentioned porous polymer substrate or non-woven fabric substrate, or when the porous polymer substrate or non-woven fabric substrate is interposed separately, it is advantageous in terms of high mechanical strength.

[0074] Specifically, the non-woven fabric substrate can be formed from polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polyester, polyamide, polyacetal, polycarbonate, polyimide, polyether ether ketone, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyethylene naphthalate, or mixtures thereof.

[0075] At this time, the pores of the porous polymer substrate or non-woven fabric substrate can have an average particle size of 10 nm to 100 μm, 100 nm to 10 μm, or 500 nm to 5 μm, and the porosity can be 10 to 98 vol%, 30 to 90 vol%, or 40 to 80 vol%.

[0076] On the other hand, a part of the solid polymer particles can be embedded in the pores of the non-woven fabric substrate. At this time, the liquid electrolyte can surround the surface of the solid polymer particles and the substrate.

[0077] On the other hand, the solid polymer particles can be located on at least one surface of the non-woven fabric substrate. At this time, the liquid electrolyte can surround the surface of the solid polymer particles and the substrate.

[0078] The "pores" in the present invention have various forms of pore structures. If the average size of the pores measured using a porosimeter or observed on an FE-SEM (Field Emission Scanning Electron Microscope) satisfies the above-described conditions, they are included in the present invention.

[0079] Another embodiment of the present invention provides a method for manufacturing an all-solid-state battery according to the following embodiments. This step is schematically shown in FIG. 2.

[0080] First, prepare a solid-liquid hybrid electrolyte membrane containing a large number of solid polymer particles and a liquid electrolyte, where the solid polymer particles are filled and in contact with each other, a pore structure is formed between the solid polymer particles, the liquid electrolyte surrounds the portions where the solid polymer particles are in surface contact or the surface of the solid polymer particles, and the content of the liquid electrolyte is 30 to 40% by weight based on the total content of the solid-liquid hybrid electrolyte membrane (S1). This step is shown in Fig. 2(a). As shown in Fig. 2(a), a composition in which a large number of polymer particles are dispersed in a solvent can be used. At this time, for the polymer particles, the description of the above-mentioned solid polymer particles can be referred to. At this time, the solvent can disperse the solid polymer particles. For example, it can be ethanol, methanol, etc.

[0081] Specifically, the step (S1) can include: (S11) preparing a composition in which a large number of polymer particles are dispersed in a solvent; (S12) coating and drying the composition on a substrate to form a pre-porous structure; (S13) pressing the product of (S2) to form a porous structure; and (S14) impregnating the porous structure with a liquid electrolyte to manufacture a solid-liquid hybrid electrolyte membrane.

[0082] At this time, for coating and drying, methods that can be used in the industry can usually be used (S12). This step is shown in Fig. 2(b). As shown in Fig. 2(b), in order to uniformly coat the polymer particles on the substrate, after dispersing the polymer particles in a solvent, a method of coating the dispersion can be used. At this time, after coating the dispersion on the substrate, it is desirable that the solvent volatilizes and a residual substance remains, but it is not limited thereto, and a residual substance may remain depending on the purpose.

[0083] Next, the result of (S12) can be pressurized to form a porous structure (S3). In one embodiment of the present invention, the solid polymer particles can form a porous structure through the pressurization step. At this time, the solid polymer particles are physically bondable by pressurization or heat and do not require a separate binder polymer.

[0084] At this time, in order to reinforce the mechanical strength of the porous structure, a porous polymer substrate or a non-woven fabric substrate can be further included separately.

[0085] Thereby, a solid-liquid hybrid electrolyte membrane with reduced resistance can be manufactured. This step is shown in (c) of FIG. 2. For example, the pressurization step can be a step of pressurizing once or several times at predetermined intervals in order to provide the desired thickness and porosity of the porous structure and / or the solid-liquid hybrid electrolyte membrane.

[0086] Next, the porous structure can be impregnated with a predetermined amount of liquid electrolyte (S14). At this time, the liquid electrolyte can be impregnated by any one of dip coating, spray coating, and drop coating, but is not limited thereto. On the other hand, the content of the liquid electrolyte can be 30 to 40% by weight based on 100% by weight of the total content of the solid-liquid hybrid electrolyte membrane. By having the content of the liquid electrolyte within a predetermined numerical range in this way, when pressure is applied after manufacturing the electrode assembly, the density of the porous structure increases, and the liquid electrolyte impregnated in the porous structure is discharged and moves into the electrode active material layer. As a result, the formed all-solid-state battery has high ionic conductivity without a separate liquid injection process, and the density of the porous structure increases due to pressurization, improving the mechanical strength. After the step of (S14), a step of removing the base material can be further included (S15). For example, a step of removing the release film can be further included. At this time, when the release film is used as the base material, since the wettability of the release film with respect to the electrolytic solution is not good, the amount of liquid leakage from the porous structure is not large. In addition, since the release film has a structure surrounding the solid-liquid hybrid electrolyte membrane, the phenomenon of electrolytic solution leakage can be reduced.

[0087] Thereafter, the solid-liquid hybrid electrolyte membrane is interposed between the electrodes to manufacture an electrode assembly (S2). The method of interposing the solid-liquid hybrid electrolyte membrane between the electrodes is not particularly limited, and an ordinary method used in the industry can be used.

[0088] Next, the electrode assembly is pressurized (S3). The pressurization step is a step in which the liquid electrolyte in the solid-liquid hybrid electrolyte membrane is discharged and impregnated into the electrodes. That is, in one embodiment of the present invention, the liquid electrolyte impregnated in the solid-liquid hybrid electrolyte membrane penetrates into the positive and negative electrodes by pressurization, and finally, an all-solid-state battery with improved ionic conductivity can be manufactured. Thus, according to the present invention, since the electrolyte is uniformly dispersed inside the electrode assembly by pressurization, a separate electrolyte injection step is not required, or only a small amount of liquid electrolyte can be injected.

[0089] On the other hand, in one embodiment of the present invention, whether the electrolyte has impregnated into the electrodes can be confirmed from the thickness of the electrode assembly before and after pressurization.

[0090] More specifically, according to one embodiment of the present invention, the ratio (B / A) of the thickness (B) of the solid-liquid hybrid electrolyte membrane after pressurization to the thickness (A) of the solid-liquid hybrid electrolyte membrane before pressurization is 86 to 92%.

[0091] In the present invention, the positive and negative electrodes include a current collector and an electrode active material layer formed on at least one surface of the current collector, and the active material layer includes a plurality of electrode active material particles and a solid electrolyte. Further, the electrode can further include one or more of a conductive material and a binder resin as needed. Further, the electrode can further include various additives for the purpose of complementing or improving the physicochemical properties of the electrode.

[0092] In the present invention, any material can be used as the negative electrode active material as long as it can be used as the negative electrode active material of a lithium-ion secondary battery. For example, the negative electrode active material is carbon such as non-graphitizable carbon and graphite-based carbon; Li x 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, Group 1, Group 2, Group 3 elements of the periodic table, halogens; metal composite oxides such as (0 < x ≤ 1; 1 ≤ y ≤ 3; 1 ≤ z ≤ 8); lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; metal oxides such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4 and Bi2O5; conductive polymers such as polyacetylene; Li-Co-Ni-based materials; titanium oxides; lithium titanium oxides, etc. One or more selected from the above can be used. In a specific embodiment, the negative electrode active material can contain a carbon-based material and / or Si.

[0093] In the case of the positive electrode, the electrode active material can be used without limitation as long as it can be used as the positive electrode active material of a lithium-ion secondary battery. For example, as the positive electrode active material, layered compounds such as lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), or compounds substituted with one or more transition metals; chemical formula Li 1+x Mn 2-x O4 (x is 0 to 0.33), lithium manganese oxides such as LiMnO3, LiMn2O3, LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiV3O4, V2O5, Cu2V2O7; chemical formula LiNi 1-x M x O2 (M = Co, Mn, Al, Cu, Fe, Mg, B or Ga, x = 0.01 to 0.3) Ni-site type lithium nickel oxide represented by; chemical formula LiMn 2-x M x O2 (M = Co, Ni, Fe, Cr, Zn or Ta, x = 0.01 to 0.1) or lithium manganese composite oxide represented by Li2Mn3MO8 (M = Fe, Co, Ni, Cu or Zn); LiNi x Mn 2-x O4 spinel structure lithium manganese composite oxide represented by; LiMn2O4 in which a part of the chemical formula Li is substituted with an alkaline earth metal ion; disulfide compounds; Fe2(MoO4)3, etc. can be mentioned, but it is not limited thereto.

[0094] In the present invention, as the current collector, a current collector having electrical conductivity such as a metal plate, which is known in the field of secondary batteries, can be appropriately used according to the polarity of the electrode.

[0095] In the present invention, the conductive material is usually added in an amount of 1 to 30% by weight based on the total weight of the mixture containing the electrode active material. Such a conductive material is not particularly limited as long as it has conductivity without inducing a chemical change in the battery. For example, it can include one or a mixture of two or more selected from graphite such as natural graphite and artificial graphite; carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black; conductive fibers such as carbon fibers and metal fibers; metal powders such as carbon fluoride, aluminum, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives.

[0096] In the present invention, the binder resin is not particularly limited as long as it is a component that assists in binding the active material, the conductive material, etc., and binding to the current collector. For example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluororubber, various copolymers, etc. The binder resin can usually be included in the range of 1 to 30% by weight, or 1 to 10% by weight, based on 100% by weight of the electrode layer.

[0097] On the other hand, in the present invention, the electrode active material layer can contain one or more additives such as an oxidation stability additive, a reduction stability additive, a flame retardant, a heat stabilizer, an antifogging agent, etc., if necessary.

[0098] In the present invention, the solid electrolyte can further include one or more of a polymer solid electrolyte, an oxide solid electrolyte, and a sulfide solid electrolyte.

[0099] In the present invention, the solid electrolyte can be different for the positive electrode and the negative electrode, or the same one can be used for two or more battery elements. For example, in the case of the positive electrode, a polymer electrolyte excellent in oxidation stability can be used as the solid electrolyte. Also, in the case of the negative electrode, it is desirable to use a polymer electrolyte excellent in reduction stability as the solid electrolyte. However, it is not limited to these. Since it mainly plays a role of transmitting lithium ions at the electrode, any material having a high ionic conductivity, for example, 10 -7 S / m or more or 10 -7 S / m or more can be used, and it is not limited to a specific component.

[0100] In the present invention, each of the polymer electrolytes can independently be a solid polymer electrolyte formed by adding a polymer resin to a solvated lithium salt, or a polymer gel electrolyte in which a polymer resin contains an organic electrolyte solution containing an organic solvent and a lithium salt.

[0101] Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

[0102] Example 1 1) Production of solid-liquid hybrid electrolyte membrane 3 mL of a dispersion liquid in which powdery polyphenylene sulfide (average particle size: 10 μm) as solid polymer particles was dispersed in ethanol at a concentration of 1 g / 4 mL was applied to a polyethylene terephthalate (PET) nonwoven fabric (porosity 78 vol%) with a thickness of 40 μm and dried to produce a pre-porous structure. Thereafter, the pre-porous structure having an overall thickness of 83 μm was roll-pressed to form a porous structure (porosity 36 vol%) with a thickness of 50 μm.

[0103] Next, 0.01 ml of a liquid electrolyte (ethylene carbonate: ethyl methyl carbonate = 3:7 (volume %), 1 M LiPF6, 0.5 volume % vinylene carbonate, 1 volume % fluoroethylene carbonate) was drop-coated inside the pores of the porous structure and dried to produce a solid-liquid hybrid electrolyte membrane. The produced solid-liquid hybrid electrolyte membrane had a thickness (A) of 50 μm and a porosity of 0%.

[0104] 2) Fabrication of the negative electrode Lithium metal (20 μm thick) manufactured by Honjo was prepared as the negative electrode.

[0105] 3) Fabrication of the positive electrode To prepare a positive electrode forming slurry, NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O2) as the positive electrode active material, VGCF (vapor grown carbon fiber) as the conductive material, and a polymer solid electrolyte (PEO + LiTFSI, [EO] / [Li + =18:1 molar ratio) were mixed at a weight ratio of 80:3:17. This was applied to an aluminum current collector with a thickness of 20 μm using a doctor blade, and the resulting product was vacuum dried at 120°C for 4 hours. Then, the resulting product of the vacuum drying was rolled using a roll press, and a positive electrode slurry with a loading of 3 mAh / cm 2 and a positive electrode with a porosity of 22% were obtained.

[0106] 4) Fabrication of the all-solid-state battery The fabricated positive electrode was punched out into a circle with a diameter of 1.4875 cm 2 and prepared. 1.7671 cm 2A circularly cut negative electrode was prepared. A solid-liquid hybrid electrolyte membrane produced in 1) was interposed between the two electrodes, and the pressure was applied at 5 MPa. The thickness (B) of the porous structure after pressurizing the electrode assembly was 45 μm. Before pressurizing the electrode assembly, specifically, the ratio (B / A) of the thickness (B) of the solid-liquid hybrid electrolyte membrane after pressurizing the electrode assembly to the thickness (A) of the solid-liquid hybrid electrolyte membrane formed by impregnating the preliminary porous structure with a liquid electrolyte by pressurizing was 90%. Then, a coin-type half cell was manufactured using the electrode assembly. At this time, no separate electrolyte injection process was performed.

[0107] Example 2 1) Manufacture of solid-liquid hybrid electrolyte membrane 3 ml of a dispersion in which powdery polyphenylene sulfide (average particle size: 10 μm) as a solid polymer particle was dispersed in ethanol at a concentration of 1 g / 4 ml was applied to a PET nonwoven fabric with a thickness of 40 μm (porosity 78%) and dried to manufacture a preliminary porous structure. Then, the preliminary porous structure with an overall thickness of 83 μm was roll-pressed to form a porous structure with a thickness of 50 μm (porosity 36%).

[0108] Next, 0.007 ml of a liquid electrolyte (ethylene carbonate: ethyl methyl carbonate = 3:7 (volume %), LiPF6 1 M, vinylene carbonate 0.5 volume %, fluoroethylene carbonate 1 volume %) was drop-coated into the pores of the porous structure and dried to manufacture a solid-liquid hybrid electrolyte membrane. The manufactured solid-liquid hybrid electrolyte membrane had a thickness (A) of 50 μm and a porosity of 5 vol%.

[0109] 2) Manufacture of all-solid-state battery After the manufactured solid-liquid hybrid electrolyte membrane was interposed between the positive electrode and the negative electrode according to Example 1, the pressure was applied at 5 MPa.

[0110] The ratio (B / A) of the thickness (B) of the solid-liquid hybrid electrolyte membrane after pressurizing the electrode assembly to the thickness (A) of the solid-liquid hybrid electrolyte membrane before pressurizing the electrode assembly was 86%. Subsequently, a coin-type half cell was fabricated using the electrode assembly. At this time, no separate electrolyte injection process was performed.

[0111] Example 3 1) Fabrication of solid-liquid hybrid electrolyte membrane A solid-liquid hybrid electrolyte membrane was fabricated in the same manner as in Example 1, except that the dispersion prepared in Example 1 was coated and dried on the positive electrode active material containing a solid electrolyte instead of the nonwoven fabric substrate.

[0112] Specifically, NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O2) as the positive electrode active material, VGCF as the conductive material, and a polymer solid electrolyte (PEO + LiTFSI, [EO] / [Li + =18:1 mol ratio) were mixed at a weight ratio of 80:3:17, and then coated and dried on an aluminum positive electrode current collector with a thickness of 10 μm to fabricate a positive electrode.

[0113] Subsequently, 3 ml of the dispersion prepared in Example 1 was coated and dried on the fabricated positive electrode to fabricate a pre-porous structure. At this time, the thickness of the fabricated pre-porous structure was 89 μm.

[0114] Next, the pre-porous structure was roll-pressed to fabricate a porous structure (porosity: 36 vol%) with a thickness of 50 μm.

[0115] Next, a liquid electrolyte (ethylene carbonate: ethyl methyl carbonate = 3:7 (volume %), LiPF6 1M, vinylene carbonate 0.5 volume %, fluoroethylene carbonate 1 volume %) was drop-coated into the pores of the porous structure and dried to fabricate a solid-liquid hybrid electrolyte membrane. The fabricated solid-liquid hybrid electrolyte membrane had a thickness (A) of 50 μm and a porosity of 0 vol%.

[0116] 2) Fabrication of all-solid-state battery After the fabricated solid-liquid hybrid electrolyte membrane was interposed so as to face the negative electrode according to Example 1, it was pressed at 5 MPa.

[0117] The ratio (B / A) of the thickness (B) of the solid-liquid hybrid electrolyte membrane after pressing the electrode assembly to the thickness (A) of the solid-liquid hybrid electrolyte membrane before pressing the electrode assembly was 92%. Thereafter, a coin-type half cell was fabricated using the electrode assembly. At this time, no separate electrolyte injection process was performed.

[0118] Comparative Example 1 - Fabrication of electrolyte membrane An electrolyte membrane was fabricated in the same manner as in Example 1, except that it was not impregnated with a liquid electrolyte.

[0119] Specifically, it was fabricated as follows.

[0120] 3 mL of a dispersion in which powdery polyphenylene sulfide (average particle size: 10 μm) as solid polymer particles was dispersed in ethanol at a concentration of 1 g / 4 mL was applied to a PET nonwoven fabric with a thickness of 40 μm (porosity 78 vol%) and dried to fabricate a pre-porous structure. Thereafter, the pre-porous structure with an overall thickness of 83 μm was roll-pressed to fabricate a porous structure with a thickness of 50 μm (porosity 36 vol%).

[0121] Comparative Example 2 1) Fabrication of electrolyte membrane Instead of impregnating the porous structure with a liquid electrolyte after its fabrication, an electrolyte membrane was fabricated by mixing a liquid electrolyte and solid polymer particles together. Specifically, it was fabricated as follows.

[0122] First, powdery polyphenylene sulfide (average particle size: 10 μm) was prepared as solid polymer particles. Also, as the liquid electrolyte, ethylene carbonate:ethyl methyl carbonate = 3:7 (volume %), 1 M LiPF6, 0.5 volume % vinylene carbonate, and 1 volume % fluoroethylene carbonate were mixed and prepared.

[0123] Thereafter, they were mixed so that the ratio of the solid polymer particles to the liquid electrolyte became 7:3 (volume %), and a dispersion in which the solid polymer particles were dispersed was produced. Thereafter, the dispersion was applied onto a polyethylene terephthalate film and dried. After this, an attempt was made to produce an electrolyte membrane by passing it through a roll press device, but the electrolyte membrane could not be produced. This is considered to be because the content of the liquid electrolyte was high, the contact surface between the solid polymer particles decreased, the adhesive force between the solid polymer particles decreased, and when passed through the roll press device, the liquid electrolyte acted like a lubricating oil and hindered the formation of the membrane.

[0124] Comparative Example 3 1) Production of electrolyte membrane An electrolyte membrane was produced in the same manner as in Comparative Example 2, except that the dispersion produced in Comparative Example 2 was applied onto a nonwoven fabric with a thickness of 38 μm (porosity: 87%) instead of a polyethylene terephthalate film and dried. That is, in Comparative Example 3, the solid polymer particles are impregnated in the pores of the nonwoven fabric substrate. When introducing the nonwoven fabric in an attempt to solve the problems of Comparative Example 2, although the electrolyte membrane itself could be formed, the ionic conductivity in the electrolyte membrane was not uniform, the adhesive strength between the nonwoven fabric and the solid polymer particles was low, and the durability decreased. As a result, there was a limit to its continuous maintenance as an electrolyte membrane.

[0125] Comparative Example 4 - Conventional solid electrolyte membrane 1) Production of solid electrolyte membrane Polyethylene oxide (PEO, Mw = 4,000,000 g / mol) was dissolved in acetonitrile (AN) as a solvent to prepare a 4 wt% polymer solution. At this time, LiTFSI was used as the lithium salt with [EO] / [Li +=18 / 1 (molar ratio) and added together. The polymer solution was stirred overnight at 70 °C so that PEO and the lithium salt were sufficiently dissolved. Next, an additive solution containing an initiator and a curing agent was prepared. As the curing agent, polyethylene glycol diacrylate (PEGDA, Mw = 575) was used, and as the initiator, benzoyl peroxide (BPO) was used. PEGDA was in an amount of 20 wt% relative to PEO, and BPO was in an amount of 1% relative to PEGDA. Acetonitrile was used as the solvent. The mixture was stirred for about 1 hour so that the components into which the additive solution was added were sufficiently mixed. Then, the additive solution was added to the polymer solution, and the two solutions were sufficiently mixed. The mixed solution was applied and coated onto a release film using a doctor blade. The coating gap was 800 μm, and the coating speed was 20 mm / min. The release film coated with the solution was transferred to a glass plate and dried overnight at room temperature while maintaining horizontal, and then vacuum dried at 100 °C for 12 hours. The first solid electrolyte layer and the second solid electrolyte layer were obtained in such a manner. The thicknesses of the obtained first solid electrolyte layer and second solid electrolyte layer were about 50 μm.

[0126] 2) Fabrication of all-solid-state battery After the obtained electrolyte membrane was interposed between the positive electrode and the negative electrode according to Example 1, it was pressed at 5 MPa to fabricate an electrode assembly.

[0127] The ratio (B / A) of the thickness (B) of the electrolyte membrane after pressurization of the electrode assembly to the thickness (A) of the electrolyte membrane before pressurization of the electrode assembly was 100%. Then, a coin-type half cell was fabricated using the electrode assembly. At this time, no separate electrolyte injection process was performed.

[0128] Comparative Example 5 1) Fabrication of solid-liquid hybrid electrolyte membrane 3 mL of a dispersion in which powdery polyphenylene sulfide (average particle size: 10 μm) as solid polymer particles was dispersed in ethanol at a concentration of 1 g / 2 mL was applied to a PET nonwoven fabric with a thickness of 40 μm (porosity 78%) and dried to produce a pre-porous structure. Thereafter, the pre-porous structure with an overall thickness of 200 μm was roll-pressed to form a porous structure with a thickness of 40 μm (porosity 21 vol%).

[0129] Next, a liquid electrolyte (ethylene carbonate: ethyl methyl carbonate = 3:7 (volume %), 1 M LiPF6, 0.5 volume % vinylene carbonate, 1 volume % fluoroethylene carbonate) was drop-coated into the pores of the porous structure and dried to produce a solid-liquid hybrid electrolyte membrane. The produced solid-liquid hybrid electrolyte membrane (A) had a thickness of 40 μm and a porosity of 0 vol%.

[0130] 2) Fabrication of all-solid-state battery After the produced solid-liquid hybrid electrolyte membrane was interposed between the positive electrode and the negative electrode according to Example 1, it was pressed at 5 MPa to produce an electrode assembly.

[0131] The ratio (B / A) of the thickness (B) of the solid-liquid hybrid electrolyte membrane after pressing of the electrode assembly to the thickness (A) of the solid-liquid hybrid electrolyte membrane before pressing of the electrode assembly was 97.5%. Thereafter, a coin-type half cell was fabricated using the electrode assembly. At this time, no separate electrolyte injection process was performed.

[0132] Evaluation experiment Measurement of porosity The porous structures and electrolyte membranes obtained in each example and comparative example were cut into a size of 1.7671 cm 2 After measuring their weight and volume (measurement of apparent density), the porosity was calculated by comparing it with the design dimensions (true density). That is, the true density of each solid electrolyte membrane was calculated from the composition ratio of the materials contained in the obtained solid electrolyte membrane and the density of each component, and the porosity was calculated from the difference between the apparent density and the true density.

[0133] Measurement of Ion Conductivity of Electrolyte Membrane The electrolyte membranes obtained in each example and comparative example were punched into a circle with a size of 1.7671 cm 2 and placed between two stainless steels to fabricate a coin cell. Using an analyzer (VMP3, manufactured by BioLogic), electrochemical impedance was measured at room temperature, with an amplitude of 10 mV and a scan range of 500 kHz to 0.1 MHz, and the ion conductivity was calculated based on this measurement.

[0134] Measurement of Content of Liquid Electrolyte in Solid-Liquid Hybrid Electrolyte Membrane It was calculated by [weight of solid-liquid hybrid electrolyte membrane - weight of porous structure].

[0135] Evaluation of Initial Discharge Capacity and Life Characteristics For the batteries manufactured in Examples 1 to 3 and Comparative Examples 1 to 5, charge and discharge were performed at room temperature or 60 °C and 0.05 C to evaluate the initial discharge capacity. Charging conditions: CC (constant current) / CV (constant voltage), (current cutoff at 4.25 V and 0.005 C) Discharging conditions: CC (constant current) condition 3 V, (0.05 C)

[0136] [Table 1]

[0137] On the one hand, in Table 1, normal temperature indicates conditions controlled at approximately 18°C to 27°C. As can be seen from Table 1, a support was formed using particles without ion conductivity, and a small amount of electrolyte was impregnated into the interior of the support to fabricate a composite electrolyte layer with excellent ion conductivity. This showed excellent characteristics in terms of physical properties and ion conductivity compared to conventional solid electrolytes typified by PEO. Also, the amount of electrolyte applied at this time was 2 to 15 μL, which is much lower than the amount of 20 to 50 μl of conventional general electrolytes. However, due to the low solubility of the support in the electrolyte, the electrolyte can be effectively repositioned to the electrodes by applying pressure during the fabrication of the electrode assembly to ensure ion conductivity and drive it as a battery. The battery level showed results far exceeding the performance of batteries to which conventional PEO was applied. However, as in Comparative Example 5, when the change in the thickness of the electrolyte membrane is small or the absolute amount is too small, it is not very useful for performance improvement.

Explanation of Signs

[0138] 100: All-solid-state battery 10: Positive electrode 11: Positive electrode active material 20: Negative electrode 21: Negative electrode active material 30: Solid-phase - liquid-phase hybrid electrolyte membrane 31: Solid polymer particles 32: Liquid electrolyte 33: Porous structure 40: Substrate

Claims

1. A solid-phase - liquid-phase hybrid electrolyte membrane comprising solid polymer particles and a liquid electrolyte, wherein the solid polymer particles are filled and in contact with each other, and the solid polymer particles are physically bonded to each other, comprising a porous structure in which a pore structure is formed between the solid polymer particles, wherein the liquid electrolyte surrounds a portion where the solid polymer particles are in surface contact with each other or the surface of the solid polymer particles, wherein the content of the liquid electrolyte is 30 to 40% by weight based on 100% by weight of the total content of the solid-phase - liquid-phase hybrid electrolyte membrane, The ionic conductivity of the solid-liquid hybrid electrolyte membrane is 1×10 －５ ~1×10 －１ S / cm, and wherein the solid polymer particles are an engineering plastic resin, a solid-phase - liquid-phase hybrid electrolyte membrane without a binder polymer.

2. The solid-phase - liquid-phase hybrid electrolyte membrane according to claim 1, further comprising a porous polymer substrate or a non-woven fabric substrate.

3. The solid-phase - liquid-phase hybrid electrolyte membrane according to claim 1, wherein the solid polymer particles comprise any one or two or more of polyphenylene sulfide, polyether ether ketone, polyimide, polyamideimide, liquid crystal polymer, polyetherimide, polysulfone, polyarylate, polyethylene terephthalate, polybutylene terephthalate, polyoxymethylene, polycarbonate, polypropylene, polyethylene, and polymethyl methacrylate.

4. The solid-phase - liquid-phase hybrid electrolyte membrane according to claim 1, wherein the porosity of the porous structure itself is 1 to 90% by volume.

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