Solid electrolyte membrane, method for manufacturing same, and all-solid-state battery comprising same

Abstract

The present invention relates to a solid electrolyte membrane, a method for manufacturing same, and an all-solid-state battery comprising same. More specifically, the solid electrolyte membrane comprises a first solid electrolyte layer and a second solid electrolyte layer, which are stacked adjacent to each other, wherein the first solid electrolyte layer has a structure where particulate binders are simply dispersed, and the second solid electrolyte layer has a structure where fibrous binders are entangled with or connected to each other, so that the solid electrolyte membrane can exhibit enhanced strength without a deterioration in the ionic conductivity.

Description

Solid electrolyte membrane, method for manufacturing the same, and all-solid-state battery comprising the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to U.S. patent application Ser. No. 18 / 390,298, filed Dec. 20, 2023, U.S. patent application Ser. No. 18 / 946,323, filed Nov. 13, 2024, and Korean patent application Ser. No. 10-2024-0174801, filed Nov. 29, 2024, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present invention relates to a solid electrolyte membrane, a method for manufacturing the same, and an all-solid-state battery including the same.

[0005] Electrified transportation continues to grow, exemplified by the widespread adoption of electric vehicles (EVs) and the emergence of urban air mobility (UAM) vehicles. Simultaneously, demand for stationary energy storage systems, particularly in residential and industrial sectors powered by solar and wind power, is growing. This shift is driven by concerns about the negative environmental and climate impacts of traditional internal combustion engines and other non-renewable power generation methods. Therefore, technological development for batteries with high energy densities while ensuring improved safety is becoming essential.

[0006] Various batteries are being studied to overcome the limitations of current lithium secondary batteries in terms of battery capacity, safety, output, large-scale development, and miniaturization.

[0007] Representative examples include metal-air batteries with much larger theoretical capacity than lithium secondary batteries, all-solid-state batteries with no risk of explosion in terms of safety, supercapacitors for output, NaS batteries or RFBs (redox flow batteries) for large-scale applications, and thin film batteries for miniaturization, all of which are being continuously researched in academia and industry.

[0008] All-solid-state batteries replace the liquid electrolytes used in conventional lithium-ion batteries with solid electrolytes. Because they do not use flammable solvents, they eliminate the risk of fire or explosion caused by decomposition reactions of conventional electrolytes, significantly improving safety. Furthermore, because they can use lithium metal or lithium alloys as a cathode material, they offer the advantage of dramatically improving the battery's energy density relative to its mass and volume.

[0009] However, while solid-state batteries can ensure safety by using the solid electrolyte, their ionic conductivity may be reduced. Furthermore, if a liquid electrolyte is used as a means to secure the ionic conductivity of the solid electrolyte, there is a problem of reduced strength.

[0010] In general, in order to ensure the safety of all-solid-state batteries while preventing degradation of battery performance and processability, both the ionic conductivity and strength of the solid electrolyte membrane must be maintained above a certain level.

[0011] However, among the solid electrolyte membranes developed to date, technological development for solid electrolytes that possess both ionic conductivity and strength properties remains minimal. Furthermore, as demand for all-solid-state batteries increases, the demand for solid electrolyte membranes within them is also increasing proportionally. Therefore, the development of solid electrolyte membranes that possess both superior ionic conductivity and strength is essential.

[0012] In addition, in an all-solid-state battery, side reactions tend to occur at the interface between the solid electrolyte membrane containing a binder and the negative electrode, which causes a decrease in the performance of the battery. Therefore, there is an increasing demand for a solid electrolyte membrane that prevents side reactions from occurring at the interface with the negative electrode.

[0013] [Prior Art Literature]

[0014] (Patent Document 1) U.S. Patent Publication No. 2020-0028156

[0015] The present inventors have conducted various studies to solve the above problems, and as a result, they have confirmed that in a solid electrolyte membrane in which two solid electrolyte layers are laminated, by applying binders in different forms, such as a particulate binder and a fibrous binder, respectively, the strength of the solid electrolyte membrane is improved without lowering the ion conductivity, and the solid electrolyte layer including the particulate binder suppresses side reactions at the interface with the negative electrode.

[0016] Accordingly, the purpose of the present invention is to provide a solid electrolyte membrane having improved strength without deteriorating ionic conductivity and a method for manufacturing the same.

[0017] Another object of the present invention is to provide an all-solid-state battery including the solid electrolyte membrane.

[0018] In order to achieve the above purpose, the present invention provides a solid electrolyte membrane comprising a first solid electrolyte layer and a second solid electrolyte layer formed on one surface of the first solid electrolyte layer,

[0019] The first solid electrolyte layer comprises a first solid electrolyte and a particulate binder,

[0020] The second solid electrolyte layer comprises a second solid electrolyte and a fibrous binder,

[0021] The above solid electrolyte membrane provides a solvent-free solid electrolyte membrane.

[0022] In one embodiment of the present invention, the weight of the particulate binder may be less than 2 wt% based on the total weight of the first solid electrolyte layer.

[0023] In one embodiment of the present invention, the weight of the fibrous binder may be 0.01 to 5 wt% based on the total weight of the second solid electrolyte layer.

[0024] In one embodiment of the present invention, the particulate binder and the fibrous binder may each include at least one selected from the group consisting of polytetrafluoroethylene (PTFE), ethylene-vinyl acetate (EVA), styrene-ethylene-butylene-styrene (SEBS), and copolymers containing the same.

[0025] In one embodiment of the present invention, the first solid electrolyte or the second solid electrolyte may be a sulfide-based solid electrolyte, a halide-based solid electrolyte, or an oxide-based solid electrolyte.

[0026] In one embodiment of the present invention, the thickness of the solid electrolyte membrane may be 20 ㎛ to 700 ㎛.

[0027] In one embodiment of the present invention, the ionic conductivity of the solid electrolyte membrane may be 0.5 mS / cm to 10 mS / cm.

[0028] In one embodiment of the present invention, the solid electrolyte membrane may be solvent-free.

[0029]

[0030] The present invention also relates to a method for manufacturing a solid electrolyte membrane, which comprises manufacturing a first solid electrolyte layer and a second solid electrolyte layer respectively and then bonding them together.

[0031] The above first solid electrolyte layer is manufactured by the following steps (A1) to (A2):

[0032] (A1) a step of mixing first solid electrolyte particles and a first binder; and

[0033] (A2) A step of applying the mixture obtained in the above step (A1) to a first calendaring process to form it into a film shape to obtain a first solid electrolyte layer;

[0034] The second solid electrolyte layer is manufactured by the following steps (B1) to (B2):

[0035] (B1) a step of mixing second solid electrolyte particles and a second binder; and

[0036] (B2) A step of applying the mixture obtained in the above step (B1) to a second calendaring process to form it into a film shape to obtain a second solid electrolyte layer.

[0037] A method for manufacturing a solid electrolyte membrane is provided, wherein the first binder is a particulate binder, and the second binder is fiberized when mixed to form a fibrous binder.

[0038] In one embodiment of the present invention, the temperatures of the first and second calendaring processes may each be 50°C to 200°C.

[0039] In one embodiment of the present invention, the first calendaring process may be performed for 1 to 10 loops, and the second calendaring process may be performed for 5 to 50 loops.

[0040] In one embodiment of the present invention, the calendaring process may be performed uniaxially or biaxially.

[0041]

[0042] The present invention also provides an all-solid-state battery comprising a positive electrode, a negative electrode, and the solid electrolyte membrane interposed therebetween.

[0043] In one embodiment of the present invention, the first solid electrolyte layer of the solid electrolyte membrane may be adjacent to the cathode.

[0044]

[0045] In one embodiment of the present invention, the first solid electrolyte layer may be composed of a first solid electrolyte and a particulate binder, and the second solid electrolyte layer may be composed of a second solid electrolyte and a fibrous binder.

[0046] In one embodiment of the present invention, a solvent may not be used in the manufacture of the first solid electrolyte layer and the second solid electrolyte layer.

[0047] According to the solid electrolyte membrane of the present invention, two solid electrolyte layers each including a particulate binder and a fibrous binder of different forms are dry-manufactured and then bonded to form a double layer, so that the strength is improved without lowering the ionic conductivity.

[0048] In addition, in an all-solid-state battery including the solid electrolyte membrane of the present invention, since the solid electrolyte layer including the particulate binder among the double layers included in the solid electrolyte membrane is arranged to be in contact with the negative electrode, there is an effect of minimizing side reactions at the interface between the solid electrolyte membrane and the negative electrode.

[0049] Figure 1a is a schematic diagram showing a cross-section of a solid electrolyte membrane according to one embodiment of the present invention.

[0050] Figure 1b is a schematic diagram showing a cross-section of an all-solid-state battery including a solid electrolyte membrane according to one embodiment of the present invention.

[0051] Figure 2a is a schematic diagram of an all-solid-state battery manufactured for performance testing according to the shape of the binder included in the sulfide-based solid electrolyte membrane.

[0052] Figure 2b is a charge / discharge curve for an all-solid-state battery having the structure shown in Figure 2a.

[0053] Figure 3a is a schematic diagram of an all-solid-state battery manufactured for performance testing according to the shape of the binder included in the sulfide-based solid electrolyte membrane.

[0054] Figure 3b is a charge / discharge curve for an all-solid-state battery having the structure shown in Figure 3a.

[0055] Figure 4 is a charge / discharge curve for the all-solid-state battery manufactured in Example 1.

[0056] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0057] The terms and words used in this specification and claims should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0058]

[0059] solid electrolyte membrane

[0060] The present invention relates to a solid electrolyte membrane, wherein the solid electrolyte membrane includes a first solid electrolyte layer and a second solid electrolyte layer, wherein the shapes of binders included in each of the first solid electrolyte layer and the second solid electrolyte layer are different.

[0061] Figure 1a is a schematic diagram showing a cross-section of a solid electrolyte membrane according to one embodiment of the present invention.

[0062] Referring to FIG. 1a, a solid electrolyte membrane (1) according to one embodiment of the present invention is a solid electrolyte membrane (1) including a first solid electrolyte layer (10) and a second solid electrolyte layer (20) formed on one surface of the first solid electrolyte layer (10), characterized in that the first solid electrolyte layer (10) includes a first solid electrolyte (10a) and a particulate binder (10b), and the second solid electrolyte layer (20) includes a second solid electrolyte (20a) and a fibrous binder (20b).

[0063] The first solid electrolyte layer is adjacent to the cathode, and since the binder contained in the first solid electrolyte layer is in a particulate form, contact with the cathode can be minimized, thereby reducing side reactions between the interface of the first solid electrolyte layer and the cathode.

[0064] The shape of the above binder can be controlled by the number of loops of the first and second calendaring processes performed during the manufacture of the first and second solid electrolyte layers. As the number of loops of the calendaring process increases, the binder can take on a fibrous form.

[0065]

[0066] In one embodiment of the present invention, the particulate binder may be included in an amount of 2 wt% or less based on the total weight of the first solid electrolyte layer. The first solid electrolyte layer has a lower binder content than the adjacent second solid electrolyte layer, and thus, when the first solid electrolyte layer is placed in contact with the negative electrode during the manufacture of an all-solid-state battery, the occurrence of a side reaction at the interface with the negative electrode can be prevented.

[0067] Specifically, the content of the particulate binder may be 2 wt% or less, 1.9 wt% or less, 1.8 wt% or less, 1.7 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, or 0.5 wt% or less. When the content of the particulate binder exceeds 2 wt%, the ionic conductivity of the solid electrolyte membrane may be reduced, and when the first solid electrolyte layer is arranged inside the all-solid-state battery so as to be in contact with the negative electrode, a side reaction may occur at the interface with the negative electrode. The lower limit of the above particle binder content is not particularly limited, and may be, for example, 0.4 wt%, 0.3 wt%, 0.2 wt% or 0.1 wt% in a range exceeding 0 wt%.

[0068] In addition, the above particle binder has an average particle diameter (D 50 ) may be 10 nm to 1 ㎛, and the average particle diameter (D 50 ) is less than 10 nm, the slurry manufacturing process for producing a solid electrolyte membrane may not proceed smoothly, and the average particle diameter (D 50 ) exceeds 1 ㎛, it may be difficult to evenly distribute the binder within the solid electrolyte membrane.

[0069] D used in this specification 50 can be defined as the particle diameter at which the cumulative volume is 50% of the particle size distribution curve (the curve of the particle size distribution graph) of each particle. D 50 can be measured, for example, using laser diffraction. Laser diffraction can typically measure particle diameters from submicron levels to several millimeters, producing highly repeatable and high-resolution results.

[0070]

[0071] In one embodiment of the present invention, the fibrous binder may be included in an amount of 0.01 to 5 wt% based on the total weight of the second solid electrolyte layer. The above fibrous binder is also, based on the total weight of the second solid electrolyte layer, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2.0 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3.0 wt%, 3.1 wt%, 3.2 wt%, 3.3 %, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, or 4.9% by weight.

[0072] If the content of the above-mentioned fibrous binder is less than 0.01 wt%, the strength of the solid electrolyte membrane may be reduced, and if it exceeds 5 wt%, the ionic conductivity of the solid electrolyte membrane may be reduced.

[0073] In addition, the fibrous binder may have an aspect ratio of 10 to 10,000. If the aspect ratio is less than 10, the cross-linked structure formed by the binder within the solid electrolyte membrane may be small, resulting in a weakened strength. If the aspect ratio is greater than 10,000, the time required for the manufacturing process may increase. The cross-linked structure formed by the binder may be described as a network structure in the form of a mesh-like network.

[0074]

[0075] In one embodiment of the present invention, the particulate binder and the fibrous binder may each include at least one selected from the group consisting of polytetrafluoroethylene (PTFE), ethylene-vinyl acetate (EVA), styrene-ethylene-butylene-styrene (SEBS), and copolymers including at least one of PTFE, EVA, and SEBS. In addition, the particulate binder and the fibrous binder may be the same as or different from each other.

[0076]

[0077] In one embodiment of the present invention, the first solid electrolyte and the second solid electrolyte may each include at least one selected from the group consisting of a sulfide-based solid electrolyte and a halide-based solid electrolyte, and these may be the same or different from each other.

[0078] The above sulfide-based solid electrolyte may include at least one selected from the group consisting of LiPSX (X = Cl, Br or I), LiGePS, and LiPS. However, the sulfide-based solid electrolyte is not limited to these, and a wide range of sulfide-based solid electrolytes commonly used in the art may be used.

[0079] Non-limiting examples of sulfide-containing solid electrolytes may include Li-PS-based glasses, Li-PS-based glass ceramics, and argyrodite-based sulfide-containing solid electrolytes.

[0080] Non-limiting examples of the above sulfide-containing solid electrolyte include: x Li2S- yP2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5, Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2 or Li2S-GeS2-ZnS, Li6PS5X (X = one or more of Cl, Br or I).

[0081] In one aspect, the sulfide-containing solid electrolyte is an LPS-based glass or glass ceramic, for example. x Li2S- y It may include at least one selected from P2S5, or an argyrodite-based sulfide-containing solid electrolyte (Li6PS5X; X = Cl, Br, I). In one aspect, the sulfide-containing solid electrolyte may be Li6PS5X.

[0082] In addition, the halide-based solid electrolyte may be represented by the following chemical formula 1:

[0083] <Chemical Formula 1>

[0084] Li 6-3a M a Br b Cl c

[0085] In the above chemical formula 1, M is a metal other than Li, and a is 0 <a<2 이고, b는 0≤b≤6 이고, c는 0≤c≤6 이며, b+c=6 이다.

[0086] For example, the halide solid electrolyte may include at least one selected from the group consisting of Li3YBr6, Li3YCl6, and Li3YBr2Cl4.

[0087]

[0088] In addition, since both the first solid electrolyte layer and the second solid electrolyte layer are manufactured by a dry process, the first solid electrolyte layer may include the first solid electrolyte and a particulate binder, and the second solid electrolyte layer may include the second solid electrolyte and a fibrous binder. Alternatively, the first solid electrolyte layer may be composed of the first solid electrolyte and a particulate binder, and the second solid electrolyte layer may be composed of the second solid electrolyte and a fibrous binder.

[0089] Additionally, a solvent may not be used in the manufacture of the first solid electrolyte layer and the second solid electrolyte layer.

[0090] Additionally, the solid electrolyte membrane may be substantially solvent-free. In one embodiment of the present invention, the phrase "substantially free" may allow for the inclusion of a small amount of solvent so that the stated objectives of the present invention can be achieved. For example, a small amount of solvent, such as less than 1 wt% based on the total weight of the solid electrolyte membrane, may be permitted. Specifically, the small amount may be less than 0.95 wt%, less than 0.90 wt%, less than 0.85 wt%, less than 0.80 wt%, less than 0.75 wt%, less than 0.70 wt%, less than 0.65%, less than 0.60 wt%, less than 0.55 wt%, less than 0.50 wt%, less than 0.45 wt%, less than 0.40 wt%, less than 0.35 wt%, less than 0.30% by weight, less than 0.25 wt%, less than 0.20 wt%, less than 0.15 wt%, less than 0.10 wt%, less than 0.05 wt%, less than 0.02 wt%, or less than 0.01 wt%, based on the total weight of the solid electrolyte membrane.

[0091]

[0092] The content of the first solid electrolyte in the first solid electrolyte layer may be 98 wt% or more, specifically 98 wt% or more, 98.1 wt% or more, 98.2 wt% or more, 98.3 wt% or more, 98.4 wt% or more, 98.5 wt% or more, 98.6 wt% or more, 98.7 wt% or more, 98.8 wt% or more, 98.9 wt% or more, 99 wt% or more, 99.1 wt% or more, 99.2 wt% or more, 99.3 wt% or more, 99.4 wt% or more, or 99.5 wt% or more. If the content of the first solid electrolyte is less than 98 wt%, the ionic conductivity of the solid electrolyte membrane may be reduced, and if it exceeds 99.5 wt%, the content of the particulate binder is relatively reduced, so the strength of the solid electrolyte membrane may be reduced.

[0093] Additionally, the content of the second solid electrolyte in the second solid electrolyte layer may be 95 to 99.99 wt%. The content of the solid electrolyte is 95.1 wt%, 95.2 wt%, 95.3 wt%, 95.4 wt%, 95.5 wt%, 95.6 wt%, 95.7 wt%, 95.8 wt%, 95.9 wt%, 96.0 wt%, 96.1 wt%, 96.2 wt%, 96.3 wt%, 96.4 wt%, 96.5 wt%, 96.6 wt%, 96.7 wt%, 96.8 wt%, 96.9 wt%, 97.0 wt%, 97.1 wt%, 97.2 wt%, 97.3 wt%, 97.4 wt%, 97.5 wt%, 97.6 wt%, 97.7 wt%, 97.8 wt%, It may be included at 97.9 wt%, 98.0 wt%, 98.1 wt%, 98.2 wt%, 98.3 wt%, 98.4 wt%, 98.5 wt%, 98.6 wt%, 98.7 wt%, 98.8 wt%, 98.9 wt%, or 99.9 wt%. If the content of the second solid electrolyte is less than 95 wt%, the strength of the solid electrolyte membrane may be reduced, and if it is more than 99.99 wt%, the strength of the solid electrolyte membrane may be reduced.

[0094]

[0095] In one embodiment of the present invention, the thickness of the solid electrolyte membrane may be 20 μm to 700 μm. If the thickness of the solid electrolyte membrane is less than 20 μm, the strength may be weak, resulting in poor processability or a short circuit may occur during battery assembly and / or operation. If the thickness exceeds 700 μm, the energy density of the battery may be reduced.

[0096] In addition, the thickness of the first solid electrolyte layer adjacent to the cathode in the solid electrolyte membrane is 10 to 400 μm, and when it falls within the above range, side reactions at the interface with the cathode can be minimized. The thickness of the second solid electrolyte layer formed adjacent to the first solid electrolyte layer can be 10 to 500 μm.

[0097]

[0098] In one embodiment of the present invention, the ionic conductivity of the solid electrolyte membrane may be 0.5 to 10 mS / cm. Specifically, the ionic conductivity may be 0.5 mS / cm or more, 0.6 mS / cm or more, 0.8 mS / cm or more, 1 mS / cm or more, 1.5 mS / cm or more, 1.6 mS / cm or more, 1.7 mS / cm or more, 1.8 mS / cm or more, 1.9 mS / cm or more, or 2 mS / cm or less, 3 mS / cm or less, 5 mS / cm or less, 8 mS / cm or less, or 10 mS / cm or less. The ionic conductivity may be measured at room temperature (25°C).

[0099] In one embodiment of the present invention, the tensile strength of the solid electrolyte membrane may be 45 to 1000 kPa. Specifically, the tensile strength of the solid electrolyte membrane may be 45 kPa or more, 50 kPa or more, 80 kPa or more, 100 kPa or more, 120 kPa or more, or 150 kPa or more, and may be 200 kPa or less, 300 kPa or less, 500 kPa or less, 700 kPa or less, 900 kPa or less, or 1000 kPa or less.

[0100]

[0101] In one embodiment of the present invention, the solid electrolyte membrane may be solvent-free.

[0102] The first and second solid electrolyte layers included in the above solid electrolyte membrane are both manufactured by a dry process that does not use a solvent, or is preferably solvent-free. For example, the first solid electrolyte layer is manufactured by a dry process that physically mixes the first solid electrolyte and the first binder, and the second solid electrolyte layer is manufactured by a dry process that physically mixes the second solid electrolyte and the second binder, and thus, they may substantially contain no solvent, or may preferably be solvent-free. In addition, when manufacturing the first solid electrolyte layer, the particulate binder may be dispersed during the dry process. Accordingly, a first solid electrolyte layer with improved strength may be manufactured by a dispersed structure formed by the particulate binder formed during the dry process. The second solid electrolyte layer may also be manufactured by the same method, and when forming the second solid electrolyte layer, the loops of the calendering process may be repeated more times to form a fibrous binder, thereby improving the strength. The solid electrolyte membrane formed by bonding the first solid electrolyte layer and the second solid electrolyte manufactured in this manner can have improved strength.

[0103] In addition, since a separate solvent is not used, the phenomenon of the crystal structure of the sulfide-based and / or halide-based solid electrolyte being destroyed by the solvent and resulting in a decrease in ionic conductivity can be prevented.

[0104]

[0105] Typically, the wet process used to manufacture solid electrolyte membranes uses a solvent capable of dissolving the binder to provide adhesion between the solid electrolyte particles. Conventional wet process solvents are polar solvents, such as N-methyl-2-pyrrolidone (NMP), water, or ethanol, which can dissolve the binder and are therefore suitable for wet processes. However, because these solvents react with the sulfide-based solid electrolyte, it has been difficult to use them together with the sulfide-based solid electrolyte. Therefore, solvents such as xylene or anisole, which do not react with the sulfide-based solid electrolyte, are used as wet process solvents. In addition, in the wet process using a solvent such as the above-mentioned xylene or anisole, nitrile-butadiene rubber (NBR), styrene ethylene / butylene styrene (SEBS), etc. are used as binders that dissolve in these solvents.

[0106] On the other hand, the dry process according to the present invention physically stretches the initial particle-shaped binder to fiberize it without using a solvent. Therefore, the structure of the binder in the manufactured solid electrolyte membrane is different from the structure formed by the wet process, and the physical properties of the solid electrolyte membrane can also be improved compared to the solid electrolyte membrane manufactured by the wet process. In the above, the initial particle-shaped binder is physically deformed by shear force during the mixing step with the electrolyte particles. To induce this physical deformation, a tumbler, ball milling, or roll press can be introduced during the mixing process. In addition, a binder that can easily induce physical deformation, such as PTFE, which is physically very weak and thus relatively prone to fiberization, can be used.

[0107]

[0108] Method for manufacturing a solid electrolyte membrane

[0109] The present invention also relates to a method for manufacturing a solid electrolyte membrane.

[0110]

[0111] The method for manufacturing a solid electrolyte membrane according to the present invention comprises manufacturing a first solid electrolyte layer and a second solid electrolyte layer, respectively, and then bonding them to manufacture a solid electrolyte membrane.

[0112] The above first solid electrolyte layer is manufactured by the following steps (A1) to (A2):

[0113] (A1) a step of mixing first solid electrolyte particles and a first binder; and

[0114] (A2) A step of applying the mixture obtained in the above step (A1) to a first calendaring process to form it into a film shape.

[0115] The second solid electrolyte layer is manufactured by the following steps (B1) to (B2):

[0116] (B1) a step of mixing a second solid electrolyte and a second binder; and

[0117] (B2) A step of applying the mixture obtained in step (B1) to a second calendaring process to form it into a film shape.

[0118] The first binder and the second binder are fiberized when mixed to form a particulate binder and a fibrous binder, respectively.

[0119] The first and second solid electrolytes and the particulate binder and fibrous binder materials and contents are the same as described above.

[0120] The shape of the above binder can be controlled by the number of loops of the first and second calendaring processes performed during the manufacture of the first and second solid electrolyte layers. As the number of loops of the calendaring process increases, the binder can take on a fibrous form.

[0121] In addition, the particle-shaped binder and the fiber-shaped binder may have substantially the same constituent materials, with only the shape of the binder being different before and after the dry process.

[0122] In addition, the above-mentioned calendaring process refers to a process of forming the target material of the calendaring process into a film shape using two rollers. The pressure applied to the target material during the calendaring process may be 5 to 200 MPa.

[0123] In one embodiment of the present invention, the method for bonding the first solid electrolyte layer and the second solid electrolyte layer is not particularly limited as long as it is a bonding method that can form a double layer in a form in which the first solid electrolyte layer and the second solid electrolyte layer are adjacently laminated.

[0124] For example, the first solid electrolyte layer and the second solid electrolyte layer may be simply laminated and bonded, or they may be bonded by applying pressure after lamination.

[0125]

[0126] In one embodiment of the present invention, the temperatures of the first and second calendaring processes may each be 50°C to 200°C. Specifically, the temperature may be 50°C or higher, 70°C or higher, or 80°C or higher, and 100°C or lower, 120°C or lower, 140°C or lower, 160°C or lower, 180°C or lower, or 200°C or lower. If the temperature is lower than 50°C, less binder islanding may occur, which may lower the strength of the solid electrolyte membrane, and if it exceeds 200°C, the strength of the solid electrolyte membrane may not increase any further even if the temperature increases, or the electrolyte or binder material may deteriorate.

[0127]

[0128] In one embodiment of the present invention, the first calendaring process may be performed for 1 to 10 loops, and the second calendaring process may be performed for 5 to 50 loops. Specifically, if the number of loops of the first calendaring process is less than 1, the binder may not be able to improve the adhesive strength between the solid electrolyte particles, and if it exceeds 10 loops, the degree of fiberization of the binder increases, so that the binder is fiberized, and thus side reactions at the interface between the fibrous binder within the first solid electrolyte layer adjacent to the negative electrode and the negative electrode may increase. In addition, if the number of loops of the second calendaring process is 5 to 10, the fiberization of the binder may not be smooth, but in this case, if the binder content is increased, even if the number of loops is reduced, the binder can be sufficiently fiberized by friction between the binders. Accordingly, when the loops of the second calendaring process are 5 to 10, the content of the second binder may be 2 to 5 wt% so that the second binder can be sufficiently fiberized. However, even if the content of the second binder is increased, if the loops of the second calendaring process are less than 5, the fiberization of the binder may be small, which may reduce the strength of the solid electrolyte membrane. In addition, if the loops of the second calendaring process are greater than 50, even if the loops increase, the strength of the solid electrolyte membrane may not increase any further, or the processability may deteriorate. The loops of the first calendaring process may be 1 or more, 2 or more, or 3 or more, and may be 8 or less, 9 or less, or 10 or less. The loops of the second calendaring process may be 5 or more, 10 or more, 15 or more, 20 or more, 23 or more, or 25 or more, and may be 35 or less, 40 or less, 45 or less, or 50 or less.

[0129]

[0130] In one embodiment of the present invention, the orientation of the first and second calendaring processes may be performed uniaxially or biaxially. Here, uniaxially means that the calendaring direction proceeds in one direction, and biaxially means that the calendaring is performed in one direction and then alternately in the horizontal and vertical directions of the solid electrolyte membrane.

[0131] When the above calendaring process is performed biaxially, fiberization can proceed evenly in various directions, further improving the strength of the solid electrolyte membrane.

[0132]

[0133] In the method for manufacturing a solid electrolyte membrane as described above, both the first solid electrolyte layer and the second solid electrolyte layer are manufactured by a dry process without using a solvent, but the present invention is not limited thereto. For example, the first solid electrolyte layer may be manufactured by a wet process using a slurry coating process using a particulate binder. Alternatively, the second solid electrolyte layer may be manufactured by a wet process using a fibrous binder in which the binder raw material itself has a fibrous shape. Alternatively, the second solid electrolyte layer may be manufactured by a dry process using a fibrous binder in which the binder raw material itself has a fibrous shape. In this case, when manufacturing the first or second solid electrolyte layer by a wet process, the binder must be included in a certain amount or more based on the total weight of the first or second solid electrolyte layer to enable forming into a membrane shape. For example, the binder may be included in an amount of 2 wt% or more based on the total weight of the first or second solid electrolyte layer.

[0134]

[0135] All-solid-state batteries

[0136] The present invention also relates to an all-solid-state battery including the solid electrolyte membrane.

[0137] An all-solid-state battery according to the present invention includes: the solid electrolyte membrane; an anode formed on one surface of the solid electrolyte membrane; and an anode formed on the other surface of the solid electrolyte membrane.

[0138] As described above, the solid electrolyte membrane includes a first solid electrolyte layer and a second solid electrolyte layer formed on one surface of the first solid electrolyte layer, wherein the first solid electrolyte layer includes a particulate binder, and the second solid electrolyte layer includes a fibrous binder.

[0139] An all-solid-state battery can be formed by allowing the first solid electrolyte layer including a particulate binder among the first and second solid electrolyte layers included in the above solid electrolyte membrane to come into contact with the negative electrode.

[0140] The second solid electrolyte layer includes a fibrous binder. The fibrous binders tend to be entangled or connected with each other to form a three-dimensional structure in a network shape. The second solid electrolyte layer can form a large number of three-dimensional structures in a network shape due to the fibrous binder. When the second solid electrolyte layer comes into contact with the negative electrode, a side reaction can occur at the interface between the second solid electrolyte layer and the negative electrode, centering on the three-dimensional structure in a network shape due to the fibrous binder.

[0141] Figure 1b is a schematic diagram showing a cross-section of an all-solid-state battery including a solid electrolyte membrane according to one embodiment of the present invention.

[0142] Similar to FIG. 1a, in FIG. 1b, the solid electrolyte membrane is a solid electrolyte membrane (1) including a first solid electrolyte layer (10) and a second solid electrolyte layer (20) formed on one surface of the first solid electrolyte layer (10), wherein the first solid electrolyte layer (10) includes a first solid electrolyte (10a) and a first fibrous binder (10b), and the second solid electrolyte layer (20) includes a second solid electrolyte (20a) and a second fibrous binder (20b), and the weight of the first fibrous binder (10b) relative to the total weight of the first solid electrolyte layer (10) is characterized in that it is less than the weight of the second fibrous binder (20b) relative to the total weight of the second solid electrolyte layer (20). In an all-solid-state battery, a solid electrolyte membrane is interposed between the positive electrode (30) and the negative electrode (40), and the first solid electrolyte layer (10) contacts the negative electrode (40), for example, directly contacts it.

[0143]

[0144] Therefore, in order to prevent side reactions at the interface between the solid electrolyte membrane and the negative electrode, an all-solid-state battery can be manufactured by placing the first solid electrolyte layer containing the particulate binder and the negative electrode adjacent to each other.

[0145]

[0146] In one embodiment of the present invention, the positive electrode may include a positive electrode active material, a conductive material, and a binder.

[0147]

[0148] In the present invention, the positive electrode included in the all-solid-state battery includes a positive electrode active material layer, and the positive electrode active material layer may be formed on one side or both sides of the positive electrode current collector.

[0149] The above positive electrode active material layer includes a positive electrode active material, a conductive material, and a binder.

[0150] In addition, the positive electrode active material is not particularly limited as long as it is a material capable of reversibly absorbing and releasing lithium ions, and examples thereof include lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), and Li[Ni x Co y Mn z M v ]O2 (wherein M is one or two or more elements selected from the group consisting of Al, Ga, and In; 0.3≤x<1.0, 0≤y, z≤0.5, 0≤v≤0.1, x+y+z+v=1), Li(Li a M b-a-b' M' b' )O 2-c A c (In the above formula, 0≤a≤0.2, 0.6≤b≤1, 0≤b'≤0.2, 0≤c≤0.2; M includes at least one selected from the group consisting of Mn and Ni, Co, Fe, Cr, V, Cu, Zn and Ti; M' is at least one selected from the group consisting of Al, Mg and B, and A is at least one selected from the group consisting of P, F, S and N.) layered compounds or compounds substituted with one or more transition metals; chemical formula Li 1+y Mn 2-y Lithium manganese oxides such as O4 (where y is 0 to 0.33), LiMnO3, LiMn2O3, LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, LiFe3O4, V2O5, Cu2V2O7; chemical formula LiNi 1-y Ni-site type lithium nickel oxide represented by MyO2 (wherein, M=Co, Mn, Al, Cu, Fe, Mg, B or Ga, and y is 0.01 to 0.3); chemical formula LiMn 2-y M yLithium manganese composite oxides represented by O2 (wherein M is Co, Ni, Fe, Cr, Zn or Ta, and y is 0.01 to 0.1) or Li2Mn3MO8 (wherein M is Fe, Co, Ni, Cu or Zn); LiMn2O4 in which a portion of Li in the chemical formula is replaced by an alkaline earth metal ion; disulfide compounds; Fe2(MoO4)3, etc., but are not limited thereto.

[0151] In addition, the positive electrode active material may be included in an amount of 60 to 80 wt% based on the total weight of the positive electrode active material layer. Specifically, the content of the positive electrode active material may be 60 wt%, 65 wt% or more, or 68 wt% or more, and may be 72 wt% or less, 75 wt% or less, or 80 wt% or less. If the content of the positive electrode active material is less than 60 wt%, battery performance may deteriorate, and if it is more than 80 wt%, mass transfer resistance may increase.

[0152]

[0153] In addition, the conductive material is not particularly limited as long as it prevents side reactions in the internal environment of the all-solid-state battery, does not cause chemical changes in the battery, and has excellent electrical conductivity. Representative examples thereof include graphite or conductive carbon, and examples thereof include graphite such as natural graphite and artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, Denka black, thermal black, channel black, furnace black, and lamp black; carbon-based materials having a crystal structure of graphene or graphite; conductive fibers such as carbon fiber and metal fiber; fluorinated carbon; metal powder such as aluminum powder and nickel powder; conductive whiskey such as zinc oxide and potassium titanate; conductive oxides such as titanium oxide; and conductive polymers such as polyphenylene derivatives; which may be used alone or in combination of two or more thereof, but are not necessarily limited thereto. Preferably, the conductive material may include vapor-grown carbon fiber (VGCF).

[0154] The conductive material may typically be included in an amount of 1 wt% to 5 wt% based on the total weight of the positive electrode active material layer, and specifically, the content of the conductive material may be 1 wt% or more, 1.5 wt% or more, or 2 wt% or more, and 4 wt% or less, 4.5 wt% or less, or 5 wt% or less. If the content of the conductive material is too low, such as less than 1 wt%, it may be difficult to expect an effect of improving electrical conductivity or the electrochemical characteristics of the battery may deteriorate, and if it exceeds 5 wt%, the amount of positive electrode active material may be relatively small, which may lower the capacity and energy density. The method of including the conductive material in the positive electrode is not particularly limited, and conventional methods known in the art, such as mixing or coating with the positive electrode active material, may be used.

[0155]

[0156] In addition, the binder is a component that assists in the bonding of the positive electrode active material and the conductive material and the bonding to the current collector, and includes styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile copolymer, acrylonitrile-butadiene rubber, nitrile butadiene rubber, acrylonitrile-styrene-butadiene copolymer, acrylic rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylene / propylene copolymer, polybutadiene, polyethylene oxide, chlorosulfonated polyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyvinyl alcohol, polyvinyl acetate, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resin, phenol resin, epoxy resin, carboxymethylcellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate It may include at least one selected from the group consisting of butyrate, cellulose acetate propionate, cyanoethylcellulose, cyanoethylsucrose, polyester, polyamide, polyether, polyimide, polycarboxylate, polycarboxylic acid, polyacrylic acid, polyacrylate, lithium polyacrylate, polymethacrylic acid, polymethacrylate, polyacrylamide, polyurethane, polyvinylidene fluoride, and poly(vinylidene fluoride)-hexafluoropropene. Preferably, the binder may include polytetrafluoroethylene (PTFE).

[0157] In addition, the binder may be included in an amount of 0.5 wt% to 4 wt% based on the total weight of the positive electrode active material layer, and specifically, the content of the binder may be 0.5 wt% or more, 1 wt% or more, or 1.5 wt% or more, and 3 wt% or less, 3.5 wt% or less, or 4 wt% or less. If the content of the binder is less than 0.5 wt%, the adhesive strength between the positive electrode active material and the positive electrode current collector may be reduced, and if it exceeds 4 wt%, the adhesive strength may be improved, but the content of the positive electrode active material may be reduced, which may lower the battery capacity.

[0158]

[0159] In addition, the positive electrode current collector supports the positive electrode active material layer and serves to transfer electrons between the external conductor and the positive electrode active material layer.

[0160] The positive electrode current collector is not particularly limited as long as it has high electronic conductivity without causing chemical changes in the all-solid-state battery. For example, the positive electrode current collector may be copper, stainless steel, aluminum, nickel, titanium, palladium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, silver, etc., or an aluminum-cadmium alloy.

[0161] The above-mentioned positive electrode current collector may have a finely irregular structure on its surface or may employ a three-dimensional porous structure to strengthen the bonding strength with the positive electrode active material layer. Accordingly, the positive electrode current collector may include various forms such as a film, sheet, foil, mesh, net, porous body, foam, or non-woven fabric.

[0162] The positive electrode as described above can be manufactured according to a conventional method, and specifically, a composition for forming a positive electrode active material layer prepared by mixing a positive electrode active material, a conductive agent, and a binder in an organic solvent phase is applied and dried on a positive electrode current collector, and optionally, to improve electrode density, it can be manufactured by compression molding the positive electrode current collector. At this time, it is preferable to use an organic solvent that can uniformly disperse the positive electrode active material, binder, and conductive agent and is easily evaporated. Specifically, examples thereof include acetonitrile, methanol, ethanol, tetrahydrofuran, water, isopropyl alcohol, and the like.

[0163]

[0164] In the present invention, the negative electrode included in the all-solid-state battery includes a negative electrode active material layer, and the negative electrode active material layer may be formed on one or both sides of a negative electrode current collector. The negative electrode active material layer may include a negative electrode active material, a binder, and a conductive material.

[0165] The above negative active material is lithium (Li + ) can be reversibly intercalated or deintercalated, a material that can react with lithium ions to form a reversibly lithium-containing compound, or a lithium metal or a lithium alloy.

[0166] The above lithium ion (Li + ) can be reversibly inserted or de-inserted, for example, crystalline carbon, amorphous carbon, or a mixture thereof. The lithium ion (Li +) can be, for example, tin oxide, titanium nitrate or silicon. The lithium alloy can be, for example, an alloy of lithium (Li) and a metal selected from the group consisting of indium (In), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), aluminum (Al) and tin (Sn).

[0167] Preferably, the negative electrode active material may be lithium metal or a lithium-indium alloy (Li-In), and specifically, may be in the form of a lithium metal or lithium and a thin film or a lithium-indium alloy thin film or powder.

[0168] The negative electrode active material may be included in an amount of 40 to 80 wt% based on the total weight of the negative electrode active material layer. Specifically, the content of the negative electrode active material may be 40 wt% or more or 50 wt% or more, and 70 wt% or less or 80 wt% or less. If the content of the negative electrode active material is less than 40 wt%, the connectivity between the wet negative electrode active material layer and the dry negative electrode active material layer may be insufficient, and if it exceeds 80 wt%, the material transfer resistance may increase.

[0169] In addition, the binder is as described above in the positive electrode active material layer.

[0170] In addition, the above-described conductive material is as described above in the positive electrode active material layer.

[0171] In addition, the negative electrode current collector is not particularly limited as long as it is conductive and does not cause a chemical change in the battery. For example, the negative electrode current collector may be made of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel surface-treated with carbon, nickel, titanium, silver, etc., an aluminum-cadmium alloy, etc. In addition, the negative electrode current collector, like the positive electrode current collector, may be made of various forms such as a film, sheet, foil, net, porous body, foam, non-woven fabric, etc. having fine irregularities formed on the surface.

[0172] The method for manufacturing the above negative electrode is not particularly limited, and can be manufactured by forming a negative electrode active material layer on the negative electrode current collector using a method for forming a layer or film commonly used in the art. For example, methods such as compression, coating, and deposition can be used. In addition, a case in which a battery is assembled on the negative electrode current collector without a lithium thin film and then a metallic lithium thin film is formed on the metal plate through initial charging is also included in the negative electrode of the present invention.

[0173]

[0174] Method for manufacturing an all-solid-state battery

[0175] The present invention also relates to a method for manufacturing an all-solid-state battery.

[0176] A method for manufacturing an all-solid-state battery according to the present invention comprises the steps of: (P1) positioning a mixture for forming a positive electrode active material layer on one surface of a solid electrolyte membrane and applying pressure to form a positive electrode on one surface of the solid electrolyte membrane; and (P2) positioning a negative electrode on the other surface of the solid electrolyte membrane and applying pressure. At this time, the solid electrolyte membrane includes a first solid electrolyte layer and a second solid electrolyte layer formed on one surface of the first solid electrolyte layer, wherein the first solid electrolyte layer includes a particulate binder and the second solid electrolyte layer includes a fibrous binder.

[0177] An all-solid-state battery can be manufactured by placing the first solid electrolyte layer and the negative electrode included in the above-described solid electrolyte membrane adjacent to each other. In this case, the particulate binder included in the first solid electrolyte layer exists in a simply dispersed form within the first solid electrolyte, and does not form a three-dimensional structure in the shape of a net that is entangled or connected with each other like a fibrous binder, so that side reactions can be prevented at the interface between the first solid electrolyte layer and the negative electrode.

[0178]

[0179] In the above step (P1), a mixture for forming a positive electrode active material layer is positioned on one side of a solid electrolyte membrane, and a positive electrode can be formed on one side of the solid electrolyte membrane by applying high temperature and pressure.

[0180] The mixture for forming the above-described positive electrode active material layer may include a positive electrode active material, a conductive agent, and a binder. The specific types and weights of these are as described above. In addition, after forming the positive electrode active material layer, a current collector may be attached to manufacture the positive electrode.

[0181] In addition, the pressurization process may be performed at a pressure of 300 MPa to 500 MPa to bond the solid electrolyte membrane and the anode while reducing the interface resistance. The pressure of the high-temperature pressurization process may be 300 MPa or more, 350 MPa or more, or 400 MPa or more, and may be 450 MPa or less, 470 MPa or less, or 470 MPa or less. If the temperature and / or pressure of the high-temperature pressurization process is below the above range, the solid electrolyte membrane and the anode may not be integrated, and if it exceeds the above range, the solid electrolyte membrane or the anode may be deformed or damaged.

[0182]

[0183] In the above step (P2), a cathode is positioned on the other side of the solid electrolyte membrane and pressurized to manufacture an all-solid-state battery. The description of the cathode is as described above.

[0184] The pressure during the pressurization may be 40 MPa to 80 MPa, and specifically, the pressure during the pressurization may be 40 MPa or more, 45 MPa or more, or 50 MPa or more, and 70 MPa or less, 75 MPa or less, or 80 MPa or less. If the pressure during the pressurization is less than 40 MPa, the interfacial resistance between the negative electrode and the solid electrolyte membrane may increase, and if it exceeds 80 MPa, the solid electrolyte or the negative electrode may be deformed or damaged.

[0185]

[0186] The all-solid-state battery manufactured in this way includes a thin solid electrolyte, so that the manufacturing cost can be reduced and the ionic conductance and energy density can be improved.

[0187] In addition, since the solid electrolyte and the anode are integrated through a high-temperature pressurization process, interface stability can be improved.

[0188]

[0189] battery module

[0190] The present invention also relates to a battery module including the all-solid-state battery as a unit battery, a battery pack including the battery module, and a device including the battery pack as a power source.

[0191] At this time, specific examples of the device include, but are not limited to, a power tool that is powered by an electric motor; an electric vehicle including an electric vehicle (EV), a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), etc.; an electric two-wheeled vehicle including an electric bicycle (E-bike) and an electric scooter (E-scooter); an electric golf cart; and a power storage system.

[0192]

[0193] Hereinafter, preferred examples are presented to help understand the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present invention, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0194] In the following examples and comparative examples, solid electrolyte membranes and all-solid-state batteries were manufactured according to the compositions and processes described in Table 1 below.

[0195]

[0196] Solid electrolyte membrane First solid electrolyte layer Second solid electrolyte layer Thickness (㎛) First solid electrolyte First binder (particle-like) Second solid electrolyte Second binder (fibrous) Material content (weight %) Material content (weight %) Material content (weight %) Material content (weight %) Example 1 Li6PS5Cl99.8PTFE0.2Li6PS5Cl99.5PTFE0.5600 Example 2 Li6PS5Cl99.8PTFE0.2Li6PS5Cl98PTFE2600 Example 3 Li6PS5Cl99.8PTFE0.2Li6PS5Cl99.5PTFE0.5400 Comparative example 1 (wet) Li6PS5Cl99.8PTFE0.2Li6PS5Cl99.5PTFE0.5 Not manufacturable Comparative example 2 (wet) Li6PS5Cl98SEBS2----50 Comparative example 3Li6PS5Cl99.8PTFE0.2----200Comparative Example 4----Li6PS5Cl99.5PTFE0.5400Comparative Example 5----Li6PS5Cl98PTFE2400

[0197]

[0198] Example 1

[0199] 1-1. Manufacturing of the first and second solid electrolyte layers

[0200] The first and second solid electrolyte layers were manufactured by a dry process without using a solvent as follows.

[0201] A mixture was obtained by mixing Li6PS5Cl powder, a sulfide-based solid electrolyte, as a first solid electrolyte, with PTFE particles (polytetrafluoroethylene, Chemours), a first binder, in a mortar, and the mixture was subjected to a calendaring loop five times using a roll press under conditions of a temperature of 90°C and a biaxial orientation, thereby manufacturing a first solid electrolyte layer having a thickness of 200 μm. The first solid electrolyte and the first binder were mixed at 99.8 wt% and 0.2 wt%, respectively.

[0202] A mixture was obtained by mixing Li6PS5Cl powder, a sulfide-based solid electrolyte, as a second solid electrolyte, with PTFE particles (polytetrafluoroethylene, Chemours), a second binder, in a cauldron. The mixture was subjected to 30 calendaring loops using a roll press at 90°C and under biaxial orientation conditions to produce a second solid electrolyte layer having a thickness of 400 μm. The second solid electrolyte and the second binder were mixed at 99.5 wt% and 0.5 wt%, respectively.

[0203]

[0204] 1-2. Manufacturing of solid electrolyte membranes

[0205] A solid electrolyte membrane was manufactured by laminating the second solid electrolyte layer on one surface of the first solid electrolyte layer and then bonding them under pressure of 5 MPa. The thickness of the solid electrolyte membrane is 600 μm.

[0206]

[0207] 1-3. All-solid-state battery manufacturing

[0208] An all-solid-state battery was manufactured by sequentially stacking a positive electrode (NCM811, LGChem), a solid electrolyte membrane manufactured in 1-2 above, and a negative electrode (Si powder, Alfa Aesar). At this time, the first solid electrolyte layer of the solid electrolyte membrane was in contact with the negative electrode.

[0209]

[0210] Example 2

[0211] A solid electrolyte membrane and an all-solid-state battery were manufactured in the same manner as in Example 1, except that 98 wt% of the second solid electrolyte and 2 wt% of the second binder were mixed and the calendaring loop was performed 30 times.

[0212]

[0213] Example 3

[0214] A solid electrolyte membrane was manufactured in the same manner as in Example 1, except that the thickness of the second solid electrolyte layer was 200 μm.

[0215]

[0216] Comparative Example 1

[0217] A solid electrolyte membrane and an all-solid-state battery were manufactured in the same manner as in Example 1, except that the first and second solid electrolyte layers were manufactured by a wet process using a solvent as follows.

[0218] For the above wet process, xylene, a solvent that is stable to sulfide-based solid electrolytes, was used.

[0219] A solution was prepared by dissolving PTFE particles, which are the first binder, in a xylene solvent at a concentration of 0.2 wt%, and the mixture was mixed with Li6PS5Cl powder, which is the first solid electrolyte, a sulfide-based solid electrolyte, and the mixture was coated on a PET (polyethylene terephthalate) release film using a doctor blade, and then vacuum-dried at 100°C for 12 hours to form a first solid electrolyte layer. However, the adhesive strength was weak, so the first solid electrolyte layer was not formed in the form of a membrane. Therefore, it was impossible to manufacture a solid electrolyte membrane in which the first solid electrolyte layer and the second solid electrolyte layer were laminated.

[0220]

[0221] Comparative Example 2

[0222] A slurry was prepared by mixing 98 wt% of Li6PS5Cl, a sulfide-based solid electrolyte, and 2 wt% of SEBS (Styrene-ethylene-butylene-styrene), a binder, with xylene, a solvent. At this time, the concentration of the slurry was set to 60 wt% of the sulfide-based solid electrolyte and 40 wt% of the solvent.

[0223] The above slurry was coated on a PET (polyethylene terephthalate) release film using a doctor blade and then dried at a temperature of 80°C to produce a solid electrolyte membrane having a thickness of 50 μm.

[0224] The binder is in particulate form because it has not been subjected to the appropriate number of calendaring processes.

[0225]

[0226] Comparative Example 3

[0227] As a solid electrolyte membrane, only the first solid electrolyte layer of Example 1 including a particle-type binder was used.

[0228]

[0229] Comparative Example 4

[0230] As a solid electrolyte membrane, only the second solid electrolyte layer of Example 1 including a fibrous binder was used.

[0231]

[0232] Comparative Example 5

[0233] Only the second solid electrolyte layer manufactured in Example 2 was used as the solid electrolyte membrane.

[0234]

[0235] Experimental Example 1: Measurement of the ionic conductivity of a solid electrolyte membrane

[0236] In order to confirm the ionic conductivity according to the shape of the binder included in the solid electrolyte membrane and the form of the solid electrolyte membrane, the ionic conductivity was measured using the following method.

[0237]

[0238] To measure the ionic conductivity of the solid electrolyte membrane, the solid electrolyte membrane was placed in a polyether ether ketone (PEEK) holder with a diameter of 10 mm, and the ionic conductivity was measured using a titanium rod as a blocking electrode.

[0239] The resistance was measured at 25°C using an electrochemical impedance spectrometer (EIS, VM3, Bio Logic Science Instrument) with an amplitude of 10 mV and a scan range of 1 Hz to 0.1 MHz, and the ionic conductivity of the solid electrolyte membrane was calculated using Equation 1 below.

[0240]

[0241] [Formula 1]

[0242]

[0243]

[0244] In the above equation 1, σi is the ionic conductivity (mS / cm) of the solid electrolyte membrane, R is the resistance (Ω) of the solid electrolyte membrane measured by the electrochemical impedance spectrometer, L is the thickness (㎛) of the solid electrolyte membrane, and A is the area (cm) of the solid electrolyte membrane. 2 ) means.

[0245] The measured ionic conductivity values ​​are listed in Table 2 below.

[0246]

[0247] Ionic Conductivity (mS / cm) Example 11.616 Example 21.532 Example 31.995 Comparative Example 1-Comparative Example 20.916 Comparative Example 32.125 Comparative Example 41.865 Comparative Example 51.26

[0248]

[0249] Referring to Table 2 above, the solid electrolyte membranes of Examples 1 to 3 exhibited ionic conductivity that could be applied to all-solid-state batteries.

[0250] In addition, Comparative Example 1 attempted to manufacture a solid electrolyte membrane including a first solid electrolyte layer and a second solid electrolyte layer by a wet process, but since the first and second binders, PTFE, have the property of dissolving in a xylene solvent, it was not manufactured in the form of a membrane, and thus ion conductivity measurement was not possible.

[0251] In addition, Comparative Example 2 used SEBS, a binder that does not dissolve in a xylene solvent, but a solid electrolyte membrane was manufactured using a wet process using a relatively large amount of binder, 2 wt%, and it was confirmed that the ionic conductivity was relatively low compared to Examples 1 to 3.

[0252] In addition, Comparative Example 3 is a solid electrolyte membrane (calendaring loop 5 times) which is the first solid electrolyte layer manufactured by the dry process in Example 1, and has a small content of the first binder of 0.2 wt%, a single layer form, and a small number of calendaring loops, so that the first binder is in a particulate form, and therefore the ionic conductivity is higher than that of Example 1. However, since it is in a single layer form, it can be predicted that the strength will be lower than that of Example 1 which is in a double layer form.

[0253] In addition, Comparative Example 4 is a solid electrolyte membrane (calendaring loop 30 times) which is a second solid electrolyte layer manufactured by a dry process in Example 1, and has a low content of the second binder of 0.5 wt% and is in a single layer form, and exhibits high ionic conductivity at a level similar to that of Example 1. However, since it is in a single layer form, it can be predicted that the strength will be weaker than that of Example 1 which is in a double layer form.

[0254] In addition, Comparative Example 5 is a solid electrolyte membrane, which is a second solid electrolyte layer manufactured by a dry process in Example 2 (calendaring loops 30 times), and since the content of the second binder is high at 2 wt% and the number of calendaring loops is high, the second binder has a fibrous form, so the strength can be increased, but the ionic conductivity was somewhat low. In addition, since the solid electrolyte membrane was in the form of a single layer, it can be predicted that the strength will be weaker compared to Example 2, which is in the form of a double layer.

[0255]

[0256] Experimental Example 2: Correlation between Binder Shape and All-Solid-State Battery Performance

[0257] An experiment was conducted to determine the effect of the binder shape included in the solid electrolyte membrane on the performance of an all-solid-state battery.

[0258] The all-solid-state battery was designed with a structure including a positive electrode (NCM811: LPSCl: VGCF (Vapor Grown Carbon Fiber) = 66:31:3 (wt%)), a negative electrode (Li, Li-In, or Si), and a sulfide-based solid-state electrolyte membrane (SSE) interposed between them.

[0259]

[0260] The sulfide-based solid electrolyte membrane included in the all-solid-state battery of Fig. 2a (a) is made so that the content of fibrous PTFE binder is 5 wt% according to the method for manufacturing the second sulfide-based solid electrolyte layer of Example 1 (5 wt% PTFE SSE).

[0261] The sulfide-based solid electrolyte membrane included in the all-solid-state battery of Fig. 2a (b) is formed as a double layer, and the double layer includes a sulfide-based solid electrolyte membrane (0 wt% PTFE SSE) that does not include a fibrous PTFE binder and a sulfide-based solid electrolyte membrane (5 wt% PTFE SSE) that has a PTFE content of 5 wt%, which is a fibrous PTFE binder. The all-solid-state battery was manufactured such that the sulfide-based solid electrolyte membrane (0 wt% PTFE SSE) that does not include a binder is in contact with the negative electrode (Li-In).

[0262]

[0263] Figure 2b is a charge / discharge curve for an all-solid-state battery having the structure shown in Figure 2a (positive electrode loading 2.5 mAhㆍcm -2 ; C rate: 0.1C). Figures 2b (a) and (b) are charge / discharge curves for the all-solid-state battery corresponding to Figure 2a (a) and (b), respectively.

[0264] Referring to (a) of Fig. 2b, it can be seen that when a sulfide-based solid electrolyte membrane containing a fibrous PTFE binder in an all-solid-state battery comes into contact with a negative electrode, normal operation of the battery is difficult due to a side reaction between the fibrous PTFE binder and the negative electrode.

[0265] Referring to (b) of Fig. 2b, it can be seen that when a sulfide-based solid electrolyte membrane that does not include a fibrous PTFE binder on the surface in contact with the negative electrode is formed, the side reaction between the fibrous PTFE binder and the negative electrode is prevented, thereby improving the lifespan of the all-solid-state battery.

[0266]

[0267] Figure 3a (a) shows the double-layer structure of a sulfide-based solid electrolyte membrane included in an all-solid-state battery. According to the method for manufacturing a sulfide-based solid electrolyte membrane of Example 1, the first solid electrolyte layer contained 0.5 wt% of a particulate PTFE binder, and the second solid electrolyte layer contained a fibrous PTFE binder. In the first solid electrolyte layer, a calendaring loop was performed 5 times so that the PTFE binder became particulate.

[0268] Figure 3a (b) shows a double-layer structure of a sulfide-based solid electrolyte membrane included in an all-solid-state battery, and the first and second solid electrolyte layers of the sulfide-based solid electrolyte membrane of Example 1 were each subjected to a calendaring process 30 times so that 0.5 wt% of a fibrous PTFE binder was included.

[0269]

[0270] Figure 3b is a charge / discharge curve for an all-solid-state battery having the structure shown in Figure 3a (positive electrode loading 2.5 mAhㆍcm -2 ; C rate: 0.1C). Figures 3b (a) and (b) are charge / discharge curves for the all-solid-state battery corresponding to Figure 3a (a) and (b), respectively.

[0271] Referring to (a) of Fig. 3b, it can be seen that when a sulfide-based solid electrolyte membrane containing a particulate PTFE binder rather than a fibrous PTFE binder comes into contact with the negative electrode in an all-solid-state battery, the side reaction between the particulate PTFE binder and the negative electrode is terminated early, thereby increasing the charging capacity of the all-solid-state battery.

[0272] Referring to (b) of Fig. 3b, it can be seen that when a sulfide-based solid electrolyte membrane containing a fibrous PTFE binder in an all-solid-state battery comes into contact with the cathode, normal operation of the battery becomes difficult due to a side reaction between the fibrous PTFE binder and the cathode. Furthermore, the side reaction may continue along the fibrous PTFE binder and eventually reach the cathode, resulting in a soft short circuit.

[0273]

[0274] Therefore, for normal operation and performance improvement of the all-solid-state battery, it was confirmed that the shape of the binder included in the sulfide-based solid electrolyte membrane adjacent to the negative electrode is more advantageous in the form of particles rather than fibers.

[0275]

[0276] Experimental Example 3: Evaluation of Cycle Characteristics of All-Solid-State Batteries

[0277] The cycle characteristics of the all-solid-state battery manufactured in Example 1 were evaluated. The all-solid-state battery manufactured in Example 1 is a full cell including a negative electrode (Si), a double-layer solid electrolyte membrane (Bilayer SSE-1), and a positive electrode (NCM).

[0278] The cycle characteristics evaluation method of the all-solid-state battery was to conduct charge and discharge at room temperature at a constant positive electrode loading amount, a constant current rate (C rate), and a constant negative electrode / positive electrode capacity ratio (N / P Ratio), and evaluate the discharge capacity retention rate.

[0279]

[0280] Figure 4 is a charge / discharge curve for the all-solid-state battery manufactured in Example 1 (positive electrode loading 2.5 mAhㆍcm -2 ; C rate: 0.1C; N / P Ratio: 1.2).

[0281] Referring to Fig. 4, it can be seen that the discharge capacity retention rate of the all-solid-state battery manufactured in Example 1 is high.

[0282]

[0283] In addition, a cycle performance test was conducted on the all-solid-state battery of Example 1 by measuring the discharge capacity up to 200 cycles (positive electrode loading 2.5 mAhㆍcm-2; C rate: 0.33C; N / P Ratio: 1.2). As a result, it was confirmed that the all-solid-state battery of Example 1 maintained the discharge capacity at a similar level up to 200 cycles.

[0284]

[0285] Although the present invention has been described above with reference to limited embodiments and drawings, the present invention is not limited thereto, and it is obvious that various modifications and variations are possible within the scope of the technical idea of ​​the present invention and the equivalent scope of the patent claims to be described below by a person having ordinary skill in the art to which the present invention pertains.

[0286]

[0287] [Brief explanation of symbols]

[0288] 1: Solid electrolyte membrane

[0289] 10: First solid electrolyte layer

[0290] 10a: First solid electrolyte, 10b: Particulate binder

[0291] 20: Second solid electrolyte layer

[0292] 20a: Second solid electrolyte, 20b: Fibrous binder

[0293] 30: Bipolar

[0294] 40: Cathode

Claims

1. A solid electrolyte membrane comprising a first solid electrolyte layer and a second solid electrolyte layer formed on one surface of the first solid electrolyte layer, The first solid electrolyte layer comprises a first solid electrolyte and a particulate binder, wherein the weight of the particulate binder is 2 wt% or less based on the total weight of the first solid electrolyte layer, The second solid electrolyte layer comprises a second solid electrolyte and a fibrous binder, wherein the weight of the fibrous binder is 0.01 to 5 wt% based on the total weight of the second solid electrolyte layer. The above solid electrolyte membrane is a solvent-free solid electrolyte membrane.

2. In paragraph 1, A solid electrolyte membrane, wherein the content of the first solid electrolyte is 98 wt% or more based on the total weight of the first solid electrolyte layer.

3. In paragraph 1, A solid electrolyte membrane, wherein the content of the second solid electrolyte is 95 to 99.99 wt% based on the total weight of the second solid electrolyte layer.

4. In paragraph 1, A solid electrolyte membrane, wherein the particulate binder and the fibrous binder each include at least one selected from the group consisting of polytetrafluoroethylene (PTFE), ethylene-vinyl acetate (EVA), styrene-ethylene-butylene-styrene (SEBS), and copolymers containing these.

5. In paragraph 1, A solid electrolyte membrane, wherein the first solid electrolyte or the second solid electrolyte is a sulfide-based solid electrolyte, a halide-based solid electrolyte or an oxide-based solid electrolyte.

6. In paragraph 1, A solid electrolyte membrane, wherein the thickness of the solid electrolyte membrane is 20 ㎛ to 700 ㎛.

7. In paragraph 1, A solid electrolyte membrane, wherein the ionic conductivity of the solid electrolyte membrane is 0.5 mS / cm to 10 mS / cm.

8. In paragraph 1, A solid electrolyte membrane, wherein the solid electrolyte membrane is solvent-free.

9. In paragraph 1, A solid electrolyte membrane, wherein the first solid electrolyte layer is composed of a first solid electrolyte and a particulate binder, and the second solid electrolyte layer is composed of a second solid electrolyte and a fibrous binder.

10. In paragraph 1, A solid electrolyte membrane, wherein no solvent is used in the manufacture of the first solid electrolyte layer and the second solid electrolyte layer.

11. In paragraph 1, A solid electrolyte membrane, wherein the particulate binder and the fibrous binder comprise polytetrafluoroethylene (PTFE), and the first solid electrolyte and the second solid electrolyte comprise Li6PS5Cl.

12. A method for manufacturing a solid electrolyte membrane, comprising the steps of manufacturing a first solid electrolyte layer and a second solid electrolyte layer respectively and then bonding them together. The above first solid electrolyte layer is manufactured by the following steps (A1) to (A2): (A1) a step of mixing first solid electrolyte particles and a first binder; and (A2) a step of applying the mixture obtained in the step (A1) to a first calendaring process to form it into a film shape to obtain a first solid electrolyte layer; The second solid electrolyte layer is manufactured by the following steps (B1) to (B2): (B1) a step of mixing a second solid electrolyte and a second binder; and (B2) a step of applying the mixture obtained in step (B1) to a second calendaring process to form it into a film shape to obtain a second solid electrolyte; A method for manufacturing a solid electrolyte membrane, wherein the first binder is a particulate binder, and the second binder is fiberized when mixed to become a fibrous binder.

13. In paragraph 12, A method for manufacturing a solid electrolyte membrane, wherein the temperatures of the first and second calendaring processes are each 50°C to 200°C.

14. In paragraph 13, A method for manufacturing a solid electrolyte membrane, wherein the first calendaring process is performed for 1 to 10 loops, and the second calendaring process is performed for 5 to 50 loops.

15. In paragraph 12, A method for manufacturing a solid electrolyte membrane, wherein the above-mentioned calendaring process is performed uniaxially or biaxially.

16. In paragraph 12, A method for manufacturing a solid electrolyte membrane, wherein the first solid electrolyte layer is composed of a first solid electrolyte and a particulate binder, and the second solid electrolyte layer is composed of a second solid electrolyte and a fibrous binder.

17. In paragraph 12, A method for producing a solid electrolyte membrane, wherein no solvent is used in the production of the first solid electrolyte layer and the second solid electrolyte layer.

18. In paragraph 12, A method for manufacturing a solid electrolyte membrane, wherein the particulate binder and the fibrous binder comprise polytetrafluoroethylene (PTFE), and the first solid electrolyte and the second solid electrolyte comprise Li6PS5Cl.

19. An all-solid-state battery comprising a positive electrode, a negative electrode, and a solid electrolyte membrane of claim 1 interposed therebetween.

20. In paragraph 19, An all-solid-state battery, wherein the first solid electrolyte layer of the above solid electrolyte membrane is adjacent to the negative electrode.

Images