Electrode for all solid state battery, and anodeless all solid state battery comprising the same

Abstract

An electrode for an all-solid-state battery according to one embodiment of the present invention comprises a current collector; an intermediate layer disposed on the current collector and including a carbon structure, wherein the carbon structure comprises: a plurality of base bodies; and a spaced-apart space formed by the base bodies being spaced apart from each other, wherein the cumulative 50% diameter (D50) according to the cumulative volume distribution of the base bodies is 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak may be 0.3° or more and 0.8° or less.

Description

Technology Field

[0001] The present invention relates to an electrode for an all-solid-state battery having an intermediate layer into which lithium is deposited, and a negative electrode all-solid-state battery comprising the same. Background Technology

[0002] Rechargeable secondary batteries are used not only in small electronic devices such as mobile phones and laptops but also in large transportation vehicles such as hybrid and electric cars. Accordingly, there is a need to develop secondary batteries with higher stability and energy density.

[0003] Most conventional secondary batteries utilize cells based on organic solvents (organic liquid electrolytes), which limits their potential for improving stability and energy density. On the other hand, all-solid-state batteries, which use inorganic solid electrolytes, are receiving significant attention recently because they are based on technology that eliminates organic solvents, allowing for the fabrication of safer and simpler cells.

[0004] Generally, an all-solid-state battery comprises a positive active material layer bonded to a positive current collector, a negative active material layer bonded to a negative current collector, and a solid electrolyte layer disposed between the positive active material layer and the negative active material layer. However, the negative active material layer includes a solid electrolyte for the movement of lithium ions in addition to a negative active material such as graphite, and since the solid electrolyte has a higher specific gravity than a liquid electrolyte, the energy density of the all-solid-state battery is lower than that of a lithium-ion battery using a liquid electrolyte.

[0005] Recently, active research is being conducted on storage-type anode-free solid-state batteries that omit the negative electrode active material layer and directly deposit lithium ions onto the negative electrode current collector using lithium metal, etc., in order to increase the energy density of solid-state batteries.

[0006] A negative electrode all-solid-state battery is equipped with an intermediate layer containing silver (Ag) and carbon material between the solid electrolyte layer and the negative electrode current collector to ensure uniform precipitation and deposition of lithium. During the charging of a negative electrode all-solid-state battery, lithium ions (Li + ) reaches the intermediate layer through the solid electrolyte layer. The lithium ions (Li + ) undergoes an alloying reaction with the above silver (Ag) and moves, after which it is deposited between the cathode current collector and the intermediate layer.

[0007] However, anode-free all-solid-state batteries have a problem where active lithium is consumed due to uncontrolled lithium dendritic growth and side reactions, and their lifespan is shortened due to internal short circuits. Prior art literature

[0008] KR 10-2020-0052707 The problem to be solved

[0009] The problem to be solved by the present invention is to provide an electrode for an all-solid-state battery in which lithium dendrite growth is suppressed and direct contact between lithium and a solid electrolyte is prevented.

[0010] Another problem to be solved by the present invention is to provide a negative electrode all-solid-state battery in which lithium dendrite growth is suppressed and direct contact between lithium and the solid electrolyte is prevented, thereby exhibiting excellent lifespan characteristics and battery characteristics by including the electrode for the all-solid-state battery. means of solving the problem

[0011] (1) The present invention comprises a current collector; an intermediate layer disposed on the current collector and comprising a carbon structure, wherein the carbon structure comprises: a plurality of base bodies; and a spaced-apart space formed by the base bodies being spaced apart from each other, and a cumulative 50% diameter (D) according to the cumulative volume distribution of the base bodies 50The present invention provides an electrode for an all-solid-state battery having a diameter of 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.3° or more and 0.8° or less.

[0012] (2) The present invention provides an electrode for an all-solid-state battery in which, in (1) above, when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.4° or more and 0.7° or less.

[0013] (3) In the present invention, when a Raman spectrum is measured for the carbon structure, a spectrum with a Raman shift range of 2600 / cm or more and 2800 / cm or less is observed as a single peak, and a fitting curve is defined by fitting the spectrum with a single Voigt profile, and then the coefficient of determination value (R) of the fitting curve for the spectrum 2 The present invention provides an electrode for an all-solid-state battery in which ) is 0.985 or higher.

[0014] (4) The present invention provides an electrode for an all-solid-state battery in any one of (1) to (3), wherein the base body is stacked and spaced apart from each other in the stacking direction.

[0015] (5) In any one of (1) to (4), the present invention relates to a 10% diameter (D) according to the cumulative volume distribution of the base body. 10 ) provides an electrode for an all-solid-state battery having a thickness of 1.5 μm or more and 4.5 μm or less.

[0016] (6) In any one of (1) to (5), the present invention relates to a 90% diameter (D) according to the cumulative volume distribution of the base body. 90 ) provides an electrode for an all-solid-state battery having a thickness of 13 μm or more and 25 μm or less.

[0017] (7) The present invention provides an electrode for an all-solid-state battery in any one of (1) to (6), wherein the base body has a SPAN value of 2.5 or less according to the following mathematical formula 1.

[0018] [Mathematical Formula 1]

[0019]

[0020] In the above mathematical formula 1,

[0021] D 10 is the cumulative 10% diameter according to the cumulative volume distribution of the base body, and

[0022] D 50 It is the cumulative 50% diameter according to the cumulative volume distribution of the base body, and

[0023] D 90 It is the cumulative 90% diameter according to the cumulative volume distribution of the base body.

[0024] (8) The present invention provides an electrode for an all-solid-state battery in which, in any one of (1) to (7), the particle size in the (002) direction of the base body is 5 nm or more and 30 nm or less.

[0025] (9) In any one of (1) to (8) above, the present invention comprises an intermediate layer having at least 85% by weight of the carbon structure and 97.5% by weight. The present invention provides an electrode for an all-solid-state battery containing less than or equal weight percent.

[0026] (10) In any one of (1) to (9) the present invention, the intermediate layer has a carbon structure of 0.8 g / cm³ 3 Above 2.0 g / cm³ 3 The present invention provides an electrode for an all-solid-state battery comprising the following:

[0027] (11) The present invention comprises a negative electrode current collector; an intermediate layer disposed on the negative electrode current collector and comprising a carbon structure; a solid electrolyte layer disposed on the intermediate layer; a positive active material layer disposed on the solid electrolyte layer and comprising a positive active material; and a positive current collector disposed on the positive active material layer, wherein the carbon structure comprises: a plurality of base bodies; and a spaced-apart space formed by the base bodies being spaced apart from each other, and a cumulative 50% diameter (D) according to the cumulative volume distribution of the base bodies 50 The present invention provides a non-anode all-solid-state battery having a diameter of 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.3° or more and 0.8° or less.

[0028] (12) The present invention provides a non-anode all-solid-state battery according to (11), wherein, in the state before the non-anode all-solid-state battery is operated, the thickness of the intermediate layer is 5 μm or more and 20 μm or less.

[0029] (13) The present invention provides a non-cathode all-solid-state battery in which, in (11) or (12), when the non-cathode all-solid-state battery is charged, lithium ions are electrodeposited within the lithium electrodeposition space.

[0030] (14) The present invention provides a non-cathode all-solid-state battery in which, in any one of (11) to (13), when the non-cathode all-solid-state battery is charged, a separate lithium electrodeposition layer is not formed between the intermediate layer and the solid electrolyte layer.

[0031] (15) The present invention provides a non-anode all-solid-state battery in which, in any one of (11) to (14), when XRD analysis is performed on the intermediate layer after the non-anode all-solid-state battery is buffered, the intensity of the Li (110) peak relative to the intensity of the LiC6 (001) peak is 0.5 or greater.

[0032] (16) The present invention provides a non-anode all-solid-state battery in which, in any one of (11) to (15), the solid electrolyte layer comprises a sulfide-based solid electrolyte.

[0033] (17) The present invention provides a method for manufacturing an electrode for an all-solid-state battery, comprising the steps of: applying energy to a mixture of carbon material and a polymer binder dissolved therein to separate and self-assemble a base body within the carbon material and rearrange it (S1); and ball milling the result of step (S1) for 55 minutes or more and 150 minutes or less to produce a carbon structure (S2).

[0034] (18) The present invention provides a method for manufacturing an electrode for an all-solid-state battery, wherein in (17), the step (S1) involves applying energy to the mixture to remove the polymer binder and form a spaced-out space.

[0035] (19) The present invention, in accordance with (17) or (18), wherein the polymer binder is a polyester, polyethylene vinyl acetate, polyester-polyethylene vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyolefin, polyvinyl chloride, polyvinyl acetate, polyethylene terephthalate, polystyrene, polyethylene ketone, polyethylene terephthalate glycol, polyethyleneimide, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene, vinylidene fluoride copolymer, hexafluoropropylene, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyimide, polyamide imide, polyacrylic acid, polyvinyl alcohol, styrene butadiene rubber-based polymer, acrylonitrile-butadiene rubber, The present invention provides a method for manufacturing an electrode for an all-solid-state battery comprising a material selected from the group consisting of acrylonitrile-butadiene-styrene rubber, acrylate-based rubber, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC), and composite polymers mixed with one or more of these.

[0036] (20) The present invention provides a method for manufacturing an electrode for an all-solid-state battery, wherein in any one of (17) to (19), the ball mill grinding is performed for 80 minutes or more and 120 minutes or less. Effects of the invention

[0037] An electrode for an all-solid-state battery according to one embodiment of the present invention suppresses lithium dendrite growth and ensures that lithium is deposited only within the electrode without being deposited in a separate layer.

[0038] A non-cathode all-solid-state battery according to one embodiment of the present invention includes an electrode for the all-solid-state battery, thereby preventing direct contact between lithium and a solid electrolyte, and thus exhibiting excellent lifespan characteristics and battery characteristics. Brief explanation of the drawing

[0039] FIG. 1 is a schematic diagram illustrating the structure according to the operating state of a negative electrode all-solid-state battery according to one embodiment of the present invention. FIG. 2 shows i) the state before lithium electrodeposition, and ii) 0.5 mAh / cm² of a negative electrode all-solid-state battery according to Example 1 of the present invention. 2 State in which lithium is electrodeposited on the intermediate layer, iii) 1.0 mAh / cm² 2 State in which lithium is electrodeposited on the intermediate layer and iv) 2.0 mAh / cm 2 This is a diagram showing SEM images and EDS mapping of cross-sections of a cathode-free all-solid-state battery via SEM-EDS for each state in which lithium is electrodeposited on an intermediate layer. Figure 3 is an SEM image of the base body for the pre-operation and post-operation states, respectively, of a negative electrode all-solid-state battery according to Example 1 of the present invention. Figure 4 is the XPS analysis result of the intermediate layer measured before operation of the anode-free all-solid-state battery according to Example 1 of the present invention. Figure 5 is the XPS analysis result of the intermediate layer measured in the post-operation state of the anode-free all-solid-state battery according to Example 1 of the present invention. Figure 6 is a STEM image of an intermediate layer of a cathode-free all-solid-state battery according to Example 1 of the present invention. Figure 7 is a Raman spectrum measured for the intermediate layer of each of the anode-free all-solid-state batteries according to Example 1 and Comparative Example 1 of the present invention. FIG. 8 is an XRD spectrum of the intermediate layer of each of the non-cathode all-solid-state batteries according to Example 1 and Comparative Example 1 of the present invention before operation. FIG. 9 shows a capacity of 2.0 mAh / cm² for each of the anode-free all-solid-state batteries according to Example 1 and Comparative Example 1 of the present invention. 2 This is the XRD spectrum of the intermediate layer measured after electrodepositing lithium into the intermediate layer. Figure 10 shows the GITT measurement results for the first discharge process of each half cell according to Example 1 and Comparative Example 1 of the present invention. FIG. 11 is a graph of the cycle performance of each of the anode-free all-solid-state batteries according to Example 1 and Comparative Example 1 of the present invention. FIG. 12 is an SEM image of a base body according to Example 1 and Comparative Example 2 of the present invention. FIG. 13 is a graph of the cycle performance of each half-cell according to Example 1 and Comparative Example 2 of the present invention. Specific details for implementing the invention

[0040] Hereinafter, the present invention will be described in more detail to aid in understanding the invention. In this case, terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0041] The terms used in this specification are used merely to describe exemplary embodiments and are not intended to limit the invention. The singular expression includes the plural expression unless the context clearly indicates otherwise.

[0042] In this specification, terms such as “comprising,” “comprising,” or “having” are intended to specify the existence of the implemented features, numbers, steps, components, or combinations thereof, and should not be understood as precluding the existence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0044] Anode-free all-solid-state battery

[0045] The present invention provides a non-cathode all-solid-state battery comprising an electrode for an all-solid-state battery.

[0046] A non-cathode all-solid-state battery according to one embodiment of the present invention comprises at least: a negative electrode current collector (40); an intermediate layer (30) disposed on the negative electrode current collector and including a carbon structure; a solid electrolyte layer (20) disposed on the intermediate layer; a positive active material layer (12) disposed on the solid electrolyte layer and including a positive active material; and a positive current collector (10) disposed on the positive active material layer, wherein the carbon structure comprises a plurality of base bodies (31); and a spaced-apart space formed by the base bodies being spaced apart from each other, and a cumulative 50% diameter (D) according to the cumulative volume distribution of the base bodies 50 ) is 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.3° or more and 0.8° or less.

[0048] Generally, an all-solid-state battery comprises a positive active material layer bonded to a positive current collector, a negative active material layer bonded to a negative current collector, and a solid electrolyte layer disposed between the positive and negative active material layers. However, the negative active material layer includes a solid electrolyte for the movement of lithium ions in addition to a negative active material such as graphite, and since the solid electrolyte has a higher specific gravity than a liquid electrolyte, the energy density of the all-solid-state battery is lower than that of a lithium-ion battery using a liquid electrolyte.

[0049] Recently, active research is being conducted on storage-type anode-free solid-state batteries that omit the negative electrode active material layer and directly deposit lithium ions onto the negative electrode current collector using lithium metal, etc., in order to increase the energy density of solid-state batteries.

[0050] Conventional anode-free all-solid-state batteries are equipped with an intermediate layer containing a carbon material between the solid electrolyte layer and the negative current collector to ensure uniform precipitation and deposition of lithium. During the charging of an anode-free all-solid-state battery, lithium ions (Li + ) reaches the intermediate layer through the solid electrolyte layer. The lithium ions (Li + ) reacts with the carbon material and moves, then precipitates between the negative electrode current collector and the intermediate layer. However, when general graphite is included as the carbon material in the intermediate layer of a non-negative all-solid-state battery, not only is active lithium consumed due to uncontrolled lithium dendrite growth and side reactions, but there was also a problem of shortened lifespan caused by lithium ions precipitating between the solid electrolyte layer and the intermediate layer due to the crystallinity of the graphite, leading to an internal short circuit.

[0052] A negative electrode all-solid-state battery according to one embodiment of the present invention has a cumulative 50% diameter (D) according to the cumulative volume distribution. 50) is a carbon structure including a base layer having a size of 5 μm or more and 12 μm or less. When XRD analysis is performed, the carbon structure having a full width at half maximum (FWHM, 2θ) of the (002) peak of 0.3° or more and 0.8° or less is used as an intermediate layer. When a negative electrode all-solid-state battery is charged and lithium ions are electrodeposited, they are not electrodeposited as a separate layer between the solid electrolyte layer and the intermediate layer, but can be electrodeposited inside the intermediate layer. Accordingly, the internal short circuit phenomenon caused by the separate formation of a lithium electrodeposited layer between the solid electrolyte layer and the intermediate layer can be prevented, thereby improving lifespan characteristics.

[0054] Hereinafter, each component constituting a negative electrode all-solid-state battery according to an embodiment of the present invention will be described in detail with reference to FIG. 1. FIG. 1 is a schematic diagram illustrating the structure according to the operating state of a negative electrode all-solid-state battery according to an embodiment of the present invention. FIG. 1 illustrates a negative electrode all-solid-state battery (1) in an initial state (i.e., a state of being completely discharged before the first charge), a negative electrode all-solid-state battery (1') in a fully charged state, and a negative electrode all-solid-state battery (1'') in a state of being completely discharged after being fully charged. In the following description of each component of the negative electrode all-solid-state battery according to an embodiment of the present invention, unless otherwise specified, the description will be based on the negative electrode all-solid-state battery (1) in the initial state.

[0056] 1. Electrode for all-solid-state battery

[0057] A non-cathode all-solid-state battery according to one embodiment of the present invention may include an electrode for an all-solid-state battery. The electrode for an all-solid-state battery comprises at least a current collector; and an intermediate layer disposed on the current collector and comprising a carbon structure, wherein the carbon structure comprises: a plurality of base bodies; and a spaced-apart space formed by the base bodies being spaced apart from each other, and a cumulative 50% diameter (D) according to the cumulative volume distribution of the base bodies 50) is 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.3° or more and 0.8° or less.

[0058] According to one embodiment of the present invention, the electrode for the all-solid-state battery is an electrode in which the negative active material layer is omitted and lithium ions are directly deposited onto a current collector, such as lithium metal, and may substantially be the negative electrode of an all-solid-state battery without a negative electrode. Accordingly, the current collector included in the electrode for the all-solid-state battery without a negative electrode will be referred to as a negative current collector (40) below.

[0060] cathode current collector

[0061] According to one embodiment of the present invention, the negative electrode current collector (40) may be a plate-shaped substrate that is electrically conductive and may include a material that does not react with lithium. Specifically, the negative electrode current collector (40) is not particularly limited as long as it is conductive without causing chemical changes in the battery, and may be one or more selected from the group consisting of aluminum (Al), nickel (Ni), titanium (Ti), tungsten (W), iron (Fe), chromium (Cr), and stainless steel, or may be an alloy thereof.

[0063] middle layer

[0064] According to one embodiment of the present invention, the intermediate layer (30) is configured to be directly disposed on the negative electrode current collector (40), and can serve to induce the deposition of lithium metal in a horizontal direction along the surface of the negative electrode current collector (40) when lithium ions are deposited in the form of lithium metal on the surface of the negative electrode current collector.

[0065] According to one embodiment of the present invention, the intermediate layer (30) has a cumulative 50% diameter (D) according to the volume cumulative distribution. 50) may include a base body (31) having a width of 5 μm or more and 12 μm or less, and may include a carbon structure having a full width at half maximum (FWHM, 2θ) of the (002) peak having a width of 0.4° or more and 0.7° or less when XRD analysis is performed.

[0067] According to one embodiment of the present invention, when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak may be 0.3° or more and 0.8° or less. Specifically, it may be 0.32° or more, 0.34° or more, 0.36° or more, 0.38° or more, or 0.4° or more, and may also be 0.78° or less, 0.76° or less, 0.74° or less, 0.72° or less, or 0.7° or less. When the above-described range is satisfied, lithium can be easily electrodeposited inside the carbon structure by satisfying the ratio of the width and number of the lithium electrodeposition spacing space (32) to be described later in the carbon structure. When XRD analysis is performed on the carbon structure, if the full width at half maximum (FWHM, 2θ) of the (002) peak is less than the above range, the size of the base body inside the carbon structure becomes larger than necessary, and the width of the space for lithium electrodeposition becomes larger than the desirable range, and consequently, lithium may not be easily electrodeposited inside the carbon structure. In addition, when XRD analysis is performed on the carbon structure, if the full width at half maximum (FWHM, 2θ) of the (002) peak exceeds the above range, the size of the base body inside the carbon structure becomes smaller than necessary, and the width of the space for lithium electrodeposition becomes smaller than necessary, and consequently, lithium may not be easily electrodeposited inside the carbon structure.

[0068] According to one embodiment of the present invention, when a Raman spectrum is measured for the carbon structure, a spectrum in the Raman shift range of 2600 / cm or higher and 2800 / cm or lower is observed as a single peak, and after defining a fitting curve by fitting the spectrum with a single Voigt profile, the coefficient of determination value (R) of the fitting curve for the spectrum 2 ) can be 0.985 or higher.

[0069] According to one embodiment of the present invention, the coefficient of determination value (R) of the fitting curve for the spectrum 2 ) may be 0.986 or higher, 0.987 or higher, 0.988 or higher, 0.989 or higher, 0.99 or higher, or 0.992 or higher. A spectrum in the Raman shift range of 2600 / cm or higher and 2800 / cm or lower is observed as a single peak, and if the spectrum satisfies the above-described range, a lithium electrodeposition space (32) having the width of the above-described range may be formed in the carbon structure. If it is less than the above range, the carbon structure may have a structure similar to graphite, and lithium may not be easily electrodeposited inside the carbon structure.

[0071] According to one embodiment of the present invention, the 50% diameter (D) according to the volume cumulative distribution measured using a laser diffraction particle size analyzer of the base body (31) 50 ) may be 5 μm or more and 12 μm or less, and as a specific example, it may be 5.5 μm or more, 6 μm or more, 6.5 μm or more, 7 μm or more, 7.5 μm or more, or 8 μm or more, and also 11.5 μm or less, 11 μm or less, 10.5 μm or less, 10 μm or less, 9.5 μm or less, or 9 μm or less. If the above range is satisfied, the lithium electrodeposition mechanism described later can be easily performed, and lithium can be smoothly electrodeposited inside the carbon structure. If, D of the base body (31) 50If the above-described range is exceeded, the lithium electrodeposition spacing (32) formed from the base body within the carbon structure is reduced, so the lithium electrodeposition mechanism described later cannot be easily performed, making it difficult to electrodepose lithium inside the carbon structure. In addition, D of the base body (31) 50 If the range described above is less than the specified range, the internal crystal structure of the base body (31) changes, making it difficult to electrodeposit lithium inside the carbon structure.

[0072] According to one embodiment of the present invention, the 10% diameter (D) according to the volume cumulative distribution measured using a laser diffraction particle size analyzer of the base body (31) 10 The range may be 1.5 μm or more and 4.5 μm or less. Specifically, it may be 1.6 μm or more, 1.7 μm or more, 1.8 μm or more, 1.9 μm or more, or 2 μm or more. Additionally, it may be 4.4 μm or less, 4.3 μm or less, 4.2 μm or less, 4.1 μm or less, or 4 μm or less. If the above range is satisfied, the lithium electrodeposition mechanism described below can be performed more easily.

[0073] According to one embodiment of the present invention, the 90% diameter (D) according to the volume cumulative distribution measured using a laser diffraction particle size analyzer of the base body (31) 90 The range may be 13 μm or more and 25 μm or less, and as specific examples, it may be 13.5 μm or more, 14 μm or more, 14.5 μm or more, 15 μm or more, 15.5 μm or more, or 16 μm or more, and may also be 24.5 μm or less, 24 μm or less, 23.5 μm or less, 23 μm or less, 22.5 μm or less, or 22 μm or less. If the above range is satisfied, the lithium electrodeposition mechanism described below can be performed more easily.

[0074] According to one embodiment of the present invention, the base body (31) may have a SPAN value of 1.9 or less according to the following mathematical formula 1.

[0076] [Mathematical Formula 1]

[0077]

[0078] In the above mathematical formula 1,

[0079] D 10 is the cumulative 10% diameter according to the cumulative volume distribution of the above base body, and

[0080] D 50 is the cumulative 50% diameter according to the cumulative volume distribution of the above base body, and

[0081] D 90 is the cumulative 90% diameter according to the cumulative volume distribution of the above base body.

[0083] According to one embodiment of the present invention, the SPAN value represented by the mathematical formula 1 may be, as specific examples, 0.5 or more, 0.6 or more, 0.8 or more, 1 or more, 1.2 or more, or 1.4 or more, and may also be 1.85 or less, 1.8 or less, 1.75 or less, 1.7 or less, or 1.65 or less. If the above range is satisfied, the lithium electrodeposition mechanism described below can be performed more easily.

[0085] According to one embodiment of the present invention, the base body (31) may be a plate-shaped particle. In the present invention, the term "plate" is understood as a concept that includes not only a flat shape having a uniform thickness profile, but also a curved shape, which is recognized as a flat shape having a uniform thickness profile that is folded and curved.

[0087] According to one embodiment of the present invention, the base body (31) may have a width in the thickness direction, that is, a particle size in the (002) direction, of 5 nm or more and 30 nm or less, and as specific examples, may be 6 nm or more, 8 nm or more, 10 nm or more, 12 nm or more, 15 nm or more, and may also be 28 nm or less, 26 nm or less, 24 nm or less, 22 nm or less, 20 nm or less. When the above range is satisfied, the lithium electrodeposition mechanism described later can be performed more easily, and lithium can be smoothly electrodeposited inside the carbon structure.

[0088] A base body (31) according to one embodiment of the present invention may be a graphene platelet in which graphene is stacked in a disordered manner, or a stratified carbon in which graphene is combined.

[0089] According to one embodiment of the present invention, a plurality of base bodies (31) are stacked and can be spaced apart from each other in the stacking direction to form a spaced-apart space. Specifically, each of the plurality of base bodies (31) can be spaced apart in whole or in part to form a spaced-apart space, and the spaced-apart space may include a lithium electrodeposition spaced-apart space (32) having a width of 0.3 nm or more and 10 nm or less.

[0090] According to one embodiment of the present invention, the ratio of the number of lithium electrodeposition spaced spaces (32) to the total number of spaced spaces may be 45% or more, and as a specific example, may be 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, or 90% or more. When the above range is satisfied, the electrodeposition of lithium ions within the intermediate layer (30) can be performed more easily.

[0091] Referring to FIG. 1, the lithium electrodeposition spacing space (32) according to one embodiment of the present invention has a width much narrower than the pores of a conventional general porous structure of graphite, and may have a width of 0.3 nm or more and 10 nm or less in the stacking direction, and as a specific example, may have a width of 0.4 nm or more, 0.6 nm or more, 0.8 nm or more, 1.0 nm or more, 1.2 nm or more, 1.4 nm or more, 1.6 nm or more, 1.7 nm or more, 1.8 nm or more, or 2.0 nm or more, and may also have a width of 9.8 nm or less, 9.6 nm or less, 9.4 nm or less, 9.2 nm or less, 9.0 nm or less, 8.8 nm or less, 8.6 nm or less, 8.4 nm or less, 8.2 nm or less, or 8.0 nm or less. When the above-described range is satisfied, when the negative electrode all-solid-state battery is charged, lithium ions are not electrodeposited between the solid electrolyte layer (20) and the intermediate layer (30), and can be fully electrodeposited inside the intermediate layer (30) without the formation of lithium dendrites.

[0093] According to one embodiment of the present invention, the intermediate layer (30) may further include a conductive material, a solid electrolyte and / or a binder.

[0094] According to one embodiment of the present invention, the conductive material may serve to further improve the conductivity of the intermediate layer (30). The conductive material is not particularly limited as long as it is conductive without causing chemical changes in the battery, and for example, carbon-based materials such as graphite; carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, SC65; conductive fibers such as carbon fibers or metal fibers; metal powders such as carbon fluoride, aluminum, or nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives may be used.

[0095] According to one embodiment of the present invention, the binder may serve to facilitate bonding between the conductive material and the carbon structure. The binder may be polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose, starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, nipril-butadiene rubber, fluororubber, and various copolymers thereof.

[0096] An intermediate layer (30) according to one embodiment of the present invention may contain the carbon structure in an amount of 85 weight% or more and 97.5 weight% or less, and as a specific example, 86 weight% or more, 87 weight% or more, 88 weight% or more, It may contain 87 weight% or more, 89 weight% or more, or 90 weight% or more, and also 97 It may contain less than or equal to 96.5% by weight, less than or equal to 96% by weight, less than or equal to 95.5% by weight, less than or equal to 95% by weight, or less than or equal to 94.5% by weight. If the above range is satisfied, lithium ions can be more easily electrodeposited within the intermediate layer (30).

[0097] An intermediate layer (30) according to one embodiment of the present invention has the carbon structure at 0.8 g / cm³ 3 Above 2.0 g / cm³ 3 It may include the following, and as a specific example, 0.85 g / cm³ 3 Above, 0.9 g / cm³ 3 Above, 0.95 g / cm³ 3 Above, 1.0 g / cm³ 3 Above, 1.1 g / cm³ 3 Above or 1.2 g / cm³ 3 It may include the above, and also 1.9 g / cm³ 3 Below, 1.8 g / cm³ 3 Below, 1.7 g / cm³ 3 Below, 1.6 g / cm³3 Below, 1.5 g / cm³ 3 Less than or equal to 1.4 g / cm³ 3 It may include the following. If the above range is satisfied, lithium ions can be more easily electrodeposited within the intermediate layer (30).

[0098] According to one embodiment of the present invention, the non-anode all-solid-state battery comprises an intermediate layer (30) made of a carbon structure including a plurality of base bodies and a lithium electrodeposition space formed by the plurality of base bodies spaced apart from each other, the distance having a width of 0.3 nm or more and 10 nm or less. When the non-anode all-solid-state battery is charged, lithium ions are electrodeposited within the lithium electrodeposition space (32) inside the intermediate layer (30), and a separate lithium electrodeposition layer may not be formed between the intermediate layer (30) and the solid electrolyte layer (20). Accordingly, direct contact between the solid electrolyte layer (20) and the electrodeposited lithium is prevented, thereby preventing an internal short circuit from occurring.

[0100] The thickness of the intermediate layer (30) of the anode-free solid-state battery according to one embodiment of the present invention may vary depending on the operating state of the anode-free solid-state battery. Specifically, when the anode-free solid-state battery is charged, the thickness of the intermediate layer (30) may increase, and when it is discharged, the thickness of the intermediate layer (30) may decrease. Referring to FIG. 1, an anode-free solid-state battery (1) in an initial state (i.e., a state of complete discharge before initial charging), an anode-free solid-state battery (1') in a fully charged state, and an anode-free solid-state battery (1'') in a state of complete discharge after charging are illustrated. Below, the lithium electrodeposition mechanism of the anode-free solid-state battery according to one embodiment of the present invention will be described in detail.

[0101] According to one embodiment of the present invention, the base body (31') of a buffered non-anode all-solid-state battery (1') may have LiC6 formed by reaction with lithium ions, and accordingly, may have a larger volume compared to the base body (31) in the pre-charged state.

[0102] According to one embodiment of the present invention, the buffered base body (31') may have a width in the thickness direction, i.e., a particle size in the (002) direction, of 7 nm or more and 41 nm or less, and as a specific example, may be 8 nm or more, 9 nm or more, 10 nm or more, 12 nm or more, or 15 nm or more, and may also be 40 nm or less, 38 nm or less, 36 nm or less, 34 nm or less, 32 nm or less, or 30 nm or less.

[0103] According to one embodiment of the present invention, LiC6 formed in a buffered base body (31') creates a passage for lithium ions to move to a lithium electrodeposition space (32'), and the lithium ions can be electrodeposited as lithium metal in the lithium electrodeposition space (32') to form a lithium electrodeposition body (33').

[0104] According to one embodiment of the present invention, a lithium electrodeposited body (33') may be formed within a lithium electrodeposited space (32') of a buffered all-solid-state battery (1') and, when XRD analysis is performed on an intermediate layer (30') containing the same, the intensity of the Li (110) peak relative to the intensity of the LiC6 (001) peak may be 0.5 or higher, and as a specific example, may be 0.6 or higher, 0.7 or higher, 0.8 or higher, 0.9 or higher, or 1 or higher.

[0105] According to one embodiment of the present invention, the width of the lithium electrodeposition space (32') in a buffered state may be increased compared to the initial state of the lithium electrodeposition space (32) by the lithium electrodeposition body (33') formed therein. This is because when the initial state of the all-solid-state battery (1) without a negative electrode is charged, lithium ions are electrodeposited within the lithium electrodeposition space (32) to form a lithium electrodeposition body, and as the lithium electrodeposition body grows, it pushes up the base body (31) forming the lithium electrodeposition space (32), thereby increasing the width of the lithium electrodeposition space (32).

[0106] According to one embodiment of the present invention, the lithium electrodeposition spacing (32') of a buffered non-anode all-solid-state battery (1') may have a width of 3 nm or more and 20 nm or less in the stacking direction, and as a specific example, may have a width of 3.5 nm or more, 4 nm or more, 4.5 nm or more, 5 nm or more, 5.5 nm or more, 6 nm or more, 6.5 nm or more, 7 nm or more, 7.5 nm or more, or 8 nm or more, and may also have a width of 19 nm or less, 18 nm or less, 17 nm or less, 16 nm or less, 15 nm or less, 14 nm or less, or 13 nm or less.

[0107] Referring to FIG. 1, as described above, when an initial state of a negative electrode all-solid-state battery (1) is charged to become a fully charged state of a negative electrode all-solid-state battery (1'), the volume of the fully charged base body (31') increases compared to the initial state base body (31), and the width of the fully charged lithium electrodeposition space (32') increases compared to the initial state lithium electrodeposition space (32). Therefore, the thickness (d2) of the intermediate layer (30') of the fully charged state of a negative electrode all-solid-state battery (1') may be thicker than the thickness (d1) of the intermediate layer (31) of the initial state of a negative electrode all-solid-state battery (1).

[0108] According to one embodiment of the present invention, when the non-anode all-solid-state battery is in an initial state (i.e., a state of complete discharge before initial charging), the thickness (d1) of the intermediate layer (30) may be 5 μm or more and 20 μm or less. Specifically, it may be 5.5 μm or more, 6 μm or more, 6.5 μm or more, 7 μm or more, 7.5 μm or more, or 8 μm or more. Additionally, it may be 19 μm or less, 18 μm or less, 17 μm or less, 16 μm or less, or 15 μm or less. When the above-described range is satisfied, lithium electrodeposition within the intermediate layer (30) becomes easier, and the energy density of the battery can be further improved.

[0109] According to one embodiment of the present invention, the thickness (d2) of the intermediate layer (30') of the buffered non-anode all-solid-state battery (1') may be 10 μm or more and 50 μm or less, and as a specific example, may be 12 μm or more, 14 μm or more, 16 μm or more, 18 μm or more, or 20 μm or more, and may also be 45 μm or less, 40 μm or less, 35 μm or less, or 30 μm or less.

[0110] According to one embodiment of the present invention, the ratio (d1 / d2) of thickness (d1) to thickness (d2) may be 2 or more, and as a specific example, may be 2.2 or more, 2.4 or more, 2.6 or more, 2.8 or more, or 3 or more.

[0111] According to one embodiment of the present invention, when a fully charged all-solid-state battery (1') is discharged to become a fully discharged all-solid-state battery (1''), lithium ions escape from the intermediate layer (30'), so the intermediate layer (30'') of the fully discharged all-solid-state battery (1'') may be in a state similar to that of the initial all-solid-state battery (1). Specifically, the thickness (d1'') of the intermediate layer (30'') in the fully discharged state after charging may be substantially the same as the thickness (d1) of the intermediate layer (30) in the initial state.

[0112] According to one embodiment of the present invention, the base body (31'') in a fully discharged state after charging may have a larger particle size compared to the base body (31) in an initial state and may have a smaller particle size compared to the base body (31') in a buffered state.

[0113] According to one embodiment of the present invention, the base body (31'') in a completely discharged state may have a width in the thickness direction, that is, a particle size in the (002) direction, of 6 nm or more and 31 nm or less, and as a specific example, may be 7 nm or more, 8 nm or more, 10 nm or more, 12 nm or more, 15 nm or more, and may also be 30 nm or less, 28 nm or less, 26 nm or less, 24 nm or less, 22 nm or less.

[0114] Accordingly, according to one embodiment of the present invention, the lithium electrodeposition spacing space (32'') in a fully discharged state after charging may have a smaller width compared to the lithium electrodeposition spacing space (32) in an initial state. Specifically, the lithium electrodeposition spacing (32'') in a fully discharged state after charging may have a width of 0.3 nm or more and 8 nm or less in the stacking direction, and as a specific example, it may have a width of 0.32 nm or more, 0.34 nm or more, 0.38 nm or more, 0.4 nm or more, 0.42 nm or more, 0.44 nm or more, 0.46 nm or more, 0.48 nm or more, or 0.5 nm or more, and may also have a width of 7.8 nm or less, 7.6 nm or less, 7.4 nm or less, 7.2 nm or less, 7.0 nm or less, 6.8 nm or less, 6.6 nm or less, 6.4 nm or less, 6.2 nm or less, or 6.0 nm or less. If the above range is satisfied, the base body (31'') in a fully discharged state after charging has a larger particle size compared to the base body (31) in an initial state, so that the lithium electrodeposition spacing space (32'') in a fully discharged state after charging has a smaller width compared to the lithium electrodeposition spacing space (32) in an initial state, lithium ions are not electrodeposited between the solid electrolyte layer (20) and the intermediate layer (30), and can be fully electrodeposited inside the intermediate layer (30) without the formation of lithium dendrites.

[0116] In one embodiment of the present invention, a non-anode all-solid-state battery uses a carbon structure having the structure described above as an intermediate layer (30), so that when the non-anode all-solid-state battery is charged, lithium ions are not electrodeposited between the solid electrolyte layer (20) and the intermediate layer (30), and can be fully electrodeposited inside the intermediate layer (30) without the formation of lithium dendrites.

[0118] According to one embodiment of the present invention, the method for manufacturing an electrode for an all-solid-state battery comprises at least: a step (S1) of separating and self-assembling a base body within the carbon material by applying energy to a mixture in which a carbon material and a polymer binder are dissolved; and a step (S2) of manufacturing a carbon structure by ball milling the result of step (S1) for 55 minutes or more and 150 minutes or less.

[0119] Specifically, the above step (S1) may be a step of applying energy to a mixture in which a carbon material, i.e., graphite, is dissolved to separate and self-assemble the base material, i.e., graphene, within the graphite and rearrange it. By the above step (S1), the full width at half maximum (FWHM, 2θ) of the (002) peak in the range described above and the Raman spectrum may be expressed.

[0120] According to one embodiment of the present invention, the mixture may additionally include a polymer binder, and as the polymer binder is removed by the energy, a plurality of spaced-out spaces may be formed at the location where the polymer binder was present, and among the spaced-out spaces, those having a thickness direction width of 0.3 nm or more and 10 nm or less may be defined as spaced-out spaces for lithium electrodeposition.

[0121] Specifically, the graphite is a carbon material containing pores, and when energy is applied to the graphite containing a polymer binder, the graphite is compressed so that the size and number of the pores are reduced, and the remaining pores can be filled by the polymer binder. Subsequently, when the polymer binder is removed by the energy, the remaining pores become spacing spaces, and the carbon structure is formed, and among the spacing spaces, those having a thickness direction width of 0.3 nm or more and 10 nm or less are defined as spacing spaces for lithium electrodeposition.

[0122] According to one embodiment of the present invention, the energy can be provided by various methods such as heat treatment, light irradiation, and ultrasonic treatment, and preferably by heat treatment.

[0123] According to one embodiment of the present invention, after the polymer binder is removed, some of the polymer binder may remain on the surface of the base body.

[0124] According to one embodiment of the present invention, the polymer binder comprises polyester, polyethylene vinyl acetate, polyester-polyethylene vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyolefin, polyvinyl chloride, polyvinyl acetate, polyethylene terephthalate, polystyrene, polyethylene ketone, polyethylene terephthalate glycol, polyethyleneimide, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene, vinylidene fluoride copolymer, hexafluoropropylene, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyimide, polyamide imide, polyacrylic acid, polyvinyl alcohol, styrene butadiene rubber-based polymer, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, acrylate-based It may include a material selected from the group consisting of rubber, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC), and composite polymers in which one or more of these are mixed.

[0125] According to one embodiment of the present invention, a lithiophilic polymer binder is used when manufacturing the carbon structure, so that the lithiophilic polymer binder may remain on the substrate. In this case, since it can attract lithium ions during the lithium plating process, lithium ions can be stably deposited uniformly at a high capacity.

[0127] According to one embodiment of the present invention, step (S2) can produce the carbon structure having a preferred range of base body particle size distribution by performing ball-mill grinding on the result of step (S1) for 55 minutes or more and 150 minutes or less. As a specific example, the ball-mill grinding may be performed for 60 minutes or more, 65 minutes or more, 70 minutes or more, 75 minutes or more, 80 minutes or more, 85 minutes or more, or 90 minutes or more, and may also be performed for 145 minutes or less, 140 minutes or less, 135 minutes or less, 130 minutes or less, 125 minutes or less, or 120 minutes or less. When the above ranges are satisfied, the cumulative 50% diameter (D) according to the cumulative volume distribution of the base body included in the carbon structure 50 ) is controlled to a level of 5 μm or more and 12 μm or less, so that the lithium electrodeposition mechanism described above can be easily performed, and accordingly, lithium can be smoothly electrodeposited inside the carbon structure.

[0129] 2. Solid electrolyte layer

[0130] A solid-state battery according to one embodiment of the present invention may include a solid electrolyte layer (20). The solid electrolyte layer (20) is disposed between the positive active material layer (12) and the intermediate layer (30) and may serve to transfer lithium ions between the positive active material layer (12) and the negative current collector (40).

[0131] According to one embodiment of the present invention, the solid electrolyte layer (20) may be disposed on an intermediate layer (30) and may include a solid electrolyte having lithium ion conductivity. The solid electrolyte may include at least one selected from the group consisting of oxide-based solid electrolytes, sulfide-based solid electrolytes, polymer electrolytes, and combinations thereof, and preferably may include a sulfide-based solid electrolyte.

[0132] According to one embodiment of the present invention, the sulfide-based solid electrolyte is Li6PS5X (X = one or more selected from the group consisting of Cl, Br, and I), Li 10 GeP2S 12 , Li3PS4, Li7P3S 11 , Li2S-P2S5, Li2S-P2S5-LiI, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2SSiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (where m and n are positive numbers, and Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li x MO y (where x and y are positive numbers, and M is one of P, Si, Ge, B, Al, Ga, In) and may include one or more selected from the group consisting of combinations thereof.

[0134] 3. Anode

[0135] A positive electrode according to one embodiment of the present invention may include a positive electrode active material layer (12) and a positive electrode current collector (11).

[0137] positive active material layer

[0138] According to one embodiment of the present invention, the positive active material layer (12) may include a positive active material, a conductive material, and a binder.

[0139] According to one embodiment of the present invention, the positive electrode active material is a lithium ion (Li +A material capable of reversibly absorbing and releasing ) may include a complex oxide of lithium and metal, namely a lithium complex metal oxide. As a specific example, the lithium complex metal oxide is a lithium-manganese-based oxide (e.g., LiMnO2, LiMn2O2). 4　 etc.), lithium-cobalt oxides (e.g., LiCoO2, etc.), lithium-nickel oxides (e.g., LiNiO2, etc.), lithium-nickel-manganese oxides (e.g., LiNi 1-Y Mn Y O2(here, 0 <Y<1), LiMn 2-z Ni z O4 (where 0 < Z < 2), etc.), lithium-nickel-cobalt oxides (e.g., LiNi 1-Y1 Co Y1 O2(here, 0 <Y1<1) 등), 리튬-망간-코발트계 산화물(예를 들면, LiCo 1-Y2 Mn Y2 O2(here, 0 <Y2<1), LiMn 2-z1 Co z1 O4 (where 0 < Z1 < 2), etc.), lithium-nickel-manganese-cobalt oxides (e.g., Li(Ni p Co q Mn r1 )O2(where, 0<p<1, 0<q<1, 0<r1<1, p+q+r1=1) or Li(Ni p1 Co q1 Mn r2 )O4 (where 0<p1<2, 0<q1<2, 0<r2<2, p1+q1+r2=2), etc.), or lithium-nickel-cobalt-transition metal (M) oxide (e.g., Li(Ni p2 Co q2 Mn r3 M S2Examples include )O2(wherein M is selected from the group consisting of Al, Fe, V, Cr, Ti, Ta, Mg and Mo, and p2, q2, r3 and s2 are each atomic fractions of independent elements, such that 0<p2<1, 0<q2<1, 0<r3<1, 0<s2<1, p2+q2+r3+s2=1), etc., and any one or more of these compounds may be included.

[0140] Among these, the lithium composite metal oxides mentioned above include LiCoO2, LiMnO2, LiNiO2, and lithium nickel manganese cobalt oxide (e.g., Li(Ni)) in that they can improve the capacity characteristics and stability of the battery. 1 / 3 Mn 1 / 3 Co 1 / 3 )O2, Li(Ni 0.6 Mn 0.2 Co 0.2 )O2, 　 Li(Ni) 0.5 Mn 0.3 Co 0.2 )O2, Li(Ni 0.7 Mn 0.15 Co 0.15 )O2 and Li(Ni 0.8 Mn 0.1 Co 0.1 )O2, etc.), or lithium nickel-cobalt-aluminum oxide (e.g., Li(Ni 0.8 Co 0.15 Al 0.05 It may be )O2, etc., and considering the significant improvement effect resulting from controlling the type and content ratio of constituent elements forming the lithium composite metal oxide, the lithium composite metal oxide is Li(Ni 0.6 Mn 0.2 Co 0.2 )O2, 　 Li(Ni) 0.5 Mn 0.3 Co 0.2 )O2, Li(Ni 0.7 Mn 0.15 Co 0.15 )O2 and Li(Ni 0.8 Mn 0.1 Co 0.1It may be O2, etc., and any one of these or a mixture of two or more may be used.

[0141] According to one embodiment of the present invention, the positive electrode active material comprises boron (B) or LiNbO and may further comprise a coating layer surrounding the lithium composite metal oxide. By further including the coating layer, the structural stability of the positive electrode active material may be improved.

[0142] In addition, the positive active material layer (12) according to one embodiment of the present invention may further include a solid electrolyte. The solid electrolyte may coat the positive active material. Accordingly, the compatibility between the positive active material layer (12) and the solid electrolyte layer (20) may be improved. Since the detailed description of the solid electrolyte is the same as that described for the solid electrolyte layer (20), a detailed description thereof will be omitted below.

[0143] According to one embodiment of the present invention, the conductive material may serve to further enhance the conductivity of the positive electrode active material. The conductive material is not particularly limited as long as it is conductive without causing chemical changes in the battery, and for example, carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal black, SC65, etc.; conductive fibers such as carbon fibers or metal fibers; metal powders such as carbon fluoride, aluminum, nickel powder, etc.; conductive whiskers such as zinc oxide, potassium titanate, etc.; conductive metal oxides such as titanium oxide, etc.; conductive materials such as polyphenylene derivatives, etc. may be used.

[0144] According to one embodiment of the present invention, the binder may serve to facilitate bonding between a conductive material, a positive active material, and a positive current collector. The binder may be polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose, starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, nipril-butadiene rubber, fluororubber, and various copolymers thereof.

[0146] positive current collector

[0147] According to one embodiment of the present invention, the positive current collector (11) is not particularly limited as long as it is conductive without causing chemical changes in the battery, and may be one or more selected from the group consisting of aluminum (Al), nickel (Ni), titanium (Ti), tungsten (W), iron (Fe), chromium (Cr), and stainless steel, or may be an alloy thereof.

[0149] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0151] Example 1

[0152] 1,000 mg of graphene was placed in a reactor containing 20 ml of acetone and dispersed, after which 20 g of an adhesive material (manufactured by Loctite, product name: loctite401) was additionally added and stirred. Subsequently, the reactor was placed in a vacuum oven and dried at 60°C for 3 hours, followed by grinding with a ball mill for 105 minutes. The ground product was subjected to CVD heat treatment by sequentially maintaining it at 120°C for 10 minutes, 400°C for 10 minutes, and 800°C for 5 minutes. The heat-treated product was sieved through a 400-mesh (37 µm) screen to obtain carbon fixative powder.

[0153] A slurry was prepared by dispersing 92.5 mg of the carbon structure powder prepared above, 2.5 mg of a conductive material (Super P, MTI), and 5 mg of a binder (PVDF, sigma-aldrich) in 300 μL of N-Methyl-2-pyrrolidone (NMP, sigma-aldrich) solvent. Subsequently, a negative electrode current collector made of nickel foil (Ni foil) with a thickness of 10 μm was prepared, and the prepared slurry was uniformly coated onto the surface of the negative electrode current collector using a doctor blade. The coated negative electrode current collector was placed in a vacuum oven and dried at 60°C for at least 12 hours to produce an electrode for an all-solid-state battery with a carbon structure layer formed thereon.

[0155] Comparative Example 1

[0156] A slurry was prepared by dispersing 92.5 mg of graphite powder, 2.5 mg of conductive material (SuperP), and 5 mg of binder (PVDF) in 300 μL of N-Methyl-2-pyrrolidone (NMP) solvent. Subsequently, a negative electrode current collector made of nickel foil (Ni foil) with a thickness of 10 μm was prepared, and the prepared slurry was uniformly coated onto the surface of the negative electrode current collector using a doctor blade. The coated negative electrode current collector was placed in a vacuum oven and dried at 60°C for at least 12 hours to produce an electrode for an all-solid-state battery with a graphite layer formed thereon.

[0158] Comparative Example 2

[0159] 1,000 mg of graphene was placed in a reactor containing 20 ml of acetone and dispersed, after which 20 g of an adhesive material (manufactured by Loctite, product name: loctite401) was additionally added and stirred. Subsequently, the reactor was placed in a vacuum oven and dried at 60°C for 3 hours, followed by grinding with a ball mill for 5 minutes. The ground product was subjected to CVD heat treatment by sequentially maintaining it at 120°C for 10 minutes, 400°C for 10 minutes, and 800°C for 5 minutes. The heat-treated product was sieved through a 400-mesh (37 µm) screen to obtain carbon fixative powder.

[0160] A slurry was prepared by dispersing 92.5 mg of the carbon structure powder prepared above, 2.5 mg of a conductive material (Super P, MTI), and 5 mg of a binder (PVDF, sigma-aldrich) in 300 μL of N-Methyl-2-pyrrolidone (NMP, sigma-aldrich) solvent. Subsequently, a negative electrode current collector made of nickel foil (Ni foil) with a thickness of 10 μm was prepared, and the prepared slurry was uniformly coated onto the surface of the negative electrode current collector using a doctor blade. The coated negative electrode current collector was placed in a vacuum oven and dried at 60°C for at least 12 hours to produce an electrode for an all-solid-state battery with a carbon structure layer formed thereon.

[0162] Experimental Example 1

[0163] Manufacture of Cathode-Free All-Solid State Batteries

[0164] For the electrode for an all-solid-state battery prepared in Example 1, a sulfide-based solid electrolyte (Li6PS5Cl) was placed in an annular mold with a diameter of 13 mm. 0.5 Br 0.5 ) 150~200 mg of powder was filled, and a solid electrolyte layer was placed by applying pressure of 400 MPa, and then an intermediate layer with a thickness of 10 μm was formed between the solid electrolyte layer and the negative current collector by applying pressure of 100 MPa.

[0165] Subsequently, on the opposite side of the solid electrolyte layer, a positive active material (LiNi 0.8 Co 0.1 Mn 0.1 O2): Solid electrolyte (Li6PS5Cl 0.5 Br 0.5 A positive electrode active material layer was formed by adding 20 mg of a mixed powder containing a binder (VGCF) in a ratio of 70:30:3 and pressing at 200 MPa, and a negative electrode all-solid-state battery was manufactured by placing a positive current collector made of Al with a thickness of 10 μm on the positive electrode active material layer and pressing at 380 MPa.

[0167] <Observation of changes in the intermediate layer according to the filling process>

[0168] i) state before lithium electrodeposition of the anode-free all-solid-state battery according to Example 1, ii) 0.5 mAh / cm 2 State in which lithium is electrodeposited on the intermediate layer, iii) 1.0 mAh / cm² 2 State in which lithium is electrodeposited on the intermediate layer and iv) 2.0 mAh / cm 2 Figure 2 shows SEM images and EDS mapping of cross-sections of a cathode-free all-solid-state battery via SEM-EDS for each state in which lithium was electrodeposited on the intermediate layer. The SEM instrument used was Thermofisher’s Apreo 2S, and the SEM-EDS instrument used was Thermofisher’s ChemiSEM.

[0169] Referring to Fig. 2, it was observed that the thickness of the intermediate layer containing layered carbon material gradually increased during the charging process of the battery. Additionally, the observation of oxygen in the cross-section of the intermediate layer in Fig. 2 indicates that lithium was oxidized by exposure to air during the measurement process, and it can be seen that lithium was electrodeposited inside the intermediate layer rather than being deposited as a separate layer between the intermediate layer and the solid electrolyte layer.

[0171] <Observation of the structure of the base body>

[0172] An SEM image of the base body taken using a scanning electron microscope (Thermofisher Apreo 2S) on the side opposite to the side in contact with the solid electrolyte layer, after separating the intermediate layer from the anode-free all-solid-state battery according to Example 1 without applying a separate current; and a capacity of 3.5 mAh / cm² in the anode-free all-solid-state battery according to Example 1 2 After electrodepositing lithium onto the intermediate layer, the intermediate layer was separated, and an SEM image of the substrate taken using a scanning electron microscope (Arpeo 2S of Thermofisher) on the opposite side of the surface in contact with the solid electrolyte layer is shown in Fig. 3.

[0173] In addition, the intermediate layer was separated from the anode-free all-solid-state battery according to Example 1 without applying a separate current, and XPS analysis was performed on the side opposite to the surface in contact with the solid electrolyte layer to obtain C1s and O1s spectra, which are shown in Fig. 4. Furthermore, the anode-free all-solid-state battery according to Example 1 has a capacity of 2.0 mAh / cm² 2 After electrodepositing lithium onto the intermediate layer, the intermediate layer was separated, and XPS analysis was performed on the opposite side of the surface in contact with the solid electrolyte layer to obtain C1s spectra, O1s spectra, and Li1s spectra, which are shown in Fig. 5. The XPS analysis was performed using a spectrometer (Thermo Scientific, K-Alpha+, acceleration voltage: 100 eV–4,000 eV, maximum resolution: 0.50 eV).

[0175] Referring to FIG. 3, it can be seen that the base material included in the layered carbon material forming the intermediate layer of Example 1 swells during filling, and referring to FIGs. 4 and 5, it can be seen that when the base material included in the layered carbon material forming the intermediate layer of Example 1 swells, LiC6 is formed in the base material.

[0177] <Observation of the structure of the separation space between base bodies>

[0178] After fully charging the anode-free all-solid-state battery according to Example 1, the intermediate layer was separated, and STEM images were obtained on the separated intermediate layer using a STEM instrument (Titan cubed G2) under an acceleration voltage of 300 kV. The obtained STEM images are shown in Fig. 6.

[0180] Experimental Example 2 - Comparison of Example 1 and Comparative Example 1

[0181] Manufacture of Cathode-Free All-Solid State Batteries

[0182] For each of the all-solid-state battery electrodes prepared in Example 1 and Comparative Example 1, a sulfide-based solid electrolyte (Li6PS5Cl) was placed in an annular mold with a diameter of 13 mm. 0.5 Br 0.5) 150~200 mg of powder was filled, and a solid electrolyte layer was placed by applying pressure of 400 MPa, and then an intermediate layer with a thickness of 10 μm was formed between the solid electrolyte layer and the negative current collector by applying pressure of 100 MPa.

[0183] Subsequently, on the opposite side of the solid electrolyte layer, a positive active material (LiNi 0.8 Co 0.1 Mn 0.1 O2): Solid electrolyte (Li6PS5Cl 0.5 Br 0.5 A positive electrode active material layer was formed by adding 20 mg of a mixed powder containing a binder (VGCF) in a ratio of 70:30:3 and pressing at 200 MPa, and a negative electrode all-solid-state battery was manufactured by placing a positive current collector made of Al with a thickness of 10 μm on the positive electrode active material layer and pressing at 380 MPa.

[0185] <Comparison of Carbon Structures 1>

[0186] The Raman spectra obtained by measuring the intermediate layers of the anode-free all-solid-state battery according to Example 1 and the anode-free all-solid-state battery according to Comparative Example 1 using a Raman spectrometer (Nanobase XperRF, using a 532 nm laser) are shown in FIG. 7. In addition, each 2D peak observed in the Raman shift range of 2600 / cm² to 2800 / cm² was fitted to a single Voigt profile (dotted curve), and the respective coefficient of determination values ​​(R²) were calculated using this. 2 ) calculated.

[0187] Referring to FIG. 7, in the Raman shift range of 2600 / cm to 2800 / cm, one peak is observed in Example 1, and the coefficient of determination (R²) 2 It can be confirmed that ) is 0.99574, and in Comparative Example 1, two peaks (2D1, 2D2) are observed, and the coefficient of determination (R) 2It was confirmed that ) was 0.97825. Through this, it was confirmed that the intermediate layer of Example 1 has a structure similar to graphene with a thin thickness, unlike the intermediate layer of Comparative Example 1.

[0189] <Comparison of Carbon Structures 2>

[0190] XRD spectra were obtained for the intermediate layer of each of the anode-free solid-state battery according to Example 1 and the anode-free solid-state battery according to Comparative Example 1 by measuring with Miniflex (Rigaku) ​​at a voltage of 40 kV, a current of 15 mA CuKα, 2θ (Bragg angle) = 10°~70°, and a scan speed of 2° / 60 sec, and are shown in Fig. 8.

[0191] Referring to Fig. 8, the full width at half maximum (FWHM) of the (002) peak observed around 24°–30° using the measured XRD spectrum was measured to be 0.528° for Example 1 and 0.264° for Comparative Example 1. Through this, it was confirmed that the intermediate layer of Example 1 has a narrow gap formed inside, unlike the intermediate layer of Comparative Example 1. This is expected to be due to the spacing between the base bodies included in the layered carbon material.

[0193] In addition, for each of the anode-free all-solid-state battery according to Example 1 and the anode-free all-solid-state battery according to Comparative Example 1, a current density of 0.5 mA / cm² 2 With a capacity of 2.0 mAh / cm² 2 After electrodepositing lithium onto each intermediate layer, each intermediate layer was separated, and an XRD spectrum was obtained by measuring the opposite side of the surface in contact with the solid electrolyte layer using Miniflex (Rigaku) ​​at a voltage of 40 kV, a current of 15 mA CuKα, 2θ (Bragg angle) = 10°~70°, and a scan speed of 2° / 60 sec, and the results are shown in Fig. 9.

[0194] By analyzing the XRD spectrum of FIG. 9, the LiC6 (001) peak intensity of the anode-free solid-state battery according to Example 1 is set to 1, and the Li (110) peak, graphite (001) peak, and LiC of the anode-free solid-state battery according to Example 1 with respect to the LiC6 (001) peak intensity of the anode-free solid-state battery according to Example 1 x (x>6) The relative intensity of each peak is listed in Table 1 below. In addition, the LiC6 (001) peak intensity of the anode-free all-solid-state battery according to Comparative Example 1 was set to 1, and the Li (110) peak, graphite (001) peak, and LiC of the anode-free all-solid-state battery according to Comparative Example 1 relative to the LiC6 (001) peak intensity of the anode-free all-solid-state battery according to Comparative Example 1 x (x>6) The relative intensity of each peak is listed in Table 1 below.

[0196] LIC6(001) Li (110) graphite (001) LiC x (x>6) Example 1 1 1.02 0 0 Comparative Example 1 1 0.08 0.23 0.51

[0197] Referring to FIG. 9 and Table 1, in the case of Example 1, after lithium electrodeposition, carbon that has reacted incompletely with lithium (LiC x , x>6) Carbon that has not completely reacted with lithium (graphite (001)) is not detected on XRD, but in the case of Comparative Example 1, it can be confirmed that LiCx (x>6) and unreacted carbon (Graphite) are detected.

[0198] In addition, in the case of Example 1, even though XRD measurements were performed on the surface in contact with the solid electrolyte layer of the intermediate layer and the opposite surface, it can be confirmed that the relative intensity of the Li (110) peak is 1.02 compared to the LiC6 (001) peak, and through this, it can be confirmed that lithium itself was precipitated between the base materials inside the intermediate layer.

[0200] <Evaluation of Lithium Ion Diffusion Behavior>

[0201] For each of the electrodes for a non-cathode battery prepared in Example 1 and Comparative Example 1, a sulfide-based solid electrolyte (Li6PS5Cl) was placed in an annular mold with a diameter of 13 mm. 0.5 Br 0.5 ) 150~200 mg of powder was filled, and a solid electrolyte layer was placed by applying pressure of 400 MPa, and then an intermediate layer with a thickness of 10 μm was formed between the solid electrolyte layer and the negative current collector by applying pressure of 100 MPa.

[0202] Afterwards, a lithium metal foil (Honjo Chemical Corp.) with a thickness of 200 μm and a diameter of 12 mm was punched into the opposite side of the solid electrolyte layer, and then T-shaped members acting as lids were inserted into the upper and lower directions of the annular mold to seal it. Subsequently, the annular mold was fastened using a pressure jig with a tightening pressure of 3 Nm to produce a half cell.

[0203] Each half-cell according to Example 1 and Comparative Example 1 (electrode loading amount is 0.9 mg / cm² each) 2 For ), GITT (Galvanostatic Intermittent Titration Technique) measurements were performed on the first discharge process under conditions of applying a current of 17.5 mA / g for 20 minutes and resting for 40 minutes at room temperature (25℃) and a driving pressure of 30 MPa. The voltage change (ΔE) during the current rest period according to the GITT execution time (h) of the intermediate layer of each half-cell according to Example 1 and Comparative Example 1 was measured. s ) and voltage change (ΔE) during current application t ) square of the ratio((ΔE s / ΔE t ) 2 The graph is shown in Fig. 10.

[0205] Referring to FIG. 10, (ΔE of Example 1 s / ΔE t ) 2It can be confirmed that the value maintains a uniform value according to the GITT execution time, and the (ΔE of Comparative Example 1 s / ΔE t ) 2 It can be observed that the value decreases sharply at 61h, 87h, 115h, and 137h. Through this, (ΔE s / ΔE t ) 2 Considering that the value is proportional to the diffusion coefficient, it can be confirmed that lithium ions diffuse stably in Example 1 containing a layered carbon material compared to Comparative Example 1 containing graphite.

[0207] Cycle Characteristics Evaluation

[0208] For each of the anode-free all-solid-state batteries prepared in Example 1 and Comparative Example 1 above, 2.52 mA / cm² under conditions of room temperature and 15 MPa 2 Charge at a current density of 2.52 mA / cm² until it reaches 4.2 V. 2 With discharging until it reaches 2.8 V at a current density defined as one cycle, the charge-discharge cycles under charging conditions are 60 th The graph showing the capacity retention rate and Coulomb efficiency per cycle was measured by repeating charge and discharge until a cycle was completed, and is shown in Fig. 11.

[0210] Referring to FIG. 11, the anode-free all-solid-state battery of Comparative Example 1 stopped operating after 26 cycles due to a short circuit, whereas the anode-free all-solid-state battery of Example 1 was found to operate stably for more than 60 cycles. This is expected to be because the cycle characteristics were improved by the lithium growth mechanism inside the intermediate layer, which causes lithium to be stably electrodeposited inside the intermediate layer without growing in a dendrite shape.

[0212] Experimental Example 3

[0213] Particle Size Distribution Measurement

[0214] Figure 12 shows a particle size distribution graph measured using a particle size analyzer (manufactured by Malvern Panalytical, product name: Mastersizer 3000) after dispersing 1 g of each carbon structure powder prepared in Example 1 and Comparative Example 2 in acetone, and D identified in the particle size distribution graph of Figure 12 10 , D 50 , D 90 , SPAN value((D 90 - D 10 ) / D 50 ) was listed in Table 2.

[0215] The above particle size distribution measurement was performed under conditions of Red light source: Max. 4mW He-Ne 632.8nm, Blue light source: Max. 10mW LED 470nm.

[0217] D 10 (㎛) D 50 (㎛) D 90 (㎛) SPAN Example 1 3.12 8.63 17 1.61 Comparative Example 2 13.1 33.0 110 2.94

[0218] <Manufacturing and Evaluation of Half Cells>

[0219] For each of the all-solid-state battery electrodes prepared in Example 1 and Comparative Example 2, a sulfide-based solid electrolyte (Li6PS5Cl) was placed in an annular mold with a diameter of 13 mm. 0.5 Br 0.5 ) 150~200 mg of powder was filled, and a solid electrolyte layer was placed by applying pressure of 400 MPa, and then an intermediate layer with a thickness of 10 μm was formed between the solid electrolyte layer and the negative current collector by applying pressure of 100 MPa.

[0220] Afterwards, a lithium metal foil (Honjo Chemical Corp.) with a thickness of 200 μm and a diameter of 12 mm was punched into the opposite side of the solid electrolyte layer, and then T-shaped members acting as lids were inserted into the upper and lower directions of the annular mold to seal it. Subsequently, the annular mold was fastened using a pressure jig with a tightening pressure of 3 Nm to produce a half cell.

[0222] 1.167 mA / cm² for each half-cell according to Example 1 and Comparative Example 2 under conditions of 25°C and 20 MPa 2 Capacitance of 3.5 mA / cm² with a current density 2 Electrodeposited lithium, 1.167 mA / cm 2 Capacitance of 3.5 mA / cm² with a current density 2 Desorbing lithium is considered one cycle, and 28 th The charging and discharging were repeated until a cycle was completed, and the Coulomb efficiency and charging capacity per cycle were measured and graphs are shown in Fig. 13.

[0224] Referring to FIGS. 12 and 13, for Example 1, 3.5 mAh / cm 2 It was confirmed that stable operation was achieved without short circuits even in a high-capacity loading environment at that level. On the other hand, in the case of Comparative Example 2, 15 th It was possible to confirm that a short circuit occurred in the cycle.

[0225] This is expected to be because, as Comparative Example 2 uses a carbon structure that does not satisfy the preferred particle size conditions of the base material as an intermediate layer, the gap space for lithium electrodeposition formed between the base materials is reduced compared to the case of Example 1, so the lithium electrodeposition mechanism described in Fig. 1 is not performed, and a separate lithium layer is precipitated between the intermediate layer and the solid electrolyte layer. Explanation of the symbols

[0226] 11: Positive current collector 12: Positive active material layer 20: Solid electrolyte layer 30, 30`, 30``: Intermediate layer 31, 31`, 31``: Base 32, 32`, 32``: Spacing for lithium electrodeposition 33`: Lithium electrodepositor 40: Cathode current collector

Claims

Claim 1 A current collector; comprising an intermediate layer disposed on the current collector and including a carbon structure, wherein the carbon structure comprises: a plurality of base bodies; and a spaced-apart space formed by the base bodies being spaced apart from each other, and a cumulative 50% diameter (D) according to the cumulative volume distribution of the base bodies 50 An electrode for an all-solid-state battery having a diameter of 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.3° or more and 0.8° or less. Claim 2 An electrode for an all-solid-state battery according to claim 1, wherein when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.4° or more and 0.7° or less. Claim 3 In claim 1, when a Raman spectrum is measured for the carbon structure, a spectrum in the Raman shift range of 2600 / cm or higher and 2800 / cm or lower is observed as a single peak, and after defining a fitting curve by fitting the spectrum with a single Voigt profile, the coefficient of determination value (R) of the fitting curve for the spectrum 2 An electrode for an all-solid-state battery in which ) is 0.985 or higher. Claim 4 In claim 1, the electrode for an all-solid-state battery is formed such that the base bodies are stacked and spaced apart from each other in the stacking direction. Claim 5 In claim 1, the 10% diameter (D) according to the cumulative volume distribution of the base body 10 ) is an electrode for an all-solid-state battery having a thickness of 1.5 μm or more and 4.5 μm or less. Claim 6 In claim 1, the 90% diameter (D) according to the cumulative volume distribution of the base body 90 ) is an electrode for an all-solid-state battery having a thickness of 13 μm or more and 25 μm or less. Claim 7 In claim 1, the electrode for an all-solid-state battery having a base body having a SPAN value of 2.5 or less according to the following mathematical formula 1: [Mathematical Formula 1] In the above mathematical formula 1, D 10 is the cumulative 10% diameter according to the cumulative volume distribution of the above base body, and D 50 is the cumulative 50% diameter according to the cumulative volume distribution of the above base body, and D 90 is the cumulative 90% diameter according to the cumulative volume distribution of the above base body. Claim 8 An electrode for an all-solid-state battery according to claim 1, wherein the particle size in the (002) direction of the base body is 5 nm or more and 30 nm or less. Claim 9 In claim 1, the intermediate layer comprises 85 weight percent or more and 97.5 weight percent of the carbon structure. Electrode for an all-solid-state battery containing less than or equal weight percent. Claim 10 In claim 1, the intermediate layer contains the carbon structure at 0.8 g / cm³ 3 Above 2.0 g / cm³ 3 An electrode for an all-solid-state battery comprising the following. Claim 11 The structure comprises: a negative electrode current collector; an intermediate layer disposed on the negative electrode current collector and including a carbon structure; a solid electrolyte layer disposed on the intermediate layer; a positive active material layer disposed on the solid electrolyte layer and including a positive active material; and a positive current collector disposed on the positive active material layer, wherein the carbon structure comprises: a plurality of base bodies; and a spaced-apart space formed by the base bodies being spaced apart from each other, and a cumulative 50% diameter (D) according to the cumulative volume distribution of the base bodies 50 A non-cathode all-solid-state battery having a diameter of 5 μm or more and 12 μm or less, and when XRD analysis is performed on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak is 0.3° or more and 0.8° or less. Claim 12 A non-cathode all-solid-state battery according to claim 11, wherein, in a state prior to operation of the non-cathode all-solid-state battery, the thickness of the intermediate layer is 5 μm or more and 20 μm or less. Claim 13 A non-cathode all-solid-state battery according to claim 11, wherein when the non-cathode all-solid-state battery is charged, lithium ions are electrodeposited within the lithium electrodeposition space. Claim 14 A non-cathode all-solid-state battery according to claim 11, wherein when the non-cathode all-solid-state battery is charged, a separate lithium electrodeposition layer is not formed between the intermediate layer and the solid electrolyte layer. Claim 15 A non-cathode all-solid-state battery according to claim 11, wherein when XRD analysis is performed on the intermediate layer after the non-cathode all-solid-state battery is charged, the intensity of the Li (110) peak relative to the intensity of the LiC6 (001) peak is 0.5 or greater. Claim 16 A non-anode all-solid-state battery according to claim 11, wherein the solid electrolyte layer comprises a sulfide-based solid electrolyte. Claim 17 A method for manufacturing an electrode for an all-solid-state battery, comprising: a step (S1) of applying energy to a mixture in which a carbon material and a polymer binder are dissolved to separate and self-assemble a base body within the carbon material and rearrange it; and a step (S2) of ball-milling the result of step (S1) for 55 minutes or more and 150 minutes or less to manufacture a carbon structure. Claim 18 A method for manufacturing an electrode for an all-solid-state battery, wherein, in claim 17, the above step (S1) involves applying energy to the mixture to remove the polymer binder and form a spaced-out space. Claim 19 In claim 17, the polymer binder is polyester, polyethylene vinyl acetate, polyester-polyethylene vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyolefin, polyvinyl chloride, polyvinyl acetate, polyethylene terephthalate, polystyrene, polyethylene ketone, polyethylene terephthalate glycol, polyethyleneimide, polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene, vinylidene fluoride copolymer, hexafluoropropylene, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyimide, polyamide imide, polyacrylic acid, polyvinyl alcohol, styrene butadiene rubber-based polymer, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, acrylate-based A method for manufacturing an electrode for an all-solid-state battery comprising a material selected from the group consisting of rubber, hydroxypropylmethylcellulose, sodium carboxymethylcellulose (CMC), and composite polymers mixed with one or more of these. Claim 20 A method for manufacturing an electrode for an all-solid-state battery according to claim 17, wherein the ball mill grinding is performed for 80 minutes or more and 120 minutes or less.

Images