Electrode for non-negative electrode all-solid-state battery and non-negative electrode all-solid-state battery including the same

Abstract

An electrode for a negative electrode-free all-solid-state battery according to an embodiment of the present application can include: a current collector; and an intermediate layer disposed on the current collector and including a carbon structure, wherein the carbon structure can include: a plurality of matrices; and interval spaces formed by the matrices spaced apart from each other, wherein the interval spaces can include lithium deposition interval spaces having a width of 0.3 nm or more and 10 nm or less, and a diameter (D 50 ) corresponding to a cumulative volume of 50% in a volume cumulative distribution of the matrices can be 5 μm or more and 12 μm or less.

Description

Technical Field

[0001] The present invention relates to an electrode for an all-solid-state battery without a negative electrode having an intermediate layer of deposited lithium, and an all-solid-state battery without a negative electrode including the electrode. Background Technology

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

[0003] Most existing rechargeable batteries are based on organic solvents (organic liquid electrolytes) to form the cells, which limits their ability to improve stability and energy density. In contrast, all-solid-state batteries using inorganic solid electrolytes, based on technologies that eliminate organic solvents, can be manufactured in a safer and simpler manner, and have therefore attracted considerable attention in recent years.

[0004] Typically, an all-solid-state battery includes a positive electrode active material layer bonded to a cathode current collector, a negative electrode active material layer bonded to a cathode current collector, and a solid electrolyte layer disposed between the positive and negative electrode active material layers. However, in addition to negative electrode active materials such as graphite, the negative electrode active material layer also contains a solid electrolyte for lithium-ion migration, and the specific gravity of the solid electrolyte is greater than that of the liquid electrolyte. Therefore, the energy density of an all-solid-state battery is lower than that of a lithium-ion battery using a liquid electrolyte.

[0005] In recent years, in order to improve the energy density of all-solid-state batteries, research is actively underway on storage-type all-solid-state batteries that omit the negative electrode active material layer and allow lithium ions to be directly deposited on the negative electrode current collector in the form of lithium metal.

[0006] To ensure uniform lithium deposition and precipitation, an intermediate layer containing silver (Ag) and carbon materials is placed between the solid electrolyte layer and the negative electrode current collector in a cathode-free all-solid-state battery. During charging of the cathode-free all-solid-state battery, lithium ions (Li) at the positive electrode... + The lithium ions (Li) reach the intermediate layer through the solid electrolyte layer. + It undergoes an alloying reaction with the silver (Ag) and migrates to precipitate between the negative electrode current collector and the intermediate layer.

[0007] However, all-solid-state batteries without a negative electrode have the following problems: active lithium is consumed due to uncontrolled lithium dendrite growth and side reactions, and battery life is shortened due to internal short circuits.

[0008] [Existing Technical Documents]

[0009] [Patent Literature]

[0010] (Patent Document 1) KR10-2020-0052707 Summary of the Invention

[0011] (a) Technical problems to be solved

[0012] The purpose of this invention is to provide an electrode for a negative electrode-free all-solid-state battery, which suppresses the growth of lithium dendrites and prevents direct contact between lithium and the solid electrolyte.

[0013] Another technical problem to be solved by the present invention is to provide a negative electrode-free all-solid-state battery, which includes an electrode for the negative electrode-free all-solid-state battery, thereby suppressing the growth of lithium dendrites and preventing direct contact between lithium and the solid electrolyte, thereby exhibiting excellent lifespan and battery characteristics.

[0014] (II) Technical Solution

[0015] (1) This invention provides an electrode for a negative electrode-free all-solid-state battery, the electrode comprising: a current collector; and an intermediate layer, the intermediate layer being disposed on the current collector and comprising a carbon structure, wherein the carbon structure comprises: a plurality of substrates; and spacers, the substrates being spaced apart to form the spacers, wherein the spacers include lithium deposition spacers having a width of 0.3 nm or more and 10 nm or less, and the diameter (D) corresponding to 50% of the cumulative volume in the cumulative volume distribution of the substrates. 50 The size is between 5μm and 12μm.

[0016] (2) The present invention provides an electrode for a negative electrode-free all-solid-state battery according to (1) above, wherein the diameter (D) corresponding to 10% of the cumulative volume in the cumulative volume distribution of the substrate is... 10 The size is between 1.5μm and 4.5μm.

[0017] (3) The present invention provides an electrode for a negative electrode-free all-solid-state battery according to (1) or (2) above, wherein the diameter (D) corresponding to 90% of the cumulative volume in the cumulative volume distribution of the substrate is... 90 The size is between 13μm and 25μm.

[0018] (4) The present invention provides an electrode for a non-negative electrode all-solid-state battery according to any one of (1) to (3) above, wherein the span (SPAN) value of the substrate according to the following mathematical formula 1 is 1.9 or less.

[0019] [Mathematical Expression 1]

[0020]

[0021] In the mathematical formula 1, D 10 D is the diameter corresponding to 10% of the cumulative volume in the cumulative volume distribution of the matrix. 50 D is the diameter corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix. 90 It is the diameter corresponding to 90% of the cumulative volume in the cumulative volume distribution of the matrix.

[0022] (5) The present invention provides an electrode for an all-solid-state battery without a negative electrode according to any one of (1) to (4) above, wherein the plurality of substrates are stacked and spaced apart from each other in the stacking direction.

[0023] (6) The present invention provides an electrode for a negative electrodeless all-solid-state battery according to any one of (1) to (5) above, wherein the proportion of the number of lithium deposition spacers is 45% or more relative to the total number of the spacers.

[0024] (7) The present invention provides an electrode for an all-solid-state battery without a negative electrode according to any one of (1) to (6) above, wherein the lithium deposition space has a width of 2 nm or more and 8 nm or less.

[0025] (8) The present invention provides an electrode for an all-solid-state battery without a negative electrode according to any one of (1) to (7) above, wherein the particle size of the substrate in the (002) direction is 5 nm or more and 30 nm or less.

[0026] (9) The present invention provides an electrode for an all-solid-state battery without a negative electrode according to any one of (1) to (8) above, wherein the intermediate layer comprises 85% by weight or more and 97.5% by weight or less of the carbon structure.

[0027] (10) The present invention provides an electrode for a negative electrode-free all-solid-state battery according to any one of (1) to (9) above, wherein the intermediate layer comprises 0.8 g / cm³. 3 Above and 2.0 g / cm 3 The following describes carbon structures.

[0028] (11) The present invention provides a negative electrode-free all-solid-state battery, the negative electrode-free all-solid-state battery comprising: 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 electrode active material layer disposed on the solid electrolyte layer and comprising a positive electrode active material; and a positive electrode current collector disposed on the positive electrode active material layer, wherein the carbon structure comprises: a plurality of substrates; and a spacer space, the substrates being spaced apart from each other to form the spacer space, wherein the spacer space comprises a lithium deposition spacer space having a width of 0.3 nm or more and 10 nm or less, and the diameter (D) corresponding to 50% of the cumulative volume in the cumulative volume distribution of the substrates. 50 The size is between 5μm and 12μm.

[0029] (12) The present invention provides a negative electrode-free all-solid-state battery according to (11) above, wherein, in the state before the negative electrode-free all-solid-state battery is in operation, the thickness of the intermediate layer is more than 5 μm and less than 20 μm.

[0030] (13) The present invention provides a cathode-free all-solid-state battery according to (11) or (12) above, wherein, when the cathode-free all-solid-state battery is charged, lithium ions are deposited in the lithium deposition space.

[0031] (14) The present invention provides a non-negative electrode all-solid-state battery according to any one of (11) to (13) above, wherein, when the non-negative electrode all-solid-state battery is charged, no additional lithium deposition layer is formed between the intermediate layer and the solid electrolyte layer.

[0032] (15) The present invention provides a non-negative electrode all-solid-state battery according to any one of (11) to (14) above, wherein, after the non-negative electrode all-solid-state battery is fully charged, when X-ray diffraction (XRD) analysis is performed on the intermediate layer, the ratio of the intensity of the Li(110) peak to the intensity of the LiC6(001) peak is 0.5 or more.

[0033] (16) The present invention provides a negative electrode-free all-solid-state battery according to any one of (11) to (15) above, wherein the solid electrolyte layer comprises a sulfide-based solid electrolyte.

[0034] (17) The present invention provides a method for manufacturing an electrode for an all-solid-state battery without a negative electrode, the method comprising the following steps: (S1) applying energy to a mixture containing dissolved carbon material and polymer binder to separate the matrix within the carbon material and rearrange it by self-assembly; and (S2) subjecting the product of step (S1) to ball milling for 55 minutes or more and 150 minutes or less to manufacture a carbon structure.

[0035] (18) The present invention provides a method for manufacturing an electrode for an all-solid-state battery without a negative electrode according to (17) above, wherein, in step (S1), energy is applied to the mixture to remove the polymer binder, thereby forming a spacer.

[0036] (19) The present invention provides a method for manufacturing an electrode for a negative electrode-free all-solid-state battery according to (17) or (18) above, wherein the polymer binder comprises a polymer binder selected from polyester, vinyl acetate, polyester-vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyolefin, vinyl acetate, polyethylene terephthalate, polystyrene, polyvinyl ketone, polyethylene terephthalate-ethylene glycol, polyethyleneimine, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyimide, polyamide-imide, polyacrylic acid, polyvinyl alcohol, styrene-butadiene rubber-based polymer, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, acrylate-based rubber, hydroxypropyl methylcellulose, carboxymethyl cellulose (CMC), and composite polymers formed by mixing one or more of these.

[0037] (20) The present invention provides a method for manufacturing an electrode for an all-solid-state battery without a negative electrode according to any one of (17) to (19) above, wherein the ball milling is performed for 80 minutes or more and 120 minutes or less.

[0038] (III) Beneficial Effects

[0039] According to one embodiment of the present invention, the electrode of the negative electrodeless all-solid-state battery suppresses the growth of lithium dendrites and causes lithium to be deposited only inside the electrode, without being deposited in the form of an additional layer.

[0040] According to one embodiment of the present invention, a cathode-free all-solid-state battery includes an electrode for the cathode-free all-solid-state battery, thereby preventing direct contact between lithium and the solid electrolyte, and thus exhibiting excellent lifespan and battery characteristics. Attached Figure Description

[0041] Figure 1The diagram illustrates the structure of a negative electrode-free all-solid-state battery according to an embodiment of the present invention, under operating conditions.

[0042] Figure 2 To illustrate the SEM images and EDS mappings of the electrodeless all-solid-state battery cross-sections according to Embodiment 1 of the present invention in the following four states obtained by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS): i) state before lithium deposition, ii) 0.5 mAh / cm² 2 The state of lithium deposition in the intermediate layer, iii) 1.0 mAh / cm 2 The state of lithium deposition in the intermediate layer and iv) 2.0 mAh / cm 2 The state of lithium deposition in the intermediate layer.

[0043] Figure 3 The figure shows SEM images of each substrate in the pre-operation and post-operation states of the electrodeless all-solid-state battery according to Embodiment 1 of the present invention.

[0044] Figure 4 A graph showing the X-ray photoelectron spectroscopy (XPS) analysis results of the intermediate layer measured in the pre-operation state of the electrodeless all-solid-state battery according to Embodiment 1 of the present invention.

[0045] Figure 5 A graph showing the XPS analysis results of the intermediate layer measured in the post-operation state of the all-solid-state battery without a negative electrode according to Embodiment 1 of the present invention.

[0046] Figure 6 A figure illustrating a scanning transmission electron microscope (STEM) image of the intermediate layer of an all-solid-state battery without a negative electrode according to Embodiment 1 of the present invention.

[0047] Figure 7 The diagram shows the Raman spectra measured for each intermediate layer of the electrodeless all-solid-state battery according to Embodiment 1 and Comparative Example 1 of the present invention.

[0048] Figure 8 This is a diagram showing the XRD patterns of each intermediate layer in the pre-operation state of the electrodeless all-solid-state battery according to Embodiment 1 and Comparative Example 1 of the present invention.

[0049] Figure 9 To demonstrate that the deposition capacity in each intermediate layer of the electrodeless all-solid-state battery according to Embodiment 1 and Comparative Example 1 is 2.0 mAh / cm², 2 The figure shows the XRD pattern of the intermediate layer after lithium was measured.

[0050] Figure 10A graph showing the results of galvanostatic intermittent titration (GITT) measurements of the first discharge process of each half-cell of Example 1 and Comparative Example 1 according to the present invention.

[0051] Figure 11 The graph illustrates the cycle performance of each negative electrode-free all-solid-state battery according to Embodiment 1 and Comparative Example 1 of the present invention.

[0052] Figure 12 Figure showing SEM images of the substrates according to Embodiment 1 and Comparative Example 2 of the present invention.

[0053] Figure 13 A graph illustrating the cycle performance of each half-cell according to Embodiment 1 and Comparative Example 2 of the present invention.

[0054] Explanation of reference numerals in the attached figures:

[0055] 1: All-solid-state battery without negative electrode (initial state)

[0056] 1': All-solid-state battery without negative electrode (fully charged)

[0057] 1``: All-solid-state battery without negative electrode (fully discharged state)

[0058] 11: Positive current collector

[0059] 12: Positive electrode active material layer

[0060] 20: Solid electrolyte layer

[0061] 30: Intermediate Layer (Initial State)

[0062] 30': Middle layer (fully charged)

[0063] 30``: Intermediate layer (fully discharged state)

[0064] 31: Matrix (Initial State)

[0065] 31': Substrate (fully charged)

[0066] 31``: Substrate (fully discharged state)

[0067] 32: Spacer for lithium deposition (initial state)

[0068] 32': Spacer for lithium deposition (fully charged)

[0069] 32``: Spacer for lithium deposition (fully discharged state)

[0070] 40: Negative electrode current collector

[0071] d1: Thickness (intermediate layer; initial state)

[0072] d2: Thickness (intermediate layer; fully charged state)

[0073] d1``: Thickness (intermediate layer; fully discharged state) Detailed Implementation

[0074] The present invention will now be described in more detail to aid in understanding. In this description and claims, the terms and phrases used should not be limited to their conventional or dictionary meanings, but rather interpreted based on the principle that the inventor can appropriately define the concepts of the terms to best describe their invention, in accordance with the meaning and concept of the technical idea of ​​the present invention.

[0075] The terminology used in this specification is for illustrative purposes only and is not intended to limit the invention. Unless the context clearly indicates otherwise, singular expressions include plural expressions.

[0076] In this specification, it should be understood that terms such as “comprising,” “including,” “possessing,” or “having” specify the presence of the implemented features, figures, steps, constituent elements, or combinations thereof, without precluding the possibility of the presence or addition of one or more other features, figures, steps, constituent elements, or combinations thereof.

[0077] <Neutral-free all-solid-state battery>

[0078] The present invention provides a negative electrode-free all-solid-state battery including electrodes for a negative electrode-free all-solid-state battery.

[0079] According to one embodiment of the present invention, a negative electrode-free all-solid-state battery includes at least: a negative electrode current collector 40; an intermediate layer 30 disposed on the negative electrode current collector and comprising a carbon structure; a solid electrolyte layer 20 disposed on the intermediate layer; a positive electrode active material layer 12 disposed on the solid electrolyte layer and comprising a positive electrode active material; and a positive electrode current collector 11 disposed on the positive electrode active material layer, wherein the carbon structure comprises: a plurality of substrates 31; and a spacer space, the substrates being spaced apart to form the spacer space, wherein the spacer space includes a lithium deposition spacer space having a width of 0.3 nm or more and 10 nm or less, and the diameter (D) corresponding to 50% of the cumulative volume in the cumulative volume distribution of the substrates. 50 The size is between 5μm and 12μm.

[0080] Typically, an all-solid-state battery includes a positive electrode active material layer bonded to a positive electrode current collector, a negative electrode active material layer bonded to a negative electrode current collector, and a solid electrolyte layer disposed between the positive and negative electrode active material layers. However, in addition to negative electrode active materials such as graphite, the negative electrode active material layer also contains a solid electrolyte for lithium-ion migration, and the specific gravity of the solid electrolyte is greater than that of the liquid electrolyte. Therefore, the energy density of an all-solid-state battery is lower than that of a lithium-ion battery using a liquid electrolyte.

[0081] In recent years, in order to improve the energy density of all-solid-state batteries, research is actively underway on storage-type all-solid-state batteries that omit the negative electrode active material layer and allow lithium ions to be directly deposited on the negative electrode current collector in the form of lithium metal.

[0082] In existing electrodeless all-solid-state batteries, a carbon-containing intermediate layer is placed between the solid electrolyte layer and the negative electrode current collector to ensure uniform lithium deposition and precipitation. During charging of the electrodeless all-solid-state battery, lithium ions (Li...) at the positive electrode... + The lithium ions (Li) reach the intermediate layer through the solid electrolyte layer. + After reacting with and migrating with carbon materials, lithium ions are deposited between the negative electrode current collector and the intermediate layer. However, when conventional graphite is included as the carbon material in the intermediate layer of an all-solid-state battery without a negative electrode, the following problems arise: active lithium is consumed due to uncontrolled growth of lithium dendrites and side reactions, and due to the crystallinity of graphite, lithium ions are deposited between the solid electrolyte layer and the intermediate layer, causing internal short circuits and thus shortening battery life.

[0083] According to one embodiment of the present invention, the intermediate layer of an all-solid-state battery without a negative electrode includes a spacer space 32 for lithium deposition, and includes a diameter (D) corresponding to 50% of the cumulative volume in the volume accumulation distribution. 50 The substrate, with a thickness of 5 μm or more and 12 μm or less, is used as the substrate for forming the spacer space 32 for lithium deposition. Therefore, when a negative electrode-less all-solid-state battery is charged and lithium deposition occurs, lithium can be deposited inside the intermediate layer, rather than as an extra layer between the solid electrolyte layer and the intermediate layer. This prevents internal short circuits caused by the formation of an extra lithium deposition layer between the solid electrolyte layer and the intermediate layer, thereby improving the battery's lifespan characteristics.

[0084] See below. Figure 1 The various components forming an all-solid-state battery without a negative electrode according to one embodiment of the present invention will be specifically described. Figure 1 The diagram illustrates the structure of a negative electrode-free all-solid-state battery according to an embodiment of the present invention, under operating conditions. Figure 1The diagram shows a negative electrode-free all-solid-state battery 1 in its initial state (i.e., fully discharged before the first charge), a negative electrode-free all-solid-state battery 1' in its fully charged state, and a negative electrode-free all-solid-state battery 1'' in its fully discharged state after being fully charged. Hereinafter, in the description of the various configurations of a negative electrode-free all-solid-state battery according to an embodiment of the present invention, unless otherwise specified, the description will be based on the negative electrode-free all-solid-state battery 1 in its initial state.

[0085] 1. Electrodes for all-solid-state batteries without negative electrodes

[0086] According to one embodiment of the present invention, a cathode-free all-solid-state battery may include an electrode for a cathode-free all-solid-state battery. The electrode for a cathode-free all-solid-state battery includes 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 substrates; and spacers, the substrates being spaced apart to form the spacers, wherein the spacers include lithium deposition spacers having a width of 0.3 nm or more and 10 nm or less, and the diameter (D) corresponding to 50% of the cumulative volume distribution of the substrates is... 50 The size is between 5μm and 12μm.

[0087] According to one embodiment of the present invention, the electrode for the electrode of the electrodeless all-solid-state battery is an electrode that omits the negative electrode active material layer and allows lithium ions to be directly deposited on the current collector in the form of lithium metal, etc. The electrode for the electrodeless all-solid-state battery can substantially function as a negative electrode in the electrodeless all-solid-state battery. Therefore, the current collector included in the electrode for the electrode of the electrodeless all-solid-state battery will be referred to as the negative electrode current collector 40 below.

[0088] Negative current collector

[0089] According to one embodiment of the present invention, the negative electrode current collector 40 is a conductive sheet-like substrate, which 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 does not cause chemical changes in the relevant battery and is conductive. The negative electrode current collector 40 may be one or more selected from aluminum (Al), nickel (Ni), titanium (Ti), tungsten (W), iron (Fe), chromium (Cr), stainless steel, or alloys thereof.

[0090] Intermediate layer

[0091] According to one embodiment of the present invention, the intermediate layer 30 is directly disposed on the negative electrode current collector 40. When lithium ions are deposited on the surface of the negative electrode current collector in the form of lithium metal, the intermediate layer 30 can induce lithium metal to be deposited in the horizontal direction along the surface of the negative electrode current collector 40.

[0092] According to one embodiment of the present invention, the intermediate layer 30 may include a carbon structure comprising a plurality of substrates 31 and a lithium deposition spacer 32, wherein the plurality of substrates 31 are spaced apart from each other to form the lithium deposition spacer 32, and the lithium deposition spacer 32 has a width of more than 0.3 nm and less than 10 nm.

[0093] According to one embodiment of the present invention, the diameter (D) corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix, as measured by a laser diffraction particle size analyzer, is... 50 The thickness can be 5 μm or more and 12 μm or less. Specific examples include 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 can be 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. When the above ranges are met, the following lithium deposition mechanism can be easily performed, allowing lithium to be deposited smoothly inside the carbon structure. When the D of the substrate 31... 50 When the above range is exceeded, the spacer space 32 for lithium deposition formed by the matrix within the carbon structure will decrease, making the following lithium deposition mechanism difficult to perform, and thus lithium may be difficult to deposit inside the carbon structure. Furthermore, when the D of the matrix 31... 50 When the value is less than the above range, the internal crystal structure of the substrate 31 may change, making it difficult for lithium to be deposited inside the carbon structure.

[0094] According to one embodiment of the present invention, the diameter (D) corresponding to 10% of the cumulative volume in the cumulative volume distribution of the matrix, measured using a laser diffraction particle size analyzer, is... 10 The thickness can be greater than 1.5 μm and less than 4.5 μm. Specific examples include thicknesses of 1.6 μm or greater, 1.7 μm or greater, 1.8 μm or greater, 1.9 μm or greater, or 2 μm or greater, and can be less than 4.4 μm, 4.3 μm or less, 4.2 μm or less, 4.1 μm or less. When these ranges are met, the following lithium deposition mechanism can be performed more easily.

[0095] According to one embodiment of the present invention, the diameter (D) corresponding to 90% of the cumulative volume in the cumulative volume distribution of the matrix, measured using a laser diffraction particle size analyzer, is... 90 The thickness can be 13 μm or larger and 25 μm or smaller. Specific examples include 13.5 μm or larger, 14 μm or larger, 14.5 μm or larger, 15 μm or larger, 15.5 μm or larger, or 16 μm or larger, and can be 24.5 μm or smaller, 24 μm or smaller, 23.5 μm or smaller, 23 μm or smaller, 22.5 μm or smaller. When the above ranges are met, the following lithium deposition mechanism can be performed more easily.

[0096] According to one embodiment of the present invention, the span value of the substrate 31 according to the following mathematical formula 1 can be 1.9 or less.

[0097] [Mathematical Expression 1]

[0098]

[0099] In the mathematical formula 1, D 10 D is the diameter corresponding to 10% of the cumulative volume in the cumulative volume distribution of the matrix. 50 D is the diameter corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix. 90 It is the diameter corresponding to 90% of the cumulative volume in the cumulative volume distribution of the matrix.

[0100] According to one embodiment of the present invention, as a specific example, the span value represented by the mathematical formula 1 can be 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 can be 1.85 or less, 1.8 or less, 1.75 or less, 1.7 or less, or 1.65 or less. When the above ranges are met, the following lithium deposition mechanism can be performed more easily.

[0101] According to one embodiment of the present invention, the substrate 31 may be plate-shaped particles. In the present invention, "plate-shaped" is understood to include not only planar shapes with a uniform thickness profile, but also the concept of a curved shape that is considered to be a planar folded and bent shape with a uniform thickness profile.

[0102] According to one embodiment of the present invention, the particle size of the substrate 31 in the thickness direction, i.e., in the (002) direction, can be 5 nm or more and 30 nm or less. Specific examples include 6 nm or more, 8 nm or more, 10 nm or more, 12 nm or more, or 15 nm or more, and can be 28 nm or less, 26 nm or less, 24 nm or less, 22 nm or less, or 20 nm or less. When the above ranges are met, the following lithium deposition mechanism can be performed more easily, thereby allowing lithium to be deposited smoothly inside the carbon structure.

[0103] According to one embodiment of the present invention, the substrate 31 can be a graphene platelet formed by disordered stacking of graphene or a layered carbon formed by combining graphene.

[0104] According to one embodiment of the present invention, a plurality of substrates 31 may be stacked and spaced apart from each other in the stacking direction to form a spacer space. Specifically, the plurality of substrates 31 may be wholly or partially spaced apart from each other to form a spacer space, the spacer space including a lithium deposition spacer space 32 having a width of more than 0.3 nm and less than 10 nm.

[0105] According to one embodiment of the present invention, the proportion of the number of lithium deposition spacers 32 relative to the total number of said spacers can be 45% or more, and as specific examples, it can 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 met, lithium ions can be deposited more easily in the intermediate layer 30.

[0106] See Figure 1 According to one embodiment of the present invention, the width of the lithium deposition spacer 32 is significantly narrower than the pore width of conventional porous graphite structures. The lithium deposition spacer 32 can have a width of 0.3 nm or more and 10 nm or less in the stacking direction. Specific examples include widths 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 widths 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 ranges are met, during charging of the electrodeless all-solid-state battery, lithium ions can be completely deposited inside the intermediate layer 30 without depositing between the solid electrolyte layer 20 and the intermediate layer 30, and lithium dendrites will not form. When the width of the lithium deposition space 32 is less than the above range, lithium ions cannot be deposited in the lithium deposition space 32 because its width is smaller than the radius of conventional metal ions. When the width of the lithium deposition space 32 exceeds the above range, lithium ions may pass through directly without being deposited and may be deposited between the solid electrolyte layer 20 and the intermediate layer 30, which may lead to an internal short circuit.

[0107] According to one embodiment of the present invention, when performing XRD analysis on the carbon structure, the full width at half maximum (FWHM, 2θ) of the (002) peak can be 0.3° or greater and 0.8° or less. Specifically, it can be 0.32° or greater, 0.34° or greater, 0.36° or greater, 0.38° or greater, or 0.4° or greater, and can 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 ranges are met, the ratio of the width to the number of lithium deposition spacers 32 in the carbon structure can satisfy the above ranges, thereby allowing lithium to be easily deposited inside the carbon structure.

[0108] According to one embodiment of the present invention, when Raman spectroscopy is performed on the carbon structure, a peak is observed in the spectrum within the Raman shift range of 2600 / cm to 2800 / cm. After fitting the spectrum using a single Voigt profile to define a fitting curve, the coefficient of determination (R²) of the fitting curve of the spectrum is... 2 It can be above 0.985.

[0109] According to one embodiment of the present invention, the coefficient of determination (R²) of the fitted curve of the spectrum is... 2 The value can 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. When a peak is observed in the spectrum within the Raman shift range of 2600 / cm or higher and 2800 / cm or lower, and the spectrum satisfies the above-mentioned range, a lithium deposition space 32 with a width within the above-mentioned range can be formed in the carbon structure.

[0110] According to one embodiment of the invention, the intermediate layer 30 may further comprise a conductive material, a solid electrolyte, and / or an adhesive.

[0111] According to one embodiment of the present invention, the conductive material can further improve the conductivity of the intermediate layer 30. The conductive material is not particularly limited, as long as it does not cause chemical changes in the relevant battery and has conductivity. For example, the conductive material can be graphite; carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal cracking black, SC65, and other carbon-based materials; conductive fibers such as carbon fibers or metal fibers; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives, etc.

[0112] According to one embodiment of the present invention, the adhesive can promote the bonding between the conductive material and the carbon structure. The adhesive can be polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, nitrile rubber, fluororubber, and various copolymers thereof.

[0113] According to one embodiment of the present invention, the intermediate layer 30 may comprise 85% by weight and 97.5% by weight of the carbon structure. Specifically, it may comprise 86% by weight or more, 87% by weight or more, 88% by weight or more, 89% by weight or more, or 90% by weight of the carbon structure, and may comprise less than 97% by weight, less than 96.5% by weight, less than 96% by weight, less than 95.5% by weight, less than 95% by weight, or less than 94.5% by weight of the carbon structure. When the above ranges are met, lithium ions can be deposited more easily within the intermediate layer 30.

[0114] According to one embodiment of the present invention, the intermediate layer 30 may include 0.8 g / cm³. 3 Above and 2.0 g / cm 3 The carbon structural bodies described below, as specific examples, may include 0.85 g / cm³. 3 Above, 0.9g / cm 3 Above, 0.95g / cm 3 Above, 1.0g / cm 3 Above, 1.1g / cm 3 Above or 1.2g / cm 3 The carbon structure described above may include 1.9 g / cm³. 3 Below, 1.8g / cm 3 Below, 1.7g / cm 3 Below, 1.6g / cm 3 Below, 1.5g / cm 3 Below or 1.4g / cm 3 The carbon structure described below. When the above range is met, lithium ions can be deposited more easily within the intermediate layer 30.

[0115] According to one embodiment of the present invention, the electrodeless all-solid-state battery includes an intermediate layer 30 formed of a carbon structure. The carbon structure includes a plurality of substrates and lithium deposition spacers, the plurality of substrates being spaced apart to form the lithium deposition spacers. The lithium deposition spacers have a width of 0.3 nm or more and 10 nm or less. Therefore, when the electrodeless all-solid-state battery is charged, lithium ions can be deposited within the lithium deposition spacers 32 inside the intermediate layer 30, and no additional lithium deposition layer needs to be formed between the intermediate layer 30 and the solid electrolyte layer 20. Thus, direct contact between the solid electrolyte layer 20 and the deposited lithium can be prevented, thereby preventing internal short circuits.

[0116] The thickness of the intermediate layer 30 in a cathode-free all-solid-state battery according to one embodiment of the present invention can vary according to the operating state of the cathode-free all-solid-state battery. Specifically, the thickness of the intermediate layer 30 can be increased when the cathode-free all-solid-state battery is charged, and the thickness of the intermediate layer 30 can be decreased when the cathode-free all-solid-state battery is discharged. See also Figure 1 The diagram shows an electrodeless all-solid-state battery 1 in its initial state (i.e., fully discharged before the first charge), an electrodeless all-solid-state battery 1' in its fully charged state, and an electrodeless all-solid-state battery 1'' in its fully discharged state after being fully charged. The lithium deposition mechanism of an electrodeless all-solid-state battery according to one embodiment of the present invention will be described in detail below.

[0117] According to one embodiment of the present invention, LiC6 can be formed in the substrate 31' of the fully charged electrodeless solid-state battery 1' through reaction with lithium ions, and thus the substrate 31 can be in a state with increased volume compared to the pre-charging state.

[0118] According to one embodiment of the present invention, the width of the fully charged substrate 31' in the thickness direction, i.e., the particle size in the (002) direction, can be 7 nm or more and 41 nm or less. As a specific example, it can be 8 nm or more, 9 nm or more, 10 nm or more, 12 nm or more or 15 nm or more, and can 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.

[0119] According to one embodiment of the present invention, the LiC6 formed in the fully charged substrate 31' can provide a path for lithium ions to migrate to the lithium deposition space 32', whereby the lithium ions can be deposited in the lithium deposition space 32' in the form of lithium metal and form lithium deposit 33'.

[0120] According to one embodiment of the present invention, a lithium deposit 33' can be formed in the lithium deposition space 32' of the fully charged negative electrode-free all-solid-state battery 1'. When XRD analysis is performed on the intermediate layer 30' including the lithium deposit 33', the ratio of the intensity of the Li(110) peak to the intensity of the LiC6(001) peak can be 0.5 or more. As a specific example, it can be 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1 or more.

[0121] According to one embodiment of the present invention, the width of the lithium deposition space 32' in the fully charged state can be greater than the width of the lithium deposition space 32 in the initial state due to the lithium deposits 33' formed inside it. This is because when the electrodeless all-solid-state battery 1 in the initial state is charged, lithium ions are deposited in the lithium deposition space 32 and form lithium deposits. As the lithium deposits grow, they push upwards to form the substrate 31 of the lithium deposition space 32, thereby increasing the width of the lithium deposition space 32.

[0122] According to one embodiment of the present invention, the lithium deposition space 32' of the fully charged negative electrode-free all-solid-state battery 1' can have a width of 3 nm or more and 20 nm or less in the stacking direction. As specific examples, it can 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 can 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.

[0123] See Figure 1 As described above, when the initial state of the electrodeless solid-state battery 1 is transformed into a fully charged state of the electrodeless solid-state battery 1', the volume of the fully charged substrate 31' increases compared to the initial state of the substrate 31, and the width of the lithium deposition space 32' increases compared to the initial state of the lithium deposition space 32. Therefore, the thickness d2 of the intermediate layer 30' of the fully charged electrodeless solid-state battery 1' can be greater than the thickness d1 of the intermediate layer 30 of the initial state of the electrodeless solid-state battery 1.

[0124] According to one embodiment of the present invention, when the electrodeless all-solid-state battery is in its initial state (i.e., fully discharged before the first charge), the thickness d1 of the intermediate layer 30 can be 5 μm or more and 20 μm or less. Specific examples include 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 can 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 ranges are met, lithium can be deposited more easily inside the intermediate layer 30, and the energy density of the battery can be further improved.

[0125] According to one embodiment of the present invention, the thickness d2 of the intermediate layer 30' of the fully charged negative electrode-free all-solid-state battery 1' can be 10 μm or more and 50 μm or less. As specific examples, it can be 12 μm or more, 14 μm or more, 16 μm or more, 18 μm or more or 20 μm or more, and can be 45 μm or less, 40 μm or less, 35 μm or less or 30 μm or less.

[0126] According to one embodiment of the present invention, the ratio of thickness d2 to thickness d1 (d2 / d1) can be 2 or more. As specific examples, it can be 2.2 or more, 2.4 or more, 2.6 or more, 2.8 or more, or 3 or more.

[0127] According to one embodiment of the present invention, when the fully charged electrodeless solid-state battery 1' is transformed into a fully discharged electrodeless solid-state battery 1'', lithium ions will desorb from the intermediate layer 30'. Therefore, the intermediate layer 30' of the fully discharged electrodeless solid-state battery 1'' can be in a state similar to that of the initial electrodeless solid-state battery 1'. Specifically, the thickness d1' of the intermediate layer 30'' in the fully discharged state after being fully charged can be substantially the same as the thickness d1 of the intermediate layer 30 in the initial state.

[0128] According to one embodiment of the present invention, the particle size of the substrate 31'' in the fully discharged state after being fully charged can be larger than the particle size of the substrate 31 in the initial state, and can be smaller than the particle size of the substrate 31' in the fully charged state.

[0129] According to one embodiment of the present invention, the width of the substrate 31'' in the thickness direction, i.e. the particle size in the (002) direction, in the fully discharged state can be 6 nm or more and 31 nm or less. As a specific example, it can be 7 nm or more, 8 nm or more, 10 nm or more, 12 nm or more or 15 nm or more, and can be 30 nm or less, 28 nm or less, 26 nm or less, 24 nm or less or 22 nm or less.

[0130] Therefore, according to one embodiment of the present invention, the width of the lithium deposition space 32'' in the fully discharged state after being fully charged can be smaller than the width of the lithium deposition space 32 in the initial state. Specifically, the lithium deposition space 32'' in the fully discharged state after being fully charged can have a width of 0.3 nm or more and 8 nm or less in the stacking direction. As specific examples, it can 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 can 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. When the above range is met, since the particle size of the substrate 31'' in the fully discharged state after being fully charged is larger than the particle size of the substrate 31 in the initial state, even if the width of the lithium deposition space 32'' in the fully discharged state after being fully charged is smaller than the width of the lithium deposition space 32 in the initial state, lithium ions can be completely deposited inside the intermediate layer 30, and will not be deposited between the solid electrolyte layer 20 and the intermediate layer 30, and lithium dendrites will not form.

[0131] In a negative electrode-free all-solid-state battery according to one embodiment of the present invention, a carbon structure having the structure described above is used as the intermediate layer 30. Therefore, when the negative electrode-free all-solid-state battery is charged, lithium ions can be completely deposited inside the intermediate layer 30 without being deposited between the solid electrolyte layer 20 and the intermediate layer 30, and lithium dendrites will not form.

[0132] According to one embodiment of the present invention, the method for manufacturing the electrode for the negative electrode-free all-solid-state battery includes at least the following steps: (S1) applying energy to a mixture containing dissolved carbon material and polymer binder to separate the matrix within the carbon material and rearrange it through self-assembly; and (S2) ball milling the product of step (S1) for more than 55 minutes and less than 150 minutes to manufacture a carbon structure.

[0133] Specifically, step (S1) can be a step of applying energy to a mixture containing dissolved carbon material (i.e., graphite) to cause the matrix (i.e., graphene) within the graphite to separate and rearrange itself through self-assembly.

[0134] According to one embodiment of the present invention, the mixture may further contain a polymer binder, and the polymer binder is removed by the energy, thereby forming the aforementioned plurality of spacers at the original location of the polymer binder. The spacers having a width in the thickness direction of 0.3 nm or more and 10 nm or less can be defined as lithium deposition spacers.

[0135] Specifically, the graphite is a porous carbon material. When a polymer binder is added to the graphite and energy is applied, the graphite is compressed, which reduces the size and number of the pores, allowing the remaining pores to be filled by the polymer binder. Subsequently, when the polymer binder is removed by the energy, the remaining pores become spacers, thereby forming the carbon structure. The spacers having a width in the thickness direction of 0.3 nm or more and 10 nm or less are defined as lithium deposition spacers.

[0136] According to one embodiment of the present invention, the energy can be applied by various methods such as heat treatment, light irradiation, and ultrasonic treatment; preferably, it can be applied by heat treatment.

[0137] According to one embodiment of the present invention, after the polymer adhesive is removed, some of the polymer adhesive may remain on the surface of the substrate.

[0138] According to one embodiment of the present invention, the polymer adhesive may include a polymer adhesive selected from polyester, vinyl polyvinyl acetate, polyester-vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyolefin, vinyl acetate, polyethylene terephthalate, polystyrene, polyvinyl ketone, polyethylene terephthalate-ethylene glycol, polyethyleneimine, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyimide, polyamide-imide, polyacrylic acid, polyvinyl alcohol, styrene-butadiene rubber-based polymer, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, acrylate-based rubber, hydroxypropyl methylcellulose, carboxymethyl cellulose (CMC), and composite polymers formed by mixing one or more of these.

[0139] According to one embodiment of the invention, during the fabrication of the carbon structure, a lithium-ion polymer binder may remain on the substrate due to its use. In this case, lithium ions can be attracted during lithium deposition, thus allowing for the uniform and stable deposition of lithium ions with high capacity.

[0140] According to one embodiment of the present invention, in step (S2), the carbon structure having a preferred range of matrix particle size distribution can be manufactured by ball-milling the product of step (S1) for 55 minutes or more and 150 minutes or less. As a specific example, the ball-milling can 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 can 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 met, the diameter (D) corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix included in the carbon structure is... 50 The depth can be adjusted to a level between 5μm and 12μm, which makes the above-mentioned lithium deposition mechanism easy to perform, thus allowing lithium to be deposited smoothly inside the carbon structure.

[0141] 2. Solid electrolyte layer

[0142] An all-solid-state battery according to one embodiment of the present invention may include a solid electrolyte layer 20. The solid electrolyte layer 20 may be disposed between the positive electrode active material layer 12 and the intermediate layer 30 to facilitate the transport of lithium ions between the positive electrode active material layer 12 and the negative electrode current collector 40.

[0143] According to one embodiment of the present invention, the solid electrolyte layer 20 may be disposed on the intermediate layer 30 and may contain a solid electrolyte having lithium-ion conductivity. The solid electrolyte may include at least one selected from oxide-based solid electrolytes, sulfide-based solid electrolytes, polymer electrolytes, and combinations thereof, preferably including a sulfide-based solid electrolyte.

[0144] According to one embodiment of the present invention, the sulfide-based solid electrolyte may include Li6PS5X (where X is one or more selected from 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, L i2SSiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m Sn (where m and n are positive numbers, and Z is one of Ge, Zn, 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 more than one of their combinations.

[0145] 3. Positive electrode

[0146] The positive electrode according to an embodiment of the present invention may include a positive electrode active material layer 12 and a positive electrode current collector 11.

[0147] Positive electrode active material layer

[0148] According to an embodiment of the present invention, the positive electrode active material layer 12 may contain a positive electrode active material, a conductive material, and an adhesive.

[0149] According to an embodiment of the present invention, the positive electrode active material is a substance that can reversibly intercalate and deintercalate lithium ions (Li + ), and the positive electrode active material may include a composite oxide of lithium and a metal, that is, a lithium composite metal oxide. As specific examples, the lithium composite metal oxide may include lithium - manganese - based oxides (e.g., LiMnO2, LiMn2O4, etc.), lithium - cobalt - based oxides (e.g., LiCoO2, etc.), lithium - nickel - based oxides (e.g., LiNiO2, etc.), lithium - nickel - manganese - based oxides (e.g., LiNi 1-Y Mn Y O2 (where 0 < Y < 1), LiMn 2-z Ni z O4 (where 0 < Z < 2), etc.), lithium - nickel - cobalt - based oxides (e.g., LiNi 1-Y1 Co Y1 O2 (where 0 < Y1 < 1), etc.), lithium - manganese - cobalt - based oxides (e.g., LiCo 1-Y2 Mn Y2 O2 (where 0 < Y2 < 1), LiMn 2-z1 Co z1 O4 (where 0 < Z1 < 2), etc.), lithium - nickel - manganese - cobalt - based 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 r2O4 (where 0 < p1 < 2, 0 < q1 < 2, 0 < r2 < 2, p1 + q1 + r2 = 2, etc.) or lithium-nickel-cobalt-transition metal (M) oxides (e.g., Li(Ni) p2 Co q2 Mn r3 M s2 O2 (where M is selected from Al, Fe, V, Cr, Ti, Ta, Mg and Mo, p2, q2, r3 and s2 are each atomic fractions of independent elements, and 0 < p2 < 1, 0 < q2 < 1, 0 < r3 < 1, 0 < s2 < 1, p2 + q2 + r3 + s2 = 1) etc., and may include any one or more of these compounds.

[0150] From the perspective of improving the capacity characteristics and stability of the battery, the lithium composite metal oxide can be LiCoO2, LiMnO2, LiNiO2, or lithium nickel manganese cobalt oxide (e.g., Li(Ni)O2). 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 When considering the significant improvement effect brought about by controlling the types and content ratios of constituent elements in the formation of lithium composite metal oxides, the lithium composite metal oxide can be Li(Ni)O2, etc. 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., and any one or a mixture of two or more of them can be used.

[0151] According to one embodiment of the present invention, the positive electrode active material may further include a coating comprising boron (B) or LiNbO and encapsulating the lithium composite metal oxide. By further including the coating, the structural stability of the positive electrode active material can be improved.

[0152] Furthermore, according to one embodiment of the present invention, the positive electrode active material layer 12 may further comprise a solid electrolyte. The solid electrolyte may coat the positive electrode active material. Therefore, the compatibility between the positive electrode active material layer 12 and the solid electrolyte layer 20 can be improved. The detailed description of the solid electrolyte is the same as that of the solid electrolyte layer 20, and therefore its detailed description is omitted below.

[0153] According to one embodiment of the present invention, the conductive material can further improve the conductivity of the positive electrode active material. The conductive material is not particularly limited, as long as it does not cause chemical changes in the relevant battery and has conductivity. For example, the conductive material can be graphite; carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, thermal cracking black, SC65, and other carbon-based materials; conductive fibers such as carbon fibers or metal fibers; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives, etc.

[0154] According to one embodiment of the present invention, the adhesive can promote the bonding between the conductive material, the positive electrode active material, and the positive electrode current collector. The adhesive can be polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene monomer, sulfonated ethylene-propylene-diene monomer, styrene-butadiene rubber, nitrile rubber, fluororubber, and various copolymers thereof.

[0155] Positive current collector

[0156] According to one embodiment of the present invention, the positive electrode current collector 11 is not particularly limited, as long as it does not cause chemical changes in the relevant battery and is conductive. The positive electrode current collector 11 can be one or more selected from aluminum (Al), nickel (Ni), titanium (Ti), tungsten (W), iron (Fe), chromium (Cr), stainless steel or alloys thereof.

[0157] The embodiments of the present invention will be described in detail below so that those skilled in the art can easily implement them. However, the present invention can be implemented in various different forms and is not limited to the embodiments described herein.

[0158] Example 1

[0159] 1000 mg of graphene was added to a reactor containing 20 ml of acetone and dispersed. Then, 20 g of a binder (manufactured by Loctite, product name: loctite401) was added and stirred. The reactor was then placed in a vacuum oven and dried at 60°C for 3 hours, followed by ball milling for 105 minutes. The pulverized product was then subjected to heat treatment via chemical vapor deposition (CVD) at 120°C for 10 minutes, 400°C for 10 minutes, and 800°C for 5 minutes. The heat-treated product was then sieved through a 400-mesh (37 μm) sieve to obtain carbon structure powder.

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

[0161] Comparative Example 1

[0162] A slurry was prepared by dispersing 92.5 mg of graphite powder, 2.5 mg of conductive material (Super P), and 5 mg of binder (PVDF) in 300 μL of N-methyl-2-pyrrolidone (NMP) solvent. Then, a negative electrode current collector made of 10 μm thick nickel foil 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 a graphite-free all-solid-state battery.

[0163] Comparative Example 2

[0164] 1000 mg of graphene was added to a reactor containing 20 ml of acetone and dispersed. Then, 20 g of a binder (manufactured by Loctite, product name: loctite401) was added and stirred. The reactor was then placed in a vacuum oven and dried at 60°C for 3 hours, followed by ball milling for 5 minutes. The pulverized product was then subjected to CVD heat treatment, sequentially held 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) sieve to obtain carbon structure powder.

[0165] A slurry was prepared by dispersing 92.5 mg of the carbon structure powder prepared above, 2.5 mg of conductive material (Super P, MTI), and 5 mg of binder (PVDF, Sigma-Aldrich) in 300 μL of N-methyl-2-pyrrolidone (NMP, Sigma-Aldrich). A negative electrode current collector made of a 10 μm thick nickel foil was then prepared, and the prepared slurry was uniformly coated onto the surface of the current collector using a doctor blade. The coated current collector was then placed in a vacuum oven and dried at 60°C for at least 12 hours to produce an electrode for a negative electrodeless all-solid-state battery with a carbon structure layer formed on it.

[0166] Experimental Example 1

[0167] Manufacturing of Electrodeless All-Solid-State Batteries

[0168] For the electrode for the negative electrode-less all-solid-state battery manufactured in Example 1, 150 mg to 200 mg of sulfide-based solid electrolyte (Li6PS5Cl) is filled into a ring mold with a diameter of 13 mm. 0.5 Br 0.5 The powder is pressurized at 400 MPa to form a solid electrolyte layer, and then pressurized at 100 MPa to form an intermediate layer with a thickness of 10 μm between the solid electrolyte layer and the negative electrode current collector.

[0169] Subsequently, 20 mg of a mixed powder (composed of positive electrode active material (LiNi)) was placed on the opposite side of the solid electrolyte layer. 0.8 Co 0.1 Mn 0.1 O2: Solid electrolyte (Li6PS5Cl) 0.5 Br 0.5 The binder (PVDF) is mixed in a ratio of 70:30:3 and pressed at 200MPa to form a positive electrode active material layer. A positive electrode current collector made of Al with a thickness of 10μm is placed on the positive electrode active material layer and pressed at 380MPa to manufacture a negative electrode-free all-solid-state battery.

[0170] <Observations on changes in the intermediate layer during charging>

[0171] Figure 2 The image shows SEM images and EDS mappings of the electrodeless all-solid-state battery cross-sections according to Example 1 in the following four states, obtained by SEM-EDS: i) state before lithium deposition, ii) 0.5 mAh / cm². 2 The state of lithium deposition in the intermediate layer, iii) 1.0 mAh / cm 2 The state of lithium deposition in the intermediate layer and iv) 2.0 mAh / cm 2 The lithium is deposited in the intermediate layer. The SEM equipment used was the Thermofisher Apreo 2S, and the SEM-EDS equipment used was the Thermofisher ChemiSEM.

[0172] See Figure 2 It can be confirmed that the thickness of the intermediate layer containing layered carbon material gradually increases during battery charging. Furthermore, in Figure 2 Oxygen was observed in the cross-section of the intermediate layer, which is because lithium was exposed to air and oxidized during the measurement process. This indicates that lithium is deposited inside the intermediate layer, rather than precipitated as an extra layer between the intermediate layer and the solid electrolyte layer.

[0173] <Observation of the matrix structure>

[0174] Figure 3 The following SEM images of the substrate are shown: SEM images of the substrate obtained by separating the intermediate layer without applying current to the electrodeless all-solid-state battery according to Example 1, and taking the images of the opposite side of the contact surface between the intermediate layer and the solid electrolyte layer using a scanning electron microscope (Thermo Fisher Scientific Apreo 2S); and a deposition capacity of 3.5 mAh / cm³ in the intermediate layer of the electrodeless all-solid-state battery according to Example 1. 2 After lithium removal, the intermediate layer was separated, and SEM images of the substrate were obtained by taking pictures of the opposite side of the contact surface between the intermediate layer and the solid electrolyte layer using a scanning electron microscope (Thermo Fisher Scientific Apreo 2S).

[0175] Furthermore, the intermediate layer was separated from the all-solid-state battery without a negative electrode according to Example 1 without applying a separate current, and XPS analysis was performed on the opposite surface of the contact surface between the intermediate layer and the solid electrolyte layer to obtain C1s and O1s spectra. The obtained C1s and O1s spectra were plotted on... Figure 4 Furthermore, the deposition capacity in the intermediate layer of the negative electrode-free all-solid-state battery according to Example 1 is 2.0 mAh / cm³.2 After lithium removal, the intermediate layer was separated, and XPS analysis was performed on the interface between the intermediate layer and the solid electrolyte layer to obtain C1s, O1s, and Li1s spectra. The obtained C1s, O1s, and Li1s spectra were plotted on... Figure 5 The XPS analysis was performed using a spectrometer (Thermo Fisher Scientific, K-α+ (K-Alpha+), accelerating voltage: 100 eV to 4000 eV, maximum resolution: 0.50 eV).

[0176] See Figure 3 It can be confirmed that during charging, the matrix contained in the layered carbon material forming the intermediate layer of Example 1 expanded. See also Figure 4 and Figure 5 It can be confirmed that when the matrix contained in the layered carbon material forming the intermediate layer of Example 1 expands, LiC6 is formed in the matrix.

[0177] <Observation of the structure of the space between the matrix>

[0178] After fully charging the electrodeless all-solid-state battery according to Example 1, the intermediate layer was separated. STEM images of the separated intermediate layer were obtained using a STEM apparatus (Titan cubed G2) at an accelerating voltage of 300 kV. The obtained STEM images are shown below. Figure 6 middle.

[0179] Experimental Example 2 - Comparison of Example 1 and Comparative Example 1

[0180] Manufacturing of Electrodeless All-Solid-State Batteries

[0181] For the electrodes of each negative electrode-less all-solid-state battery manufactured in Example 1 and Comparative Example 1, 150 mg to 200 mg of sulfide-based solid electrolyte (Li6PS5Cl) was filled into a ring mold with a diameter of 13 mm. 0.5 Br 0.5 The powder is pressurized at 400 MPa to form a solid electrolyte layer, and then pressurized at 100 MPa to form an intermediate layer with a thickness of 10 μm between the solid electrolyte layer and the negative electrode current collector.

[0182] Subsequently, 20 mg of a mixed powder (composed of positive electrode active material (LiNi)) was placed on the opposite side of the solid electrolyte layer. 0.8 Co 0.1 Mn 0.1 O2: Solid electrolyte (Li6PS5Cl) 0.5 Br 0.5The binder (PVDF) is mixed in a ratio of 70:30:3 and pressed at 200MPa to form a positive electrode active material layer. A positive electrode current collector made of Al with a thickness of 10μm is placed on the positive electrode active material layer and pressed at 380MPa to manufacture a negative electrode-free all-solid-state battery.

[0183] <Comparison of the Structures of Carbon Structures 1>

[0184] Raman spectra were obtained by measuring the intermediate layers of the electrodeless all-solid-state battery according to Example 1 and the electrodeless all-solid-state battery according to Comparative Example 1 using a Raman spectrometer (Nanobase XperRF, using a 532nm laser). The obtained Raman spectra are shown below. Figure 7 Furthermore, each 2D peak observed in the Raman shift range of 2600 / cm to 2800 / cm was fitted using a single Voigt function (point curve), and then the coefficient of determination (R²) was used to calculate the values. 2 ).

[0185] See Figure 7 Within the Raman shift range of 2600 / cm to 2800 / cm, a peak observed in Example 1 can be confirmed, with a coefficient of determination value (R0). 2 The coefficient of determination (R) was 0.99574, and it was confirmed that two peaks (2D1, 2D2) were observed in Comparative Example 1, indicating a high degree of certainty. 2 The value is 0.97825. Therefore, it can be confirmed that, unlike the intermediate layer of Comparative Example 1, the intermediate layer of Example 1 has a structure similar to that of graphene with a thin thickness.

[0186] <Comparison of the Structures of Carbon Structures 2>

[0187] Using a Miniflex (Rigaku Corporation), XRD patterns were measured on each intermediate layer of the electrodeless all-solid-state battery according to Example 1 and the electrodeless all-solid-state battery according to Comparative Example 1 under the conditions of 40 kV, 15 mA, CuKα, 2θ (Bragg angle) = 10° to 70°, and scan speed = 2° / 60 seconds. The obtained XRD patterns were plotted on... Figure 8 middle.

[0188] See Figure 8It can be confirmed that the full width at half maximum (FWHM) of the (002) peak observed around 24° to 30° using the measured XRD patterns yielded a result of 0.528° for Example 1 and 0.264° for Comparative Example 1. Therefore, it can be confirmed that, unlike the intermediate layer of Comparative Example 1, the intermediate layer of Example 1 has narrow gaps formed within it. This is presumably due to the space between the matrix components contained in the layered carbon material.

[0189] In addition, at 0.5 mA / cm 2 The current density deposited in each intermediate layer of the electrodeless all-solid-state battery according to Example 1 and the electrodeless all-solid-state battery according to Comparative Example 1 is 2.0 mAh / cm³. 2 The lithium was extracted, and then the intermediate layers were separated. Using a Miniflex (Rigaku Corporation) XRD pattern, the contact surfaces between the intermediate layers and the solid electrolyte layer were measured under the following conditions: voltage 40 kV, current 15 mA, CuKα, 2θ (Bragg angle) = 10° to 70°, and scan rate = 2° / 60 seconds. The obtained XRD patterns were plotted on... Figure 9 middle.

[0190] right Figure 9 The XRD patterns were analyzed. The intensity of the LiC6(001) peak of the electrodeless all-solid-state battery according to Example 1 was set to 1. The intensity of the Li(110) peak, graphite(001) peak, and LiC6(001) peak of the electrodeless all-solid-state battery according to Example 1 were also analyzed. x The relative intensities of the (x>6) peaks relative to the LiC6(001) peak intensity of the electrodeless all-solid-state battery according to Example 1 are listed in Table 1 below. Furthermore, the LiC6(001) peak intensity of the electrodeless all-solid-state battery according to Comparative Example 1 is set to 1, and the Li(110) peak, graphite(001) peak, and LiC6(001) peak intensity of the electrodeless all-solid-state battery according to Comparative Example 1 are also listed. x The relative intensities of the (x>6) peaks relative to the LiC6(001) peak intensity of the electrodeless all-solid-state battery according to Comparative Example 1 are recorded in Table 1 below.

[0191] [Table 1]

[0192] <![CDATA[LiC6(001)]]> Li(110) Graphite (001) <![CDATA[LiC x (x>6)]]> Example 1 1 1.02 0 0 Comparative Example 1 1 0.08 0.23 0.51

[0193] See Figure 9 As confirmed in Table 1, in the case of Example 1, no incompletely reacted carbon (LiC) was detected on XRD after lithium deposition. x In the case of Comparative Example 1, LiC was detected (x>6) and unreacted carbon (graphite (001)), but in the case of Comparative Example 1, LiC was detected. x(x>6) and unreacted carbon (graphite).

[0194] Furthermore, in the case of Example 1, it can be confirmed that although XRD measurements were performed on the opposite surfaces of the contact surfaces between the intermediate layer and the solid electrolyte layer, the relative intensity of the Li(110) peak was 1.02 relative to the LiC6(001) peak, thus confirming that lithium itself is deposited between the matrix inside the intermediate layer.

[0195] Evaluation of Lithium-ion Diffusion Behavior

[0196] For the electrodes of each negative electrode-less all-solid-state battery manufactured in Example 1 and Comparative Example 1, 150 mg to 200 mg of sulfide-based solid electrolyte (Li6PS5Cl) was filled into a ring mold with a diameter of 13 mm. 0.5 Br 0.5 The powder is pressurized at 400 MPa to form a solid electrolyte layer, and then pressurized at 100 MPa to form an intermediate layer with a thickness of 10 μm between the solid electrolyte layer and the negative electrode current collector.

[0197] Next, a lithium metal foil (Honjo Chemical Corp.) stamped to a diameter of 12 mm and a thickness of 200 μm is inserted into the opposite side of the solid electrolyte layer. Then, a T-shaped component acting as a cap is inserted and sealed along the vertical direction of the annular mold. Afterward, the annular mold is tightened using a pressure clamp with a torque of 3 Nm to fabricate the half-cell.

[0198] For each half-cell according to Example 1 and Comparative Example 1 (electrode loading of 0.9 mg / cm³), 2 The first discharge process was measured by galvanostatic intermittent titration technique (GITT) under the conditions of room temperature (25℃) and operating pressure of 30MPa, with a current of 17.5mA / g applied for 20 minutes and left to stand for 40 minutes. Figure 10 The figure shows the voltage change (ΔE) of the intermediate layer of each half-cell according to Example 1 and Comparative Example 1 during the period of time (hours) of current cessation according to GITT for the intermediate layer. s ) and the voltage change (ΔE) during the applied current t The square of the ratio ((ΔE) s / ΔE t ) 2 (The image is missing.)

[0199] See Figure 10 It can be confirmed that (ΔE) in Example 1 s / ΔEt ) 2 The value remains stable over time according to GITT, and the (ΔE) of Comparative Example 1 can be confirmed. s / ΔE t ) 2 The value decreases rapidly at 61 hours, 87 hours, 115 hours, and 137 hours. Therefore, it can be confirmed that when considering (ΔE) s / ΔE t ) 2 When the value is proportional to the diffusion coefficient, lithium ions diffuse more stably in Example 1, which contains layered carbon material, compared to Comparative Example 1 containing graphite.

[0200] <Evaluation of Cyclic Characteristics>

[0201] For each of the negative electrode-free all-solid-state batteries manufactured in Example 1 and Comparative Example 1 above, under the conditions of room temperature and 15 MPa, the current is 2.52 mA / cm. 2 The current density is charged to 4.2V and at 2.52mA / cm. 2 Discharge to 2.8V at a current density of 1 volt constitutes one cycle. Repeat the charge-discharge cycle until the 60th charge-discharge cycle is reached. th (cycle), plotting the capacity retention and coulombic efficiency measured in each cycle on... Figure 11 middle.

[0202] See Figure 11 It can be confirmed that the electrodeless all-solid-state battery of Comparative Example 1 experienced a short circuit and stopped operating during the 26th cycle, while the electrodeless all-solid-state battery of Example 1 could operate stably for more than 60 cycles. It is speculated that this is because, according to the lithium growth mechanism inside the intermediate layer, lithium is stably deposited inside the intermediate layer and does not grow in the form of dendrites, thereby improving the cycle characteristics.

[0203] Experimental Example 3

[0204] <Measurement of Particle Size Distribution>

[0205] 1 g of each carbon structure powder prepared in Example 1 and Comparative Example 2 was dispersed in acetone, and then the particle size distribution was measured using a particle size analyzer (Malvern Panalytical, product name: Mastersizer 3000). The measured particle size distribution was plotted on... Figure 12 In, and will Figure 12 The specific D in the particle size distribution diagram 10 D 50 D 90 and span value ((D) 90 -D 10 ) / D 50The information is recorded in Table 2.

[0206] The above particle size distribution measurements were performed under the conditions of a red light source (Max.) of 4mW He-Ne at 632.8nm and a blue light source (Max.) of 10mW LED at 470nm.

[0207] [Table 2]

[0208] <![CDATA[D 10 (μm)]]> <![CDATA[D 50 (μm)]]> <![CDATA[D 90 (μm)]]> span Example 1 3.12 8.63 17 1.61 Comparative Example 2 13.1 33.0 110 2.94

[0209] <Manufacturing and Evaluation of Half-Cells>

[0210] For the electrodes of the all-solid-state batteries without a negative electrode manufactured in Example 1 and Comparative Example 2, 150 mg to 200 mg of sulfide-based solid electrolyte (Li6PS5Cl) was filled into a ring mold with a diameter of 13 mm. 0.5 Br 0.5 The powder is pressurized at 400 MPa to form a solid electrolyte layer, and then pressurized at 100 MPa to form an intermediate layer with a thickness of 10 μm between the solid electrolyte layer and the negative electrode current collector.

[0211] Next, a lithium metal foil (Honjo Chemical Co., Ltd.) stamped to a diameter of 12 mm and a thickness of 200 μm is inserted into the opposite side of the solid electrolyte layer. Then, a T-shaped component acting as a cap is inserted and sealed along the vertical direction of the annular mold. Afterward, the annular mold is tightened using a pressure clamp with a torque of 3 Nm to fabricate the half-cell.

[0212] For each half-cell according to Example 1 and Comparative Example 2, under conditions of 25°C and 20 MPa, the current is 1.167 mA / cm². 2 The current density deposition capacity is 3.5 mA / cm². 2 Lithium at 1.167 mA / cm 2 The current density desorption capacity is 3.5 mA / cm². 2 The lithium was used as one cycle, and repeated charging and discharging was performed until the 28th cycle was reached. The coulombic efficiency and charge capacity of each cycle were measured and plotted on the graph. Figure 13 middle.

[0213] See Figure 12 and Figure 13 It can be confirmed that, in the case of Example 1, even at 3.5 mAh / cm³, 2 It can operate stably under high-capacity load conditions without short circuits. On the other hand, it can be confirmed that a short circuit occurred during the 15th cycle in Comparative Example 2.

[0214] This is presumably because, since Comparative Example 2 uses a carbon structure that does not meet the preferred particle size conditions of the substrate as an intermediate layer, the space for lithium deposition between the substrates is reduced compared to Example 1, making it impossible to perform the deposition. Figure 1 The lithium deposition mechanism shown allows for the deposition of an additional lithium layer between the intermediate layer and the solid electrolyte layer.

Claims

1. An electrode for a negative electrode-free all-solid-state battery, comprising: current collector; as well as An intermediate layer, disposed on the current collector and comprising a carbon structure, The carbon structure includes: Multiple matrix; and The spacers are formed by the substrates being spaced apart from each other. The spacer space includes a lithium deposition space having a width of 0.3 nm or more and 10 nm or less. The diameter D corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix. 50 It is between 5μm and 12μm.

2. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The diameter D corresponding to 10% of the cumulative volume in the cumulative volume distribution of the matrix. 10 It is between 1.5μm and 4.5μm.

3. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The diameter D corresponding to 90% of the cumulative volume in the cumulative volume distribution of the matrix 90 It is between 13μm and 25μm.

4. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The span value of the matrix according to the following mathematical formula 1 is 1.9 or less: [Mathematical Expression 1] In the mathematical formula 1, D 10 It is the diameter corresponding to 10% of the cumulative volume in the cumulative volume distribution of the matrix. D 50 It is the diameter corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix. D 90 It is the diameter corresponding to 90% of the cumulative volume in the cumulative volume distribution of the matrix.

5. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The plurality of substrates are stacked and spaced apart from each other in the stacking direction.

6. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The proportion of the number of lithium deposition spacers relative to the total number of spacers is 45% or more.

7. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The lithium deposition space has a width of more than 2 nm and less than 8 nm.

8. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The particle size of the matrix in the (002) direction is greater than 5 nm and less than 30 nm.

9. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The intermediate layer comprises more than 85% by weight and less than 97.5% by weight of the carbon structure.

10. The electrode for a negative electrode-free all-solid-state battery according to claim 1, wherein, The intermediate layer comprises 0.8 g / cm³ 3 Above and 2.0 g / cm 3 The following describes carbon structures.

11. A negative electrode-free all-solid-state battery, comprising: Negative electrode current collector; An intermediate layer, wherein the intermediate layer is disposed on the negative electrode current collector and comprises a carbon structure; A solid electrolyte layer is disposed on the intermediate layer; A positive electrode active material layer, wherein the positive electrode active material layer is disposed on the solid electrolyte layer and contains a positive electrode active material; as well as A positive electrode current collector is disposed on the positive electrode active material layer. The carbon structure includes: Multiple matrix; and The spacers are formed by the substrates being spaced apart from each other. The spacer space includes a lithium deposition space having a width of 0.3 nm or more and 10 nm or less. The diameter D corresponding to 50% of the cumulative volume in the cumulative volume distribution of the matrix. 50 It is between 5μm and 12μm.

12. The all-solid-state battery without a negative electrode according to claim 11, wherein, Before the negative electrode-free all-solid-state battery is put into operation, the thickness of the intermediate layer is more than 5 μm and less than 20 μm.

13. The all-solid-state battery without a negative electrode according to claim 11, wherein, During the charging of the electrodeless all-solid-state battery, lithium ions are deposited in the lithium deposition space.

14. The all-solid-state battery without a negative electrode according to claim 11, wherein, When the negative electrode-free all-solid-state battery is charged, no additional lithium deposition layer is formed between the intermediate layer and the solid electrolyte layer.

15. The all-solid-state battery without a negative electrode according to claim 11, wherein, When the negative electrode-free all-solid-state battery is fully charged, X-ray diffraction (XRD) analysis of the intermediate layer shows that the ratio of the intensity of the Li(110) peak to the intensity of the LiC6(001) peak is greater than 0.

5.

16. The all-solid-state battery without a negative electrode according to claim 11, wherein, The solid electrolyte layer contains a sulfide-based solid electrolyte.

17. A method for manufacturing an electrode for a negative electrode-free all-solid-state battery, comprising the following steps: (S1) Apply energy to a mixture containing dissolved carbon material and polymer binder to cause the matrix within the carbon material to separate and rearrange itself through self-assembly; as well as (S2) The product of step (S1) is ball-milled for more than 55 minutes and less than 150 minutes to produce carbon structures.

18. The method for manufacturing an electrode for a negative electrode-free all-solid-state battery according to claim 17, wherein, In step (S1), energy is applied to the mixture to remove the polymer binder, thereby forming spacers.

19. The method for manufacturing an electrode for a negative electrode-free all-solid-state battery according to claim 17, wherein, The polymer adhesive includes polymer adhesives selected from polyester, vinyl polyvinyl acetate, polyester-vinyl acetate copolymer, polyvinyl chloride, polyethylene, polypropylene, polybutadiene, polyolefin, polyvinyl acetate, polyethylene terephthalate, polystyrene, polyvinyl ketone, polyethylene terephthalate-ethylene glycol, polyethyleneimine, polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymer, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, polyimide, polyamide-imide, polyacrylic acid, polyvinyl alcohol, styrene-butadiene rubber-based polymer, acrylonitrile-butadiene rubber, acrylonitrile-butadiene-styrene rubber, acrylate-based rubber, hydroxypropyl methylcellulose, carboxymethyl cellulose (CMC), and composite polymers formed by mixing one or more of these.

20. The method for manufacturing an electrode for a negative electrode-free all-solid-state battery according to claim 17, wherein, The ball mill grinding process is carried out for more than 80 minutes and less than 120 minutes.

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