All-solid-state battery and method for preparing same

Abstract

The present invention relates to: an all-solid-state battery in which lithium or a lithium alloy is used as a negative electrode active material, the all-solid-state battery comprising a positive electrode, a solid electrolyte layer, a non-negative electrode coating layer, and a negative electrode current collector, wherein the ratio of the thickness of the solid electrolyte layer to the planar area of the negative electrode current collector is greater than 0.125 µm / cm2 and less than 1.25 µm / cm2; and a method for preparing same. According to the present invention, it is possible to provide an all-solid-state battery having excellent energy density characteristics as well as excellent output performance and cycle performance without cycle-dependent short circuiting, and a method for preparing same.

Description

All-solid-state battery and method for manufacturing the same

[0001] The present invention relates to an all-solid-state battery using lithium or a lithium alloy as a negative electrode active material and a method for manufacturing the same. The present application claims the benefit of priority based on Korean Patent Application No. 2024-0152485 filed on October 31, 2024, and all contents disclosed in the document of said Korean patent application are incorporated herein as part of the specification.

[0002] Recently, there has been growing interest in anodeless solid-state batteries, which allow a lithium metal layer to be formed during the charging process without forming a separate negative active material layer on the negative current collector during the battery manufacturing process. Anodeless solid-state batteries are useful for electric vehicles as they offer excellent stability and high energy density, which can increase the driving range on a single charge. However, even for anodeless solid-state batteries, further improving energy density remains a challenge, and there is also a need to further enhance output performance and cycle performance.

[0003] The present invention aims to solve the above problem and provides an all-solid-state battery and a method for manufacturing the same that have excellent energy density characteristics, as well as output performance and cycle performance, without short circuits during cycling.

[0004] One aspect of the present invention is an all-solid-state battery using lithium or a lithium alloy as a negative electrode active material, comprising a positive electrode, a solid electrolyte layer, a non-negative electrode coating layer, and a negative electrode current collector, wherein the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector is 0.125 μm / cm² 2 Exceeding 1.25 µm / cm 2 This relates to an all-solid-state battery characterized by being less than

[0005] In one embodiment, the ratio of the thickness of the solid electrolyte layer to the thickness of the non-cathode coating layer may be greater than 0.5 and less than 5.

[0006] In one embodiment, the thickness of the solid electrolyte layer may be 5 to 100 μm.

[0007] In one embodiment, the non-cathode coating layer may be characterized by including amorphous carbon.

[0008] In one embodiment, the amorphous carbon may be characterized as being one or more selected from the group consisting of carbon black, acetylene black, furnace black, Ketjen black, and graphene.

[0009] In one embodiment, the non-cathode coating layer may be characterized by further including a lithium-affinity element that forms an alloy or compound with lithium.

[0010] In one embodiment, the lithium affinity element may be characterized as being one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn).

[0011] In one embodiment, the non-cathode coating layer may be characterized by containing a lithium-affinity element in a range of 10 to 50 parts by weight relative to 100 parts by weight of amorphous carbon.

[0012] In one embodiment, the non-cathode coating layer may be characterized by further including a binder.

[0013] In one embodiment, the non-cathode coating layer may be characterized by containing a binder in a range of 1 to 20 parts by weight per 100 parts by weight of amorphous carbon.

[0014] In one embodiment, the solid electrolyte layer may be characterized by comprising a sulfide-based solid electrolyte.

[0015] In one embodiment, the sulfide-based solid electrolyte is Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, M is one of P, Si, Ge, B, Al, Ga, and In), Li2S-SiS2-P2S5-LiI,Li2S-P2S5,Li2S-P2S5-LiX (X is a halogen element), Li2S-B2S3,Li2S-P2S5-Z m S n (m, n are positive numbers), Z is one of Ge, Zn, or Ga, L i2 S-GeS2,Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2) and Li 7-x PS 6-x I x It can be characterized as being one or more types selected from (0≤x≤2).

[0016] In one embodiment, the all-solid-state battery of the present invention may be characterized in that the ratio of the 1C discharge capacity to the 0.1C discharge capacity is 90% or more.

[0017] In one embodiment, the all-solid-state battery of the present invention may be characterized by having an energy density of 700 Wh / L or more per volume.

[0018] Another aspect of the present invention is a method for manufacturing an all-solid-state battery using lithium or a lithium alloy as a negative electrode active material, comprising the steps of: forming a negative electrode coating layer on a negative electrode current collector; forming a solid electrolyte layer on the negative electrode coating layer; stacking an anode on the solid electrolyte layer; and performing a hydrostatic pressing process, wherein the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector is 0.125 μm / cm² 2 Exceeding 1.25 µm / cm 2 It may be a method for manufacturing an all-solid-state battery characterized by being less than

[0019] In one embodiment, the step of forming a solid electrolyte layer on the non-cathode coating layer may be characterized by including the step of applying a solid electrolyte slurry on the non-cathode coating layer; and the step of drying the applied solid electrolyte slurry.

[0020] The present invention can provide an all-solid-state battery and a method for manufacturing the same, which have excellent energy density characteristics as well as output performance and cycle performance without short circuits during cycling.

[0021] The drawings in this specification are merely for the purpose of facilitating an understanding of the invention, and the scope of the invention should not be interpreted as being limited to the embodiments described in the drawings in this specification.

[0022] Figure 1 is a graph showing the output performance evaluation results according to Evaluation Example 1.

[0023] Figure 2 is a graph showing the cycle performance evaluation results according to Evaluation Example 1.

[0024] FIG. 3 is a flowchart illustrating a method for manufacturing an all-solid-state battery according to one embodiment of the present invention.

[0025] Figure 4 is an image showing an example of a cell jig.

[0026] Terms and words used in this specification and claims shall not be interpreted as being limited to their ordinary or dictionary meanings, but shall 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.

[0027] Therefore, it should be understood that the configuration of the embodiments described in this specification is merely one of the most preferred embodiments of the present invention and does not represent all of the technical ideas of the present invention, and that various equivalents and modifications that can replace them may exist at the time of filing this application.

[0028] In this specification, singular expressions include plural expressions unless the context clearly indicates otherwise.

[0029] In this specification, when a part is described as “comprising” a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Thus, for example, a composition comprising compound A may include compounds other than A. However, the term “comprising” also encompasses, in a more restrictive sense as a specific embodiment thereof, “essentially / essentially composed of” and “composed of,” so, for example, a “composition comprising compound A” may also be (essentially / essentially) composed of compound A.

[0030] In connection with this, terms such as “comprising” or “having,” as described in this specification, 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.

[0031] In this specification, when any layer is described as being located “on” or “between” another arbitrary layer, this includes not only cases where any layer is in contact with another arbitrary layer, but also cases where another layer or material, etc., exists between the two layers.

[0032] Where in this specification a quantity, concentration, or other value or parameter is given as an enumeration of a range, a preferred range, a preferred upper limit, and a preferred lower limit, it should be understood that any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the range is disclosed separately, specifically discloses all ranges that may be formed. Where a range of numerical values ​​is mentioned in this specification, unless otherwise stated, for example, without limiting terms such as greater than or less than, the range is intended to include its endpoint value and all integers and fractions within that range. The scope of the invention is not intended to be limited to the specific value mentioned when defining the range.

[0033] In the present specification, where “about” is written before a specific numerical value or the upper and lower limits of a specific numerical range, unless specifically otherwise stipulated, it means that the numerical value or the upper and lower limits of the numerical range following “about” may be a value within an error range without departing from the technical concept of the present invention. In this case, for example, the error range may be ±5%, and in this case, the description “about 1 mm” means that it may be “0.95 mm to 1.05 mm”.

[0034] Among the physical properties mentioned in this specification, if the measured temperature affects the property, the property is measured at room temperature unless specifically otherwise specified. The term "room temperature" refers to a natural temperature that has not been heated or cooled, and may mean, for example, any temperature within the range of about 10°C to 30°C, about 23°C, or about 25°C. Furthermore, unless specifically otherwise specified, the unit of temperature in this specification is °C.

[0035] In addition, among the physical properties mentioned in this specification, if the measured pressure affects the physical property, unless specifically otherwise specified, the physical property is measured at normal pressure, that is, atmospheric pressure (about 1 atmosphere).

[0036] The first aspect of the present invention relates to an all-solid-state battery using lithium or a lithium alloy as a negative electrode active material.

[0037] The all-solid-state battery of the present invention may include, for example, a positive electrode, a solid electrolyte layer, a non-negative electrode coating layer and / or a negative electrode current collector.

[0038] In this specification, "all-solid-state battery" may mean an all-solid-state secondary battery and may be referred to as a cell, secondary battery, or battery, etc.

[0039] In this specification, the term "non-cathode coating layer" refers to a coating layer formed between a negative electrode current collector and a solid electrolyte layer in an all-solid-state battery in which lithium is adsorbed in the non-cathode coating layer during charging, and after the charging capacity of the non-cathode coating layer is exceeded, lithium is precipitated between the negative electrode current collector and the non-cathode coating layer to form a metal layer, and during discharge, lithium in the non-cathode coating layer and the lithium metal layer is ionized and moves toward the positive electrode. The composition and operating mechanism may differ from that of a conventional negative electrode active material layer. The non-cathode coating layer can cover the lithium metal layer formed on the negative electrode current collector during the charging process to serve as a protective layer for the lithium metal layer and can suppress the precipitation growth of lithium dendrites. Through this, short circuits and capacity degradation of the all-solid-state battery can be suppressed, and performance, etc., can be improved. However, unintended dendrites may still be formed during the charging process, which may cause damage to the solid electrolyte layer, etc., and lead to short circuits, etc. The present invention aims to solve these problems and provide an all-solid-state battery having excellent energy density, output characteristics, and cycle performance, which can be realized particularly by each of the configurations described below or combinations thereof.

[0040] The all-solid-state battery of the present invention, for example, has a ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector of 0.125 μm / cm² 2 Exceeding 1.25 µm / cm 2It may be characterized as being less than. Unless specifically otherwise described in this specification, "thickness" may refer to the thickness after performing the hydrostatic pressing process described below. In this specification, thickness may be a maximum thickness, a minimum thickness, and / or an average thickness, and may be measured in a known manner. In this specification, the thickness of the solid electrolyte layer may refer to, for example, the thickness of the solid electrolyte layer in a sintered state after performing a hydrostatic pressing process. In another example, the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the cathode current collector is 1.2 μm / cm² 2 Less than, 1.15 µm / cm² 2 Less than, 1.1 µm / cm² 2 Less than, 1.05 µm / cm² 2 Less than 1 µm / cm² 2 Less than, 0.95 µm / cm 2 Less than, 0.9 µm / cm 2 Less than, 0.85 µm / cm² 2 Less than, 0.8 µm / cm² 2 Less than, 0.75 µm / cm 2 Less than, 0.7 µm / cm 2 Less than, 0.65 µm / cm 2 Less than, 0.6 µm / cm² 2 Less than, 0.55 µm / cm² 2 Less than, 0.5 µm / cm 2 Less than, 0.45 µm / cm 2 Less than, 0.4 µm / cm 2 Less than, 0.35 µm / cm 2 Less than or 0.3 µm / cm 2 Less than or 0.13 µm / cm 2 Exceeding 0.135 µm / cm² 2 Exceeding 0.14 µm / cm² 2 Exceeding 0.145 µm / cm² 2 Exceeding 0.15 µm / cm² 2 Exceeding 0.155 µm / cm² 2 Exceeding 0.16 µm / cm² 2 Exceeding 0.165 µm / cm² 2 Exceeding 0.17 µm / cm² 2Exceeding 0.175 µm / cm² 2 Exceeding 0.18 µm / cm² 2 Exceeding 0.185 µm / cm² 2 Exceeding 0.19 µm / cm² 2 Exceeding 0.195 µm / cm² 2 Exceeding 0.20 µm / cm² 2 Exceeding 0.205 µm / cm² 2 Exceeding 0.21 µm / cm² 2 Exceeding 0.215 µm / cm² 2 Exceeding 0.22 µm / cm² 2 Exceeding 0.225 µm / cm² 2 Exceeding 0.23 µm / cm² 2 Exceeding 0.235 µm / cm² 2 Exceeding 0.24 µm / cm² 2 Exceeding or 0.245㎛ / cm 2 It may exceed.

[0041] The present invention can provide an all-solid-state battery with excellent energy density characteristics, as well as output performance and cycle performance, without short circuits during cycles by controlling the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector in the all-solid-state battery as described above. In particular, the present invention can exhibit such excellent effects for an anodeless all-solid-state battery by controlling the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector as described above. Although the exact reason is not known, in the case of an anodeless all-solid-state battery, lithium is precipitated between the anode coating layer and the negative electrode current collector during the charging process to form a lithium metal layer; at this time, some of it may form unintended dendrites, which can damage the solid electrolyte layer. In this case, if a solid electrolyte layer that is excessively thin or excessively thick relative to the planar area of ​​the negative electrode current collector is introduced, a short circuit may occur due to damage to the solid electrolyte layer, or it may lead to a decrease in energy density, output performance, and / or cycle performance. To solve these problems, the present invention specifically controls the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector for a negative electrode-free all-solid-state battery as described above, and as a result, it has been confirmed that an all-solid-state battery with excellent energy density characteristics, as well as output performance and cycle performance, can be provided without short circuits during cycling.

[0042] The planar area of ​​the above cathode current collector is, for example, 10 cm² 2 up to 1000 cm 2 It may be. In another example, the planar area of ​​the above-mentioned cathode current collector is 20 cm² 2 Over, 30 cm 2 Over, 40 cm 2 Over, 50 cm 2 Over, 100 cm 2 Over, 150 cm 2 More than or equal to 200 cm 2 or more, or 900 cm 2Below, 800 cm 2 Below, 700 cm 2 Below, 600 cm 2 Below, 500 cm 2 Below, 400 cm 2 Below, 300 cm 2 Below, 200 cm 2 Below, 150 cm 2 Below, 100 cm 2 Below, 90 cm 2 Below, 80 cm 2 Below, 70 cm 2 Below, 60 cm 2 Less than or equal to 50 cm 2 It may be less than, but is not limited to.

[0043] The all-solid-state battery of the present invention may be characterized, for example, by the ratio of the thickness of the solid electrolyte layer to the thickness of the non-cathode coating layer being greater than 0.5 and less than 5. In other examples, the ratio of the thickness of the solid electrolyte layer to the thickness of the non-cathode coating layer may be greater than 0.55, greater than 0.6, greater than 0.65, greater than 0.7, greater than 0.75, greater than 0.8, greater than 0.85, greater than 0.9, or greater than 0.95, or less than 4.5, less than 4, less than 3.5, less than 3, less than 2.5, less than 2, or less than 1.5. By controlling the ratio of the thickness of the solid electrolyte layer to the thickness of the non-cathode coating layer together with the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the aforementioned negative electrode current collector as described above, the all-solid-state battery of the present invention can provide an all-solid-state battery with superior energy density characteristics, as well as output performance and cycle performance, without short circuits during cycles. These effects can be further enhanced by controlling the thickness of the solid electrolyte layer described below.

[0044] The thickness of the solid electrolyte layer may be characterized as, for example, 5 to 100 μm. In other examples, the thickness of the solid electrolyte layer may be 6 μm or more, 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more, or 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 20 μm or less.

[0045] The above-mentioned non-cathode coating layer may be characterized by including, for example, amorphous carbon.

[0046] The above amorphous carbon may be characterized as being one or more selected from the group consisting of, for example, carbon black, acetylene black, furnace black, Ketjen black, and graphene.

[0047] The average particle size of the primary particles of the above-mentioned amorphous carbon may be characterized as, for example, less than 100 nm. The average particle size of the above-mentioned primary particles is the volume-based average particle size (D 50 It may mean ). The average particle size of the primary particle may be measured, for example, by TEM, but is not limited thereto and may be measured by a known method commonly used in the industry. In other examples, the average particle size of the primary particle of the amorphous carbon may be 95 nm or less, 90 nm or less, 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, or 45 nm or less, or 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, or 40 nm or more. The present invention controls the average particle size of primary particles of amorphous carbon to the range described above, thereby reducing the occurrence of cracks during charging of an all-solid-state battery and improving the battery's lifespan, and further improves performance by providing a pathway through which lithium ions can move efficiently.

[0048] The above amorphous carbon may be included in an amount of 40 parts by weight or more based on 100 parts by weight (dry weight) of the anode coating layer, for example. In other examples, the above amorphous carbon may be included in an amount of 45 parts by weight or more, 50 parts by weight or more, 55 parts by weight or more, 60 parts by weight or more, or 65 parts by weight or more based on 100 parts by weight (dry weight) of the anode coating layer, or in an amount of 95 parts by weight or less, 90 parts by weight or less, 85 parts by weight or less, 80 parts by weight or less, or 75 parts by weight or less.

[0049] The above-mentioned non-cathode coating layer may be characterized by further including, for example, a lithium-affinity element that forms an alloy or compound with lithium.

[0050] The above lithium-affinity elements may be one or more selected from the group consisting of, for example, gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn).

[0051] The above-described non-cathode coating layer may be characterized by containing a lithium-affinity element in a range of, for example, 10 to 50 parts by weight relative to 100 parts by weight of amorphous carbon. In other examples, the all-solid-state battery of the present invention may contain the lithium-affinity element in an amount of 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, or 30 parts by weight or more relative to 100 parts by weight of amorphous carbon, or in an amount of 45 parts by weight or less, 40 parts by weight or less, or 35 parts by weight or less. By introducing the lithium-affinity element together with amorphous carbon having the above-described characteristics, the all-solid-state battery of the present invention can provide an all-solid-state battery having excellent cycle characteristics.

[0052] The ratio of the average particle size of the lithium-affinity element to the average particle size of the primary particle of the amorphous carbon may be characterized as being, for example, within a range of 0.5 to 5. In other examples, the ratio of the average particle size of the lithium-affinity element to the average particle size of the primary particle of the amorphous carbon may be characterized as being 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, 1.0 or more, 1.1 or more, 1.2 or more, 1.3 or more, or 1.4 or more, or 4.5 or less, 4.0 or less, 3.5 or less, 3.0 or less, 2.5 or less, 2.0 or less, or 1.5 or less. By controlling the ratio of the average particle size as described above, lithium ions can be uniformly formed or detached between the non-cathode coating layer and the negative electrode current collector during the charging and discharging process, which can improve the cycle characteristics and stability of the battery.

[0053] The particle size of the above lithium-affinity element may be, for example, within a range of 10 to 1000 nm. The above particle size may refer to a maximum particle size, a minimum particle size, or an average particle size. In other examples, the particle size of the above lithium-affinity element may be 20 nm or more, 30 nm or more, 40 nm or more, or 50 nm or more, or 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, or 100 nm or less.

[0054] The non-cathode coating layer of the present invention may further include, for example, a binder. For example, a water-based binder, an organic binder, or a combination thereof may be used as the binder. For example, the binder may be polyvinyl alcohol, carboxymethylcellulose, hydroxypropylcellulose, diacetylcellulose, polyvinylidene fluoride, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, a polymer comprising ethylene oxide, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylate styrene-butadiene rubber, epoxy resin, nylon, or a combination thereof. For example, the water-based binder may be styrene-butadiene rubber, carboxymethylcellulose, or a combination thereof. For example, polytetrafluoroethylene, polyvinylidene fluoride, or a combination thereof may be used as the above organic binder.

[0055] The binder may be characterized by being included in a range of 1 to 20 parts by weight relative to 100 parts by weight of amorphous carbon, for example. The weight ratio of the binder to the amorphous carbon may refer to a value converted based on the solid content of the binder, i.e., the dry weight. In other examples, the binder may be included in an amount of 2 parts by weight or more, 3 parts by weight or more, 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, or 8 parts by weight or more relative to 100 parts by weight of amorphous carbon, or 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, or 10 parts by weight or less.

[0056] The present invention can provide an all-solid-state battery having excellent performance and stability by controlling the weight ratio between the compositions included in the cathode-free coating layer as described above.

[0057] The cathode-free coating layer of the present invention may further include, for example, a solvent. In this specification, the meaning of the cathode-free coating layer further including a solvent may mean that a solvent is used during the manufacturing process of the cathode-free coating layer, and may not mean that the final cathode-free coating layer manufactured through drying, etc., contains a solvent. Water, N-methylpyrrolidone (NMP), etc., may be used as the solvent.

[0058] The non-cathode coating layer of the present invention may further include, for example, other additives. As long as it does not impede the purpose of the present invention, fillers, coating agents, dispersants, ion conductivity aids, etc. used in conventional all-solid-state batteries may be used without limitation as said other additives.

[0059] The non-cathode coating layer of the present invention can be manufactured, for example, by applying and drying a slurry in which the material constituting the non-cathode coating layer is dispersed onto a cathode current collector.

[0060] The thickness of the non-cathode coating layer of the present invention may be 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less of the thickness of the positive active material layer described later. The thickness of the non-cathode coating layer may be, for example, within a range of 1 to 20 μm, 5 to 18 μm, or 9 to 15 μm. By controlling the thickness of the non-cathode coating layer as described above, the breakdown of the non-cathode coating layer by lithium dendrites formed between the non-cathode coating layer and the negative current collector described later can be controlled, thereby improving cycle characteristics, further improving energy density, and reducing the internal resistance of the all-solid-state battery.

[0061] The non-cathode coating layer of the present invention may, for example, have a porosity in the range of 30 to 90%. The porosity of the non-cathode coating layer may be measured in a known manner. In other examples, the porosity of the non-cathode coating layer may be 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, or 65% or more, or 85% or less, 80% or less, 75% or less, or 70% or less.

[0062] The above anode may include, for example, an anode current collector and / or an anode active material layer.

[0063] The above positive current collector may be a known metal that can be used as a current collector for an all-solid-state battery. The above positive current collector may be, for example, a plate, mesh, or foil made of copper (Cu), nickel (Ni), aluminum (Al), vanadium (V), gold (Au), platinum (Pt), chromium (Cr), iron (Fe), zinc (Zn), indium (In), germanium (Ge), lithium (Li), magnesium (Mg), stainless steel, titanium (Ti), cobalt (Co), or an alloy thereof. The positive current collector may be omitted depending on the case.

[0064] The above positive active material layer may include, for example, a positive active material, a solid electrolyte, a binder and / or a conductive material.

[0065] The above-mentioned positive electrode active material reversibly absorbs and desorbs lithium ions. The positive electrode active material may be, for example, lithium transition metal oxides such as lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganese oxide (lithium manganate), lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, but is not limited thereto; any material used as a positive electrode active material in the relevant technical field may be used. The positive electrode active materials may be used individually or in a mixture of two or more types.

[0066] The above lithium transition metal oxide is, for example, Li a A 1-b B b D2 (wherein 0.90≤a≤1, and 0≤b≤0.5); Li a Ni 1-b-c Co b B c O 2-α F2(wherein 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni 1-b-c Mn b B c D α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0≤α≤2); Li a Ni 1-b-c Co b B c D α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2); Li a E 1-b B b O 2-c D c(In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05); LiE 2-b B b O 4-c D c (In the above formula, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b B c O 2-α F α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a CoG b O2(wherein the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a MnG b O2(wherein the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a Mn2GbO4 (wherein the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a Ni 1-b-c Mn b B c O 2-α F α (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni 1-b-c Mn b B c O 2-α F2(wherein 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni b E c G d O2(wherein 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1); Li a Ni b Co c Mn d GeO2 (wherein the above formula, 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0 ≤d≤0.5, 0.001≤e≤0.1); Li a NiG bO2(wherein 0.90≤a≤1, 0.001≤b≤0.1); QO2;QS2;LiQS2;V2O5;LiV2O5;LiIO2;LiNiVO4;Li (3- f) J2(PO4)3(0≤f≤2); Li (3-f) Fe2(PO4)3(0≤f≤2); it may be a compound represented by any one of the chemical formulas of LiFePO4. In such a compound, A is Ni, Co, Mn, or a combination thereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; F is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; I is Cr, V, Fe, Sc, Y, or a combination thereof; and J may be V, Cr, Mn, Co, Ni, Cu, or a combination thereof. As a positive electrode active material, a compound having a coating layer added to the surface of such a compound may be used, or a mixture of the compound described above and the compound having a coating layer added may be used. A coating layer added to the surface of such compounds may contain, for example, a lithium ion conductive oxide. The lithium ion conductive oxide is, for example, LiNbO3,Li4Ti5O 12 Examples include Li3PO4, but are not limited thereto. The compounds forming this coating layer may be amorphous or crystalline. Methods for forming the coating layer may include, for example, spray coating or immersion methods, but can be selected without limitation as long as they do not adversely affect the physical properties of the cathode active material.

[0067] When the above-mentioned cathode active material is a ternary lithium transition metal oxide such as NCA or NCM and contains nickel (Ni), it may be possible to increase the capacity density of the all-solid-state battery and reduce the metal leaching of the cathode active material in the charged state. Accordingly, the cycle characteristics of the all-solid-state battery in the charged state may be improved.

[0068] The shape of the above-mentioned positive electrode active material may be a particle shape, for example, a sphere, an elliptical sphere, etc. The particle size of the positive electrode active material is not particularly limited and must be within a range applicable to the positive electrode active material of a conventional all-solid-state battery. The content of the positive electrode active material is also not particularly limited and must be within a range applicable to the positive electrode of a conventional all-solid-state battery.

[0069] The solid electrolyte included in the above-mentioned positive electrode active material layer may be, for example, the same as or different from the solid electrolyte included in the solid electrolyte layer. The solid electrolyte included in the above-mentioned positive electrode active material layer may be a sulfide-based solid electrolyte, an oxide-based solid electrolyte, a phosphoric acid-based solid electrolyte, or a halide-based solid electrolyte, but is not limited thereto and may be any that is commonly used in all-solid-state batteries.

[0070] The solid electrolyte included in the above positive active material layer may, for example, have a smaller average particle size compared to the solid electrolyte included in the solid electrolyte layer. For example, the average particle size of the solid electrolyte included in the positive active material layer may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the average particle size of the solid electrolyte included in the solid electrolyte layer.

[0071] The binder included in the above positive active material layer may be, for example, acrylonitrile butadiene rubber (ABR), butadiene rubber (BR), styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc.

[0072] The conductive material included in the above positive active material layer may be, for example, graphite, carbon black, acetylene black, kezen black, carbon fiber, or metal powder.

[0073] In addition to the above, the positive active material layer may further include additives such as fillers, coating agents, dispersants, and ion conductivity aids, and these additives may be used without limitation as long as they are known materials generally used in electrodes of all-solid-state batteries.

[0074] The above solid electrolyte layer may include, for example, a sulfide-based solid electrolyte. The above sulfide-based solid electrolyte is, for example, Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, M is one of P, Si, Ge, B, Al, Ga, and In), Li2S-SiS2-P2S5-LiI,Li2S-P2S5,Li2S-P2S5-LiX (X is a halogen element), Li2S-B2S3,Li2S-P2S5-Z m S n (m, n are positive numbers), Z is one of Ge, Zn, or Ga, L i2 S-GeS2,Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x(0≤x≤2) and Li 7-x PS 6-x I x It may be one or more selected from (0≤x≤2). Sulfide-based solid electrolytes can be manufactured by processing starting materials, such as Li2S or P2S5, by methods such as melt quenching or mechanical milling. Additionally, heat treatment may be performed after such processing. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. In the present invention, the sulfide-based solid electrolyte may, for example, include sulfur (S), phosphorus (P), and lithium (Li) as at least constituent elements among the above-mentioned sulfide-based solid electrolyte materials.

[0075] The above sulfide-based solid electrolyte is, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound comprising one or more selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0076] The density of the above-mentioned azyrodite-type solid electrolyte may be, for example, 1.5 to 2.0 g / cc. Since the above-mentioned azyrodite-type solid electrolyte has a density of 1.5 g / cc or higher, the internal resistance of the all-solid-state battery is reduced, and penetration of the solid electrolyte by Li can be effectively suppressed.

[0077] The elastic modulus of the above solid electrolyte may be, for example, 15 to 35 GPa.

[0078] The above-mentioned solid electrolyte layer may include, for example, a binder. The binder included in the solid electrolyte layer may be, for example, one of the types of binders included in the above-mentioned positive active material layer and / or negative electrode coating layer, but is not limited thereto and any binder used in the relevant technical field may be possible. The binder included in the solid electrolyte layer may be the same as or different from the binder included in the aforementioned positive active material layer and / or negative electrode coating layer.

[0079] The above-mentioned solid electrolyte layer may further include, for example, a solvent. In this specification, the meaning of the solid electrolyte layer further including a solvent may be that a solvent is used during the manufacturing process of the solid electrolyte layer, and may not mean that the solid electrolyte layer finally manufactured through drying, etc. Examples of solvents included in the above-mentioned solid electrolyte layer include butyrate.

[0080] For the above-mentioned negative electrode current collector, known metals that can be used as current collectors for all-solid-state batteries may be used. For example, the above-mentioned negative electrode current collector may be a material that does not form alloys or compounds with lithium. For example, the above-mentioned negative electrode current collector may be selected from the group consisting of copper (Cu), nickel (Ni), aluminum (Al), vanadium (V), gold (Au), platinum (Pt), magnesium (Mg), iron (Fe), titanium (Ti), cobalt (Co), chromium (Cr), zinc (Zn), germanium (Ge), indium (In), and stainless steel, but is not limited thereto; any material used as an electrode current collector in the relevant technical field may be used as long as it does not impede the purpose of the present invention. The above-mentioned negative electrode current collector may be composed of one of the metals described above, or may be composed of an alloy of two or more metals or a coating material. The above-mentioned negative electrode current collector may be in the form of a plate, mesh, or foil, for example, but is not limited thereto.

[0081] The all-solid-state battery of the present invention may further include, for example, a metal comprising lithium or a lithium alloy and / or a metal (layer) thereof between the negative electrode current collector and the non-negative electrode coating layer and / or within the non-negative electrode coating layer upon charging. The lithium alloy may be, for example, a Li-Al alloy, a Li-Sn alloy, a Li-In alloy, a Li-Ag alloy, a Li-Au alloy, a Li-Zn alloy, a Li-Ge alloy, a Li-Si alloy, etc., but is not limited thereto and any alloy used as a lithium alloy in the relevant technical field is acceptable. The metal or metal layer included between the negative electrode current collector and the non-negative electrode coating layer and / or within the non-negative electrode coating layer may be composed of one of these alloys or lithium, or may be composed of various types of alloys.

[0082] The thickness of the metal layer containing the lithium or lithium alloy may be, for example, within the range of 1 to 1000 μm, 1 to 500 μm, 1 to 200 μm, 1 to 150 μm, 1 to 100 μm, or 1 to 50 μm. It is necessary to control the thickness as above so that the metal layer can perform its role as a lithium reservoir effectively and improve cycle characteristics.

[0083] The above metal layer may be formed, for example, by precipitation between the negative current collector and the non-negative coating layer through charging after assembly of the all-solid-state battery. When a metal layer is formed between the negative current collector and the non-negative coating layer through charging after assembly of the all-solid-state battery, the negative current collector, the non-negative coating layer, and the region between them may be, for example, a lithium-free (Li-Free) region that does not contain lithium in the initial state or after discharge state of the all-solid-state battery.

[0084] The all-solid-state battery of the present invention may be characterized, for example, having a ratio of 1C discharge capacity to 0.1C discharge capacity of 90% or more. In this specification, the ratio of 1C discharge capacity to 0.1C discharge capacity may refer to a value measured in accordance with the evaluation example described below. The evaluation may be performed by applying pressure ranging from several to tens of megapascals (MPa) to the all-solid-state battery, and pressure may be applied using an external device such as that shown in FIG. 4, for example, but is not limited thereto. In this specification, the pressure applied to the all-solid-state battery using the external device is referred to as "battery driving pressure." In another example, the all-solid-state battery of the present invention may have a ratio of 1C discharge capacity to 0.1C discharge capacity of 91% or more, 92% or more, 93% or more, or 94% or more, and the upper limit may be 100% or less, 99% or less, or 95% or less, although the upper limit is not particularly limited.

[0085] The all-solid-state battery of the present invention may be characterized, for example, having an energy density per volume of 700 Wh / L or more. In this specification, the energy density per volume of the all-solid-state battery may refer to a value measured or calculated in accordance with the evaluation example described below. In other examples, the all-solid-state battery of the present invention may have an energy density per volume of 750 Wh / L or more, 800 Wh / L or more, 850 Wh / L or more, 900 Wh / L or more, or 950 Wh / L or more, or 2000 Wh / L or less, 1500 Wh / L or less, or 1000 Wh / L or less.

[0086] A second aspect of the present invention may be a method for manufacturing an all-solid-state battery using lithium or a lithium alloy as a negative electrode active material.

[0087] The details regarding the first aspect of the present invention may be applied in the same way to the details regarding the second aspect unless specifically described otherwise.

[0088] The method for manufacturing an all-solid-state battery according to the present invention may include, for example, the step of forming a non-cathode coating layer on a negative electrode current collector; the step of forming a solid electrolyte layer on the non-cathode coating layer; the step of stacking an anode on the solid electrolyte layer; and / or the step of performing a hydrostatic pressing process, wherein the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the negative electrode current collector is 0.125 μm / cm² 2 Exceeding 1.25 µm / cm 2 It can be characterized as being less than

[0089] The step of forming a non-cathode coating layer on the above-mentioned cathode current collector may include, for example, a step of applying a non-cathode coating layer slurry onto the cathode current collector; and / or a step of drying the applied non-cathode coating layer slurry. In this specification, application may be performed by methods such as dip coating, comma coating, gravure coating, lip die coating, micro-gravure coating, or slot die coating, but is not limited thereto, and known methods may be applied. The non-cathode coating layer slurry may include, for example, the aforementioned amorphous carbon, lithium-affinity element, binder, and / or solvent. The step of drying the applied non-cathode coating layer slurry may include, for example, a step of drying at 60 to 100°C for 10 to 30 minutes; and / or a step of vacuum drying at 80 to 120°C for 8 to 12 hours.

[0090] The step of forming a solid electrolyte layer on the above-mentioned non-cathode coating layer may include, for example, a step of applying a solid electrolyte slurry on the non-cathode coating layer; and / or a step of drying the applied solid electrolyte slurry. The solid electrolyte slurry may include, for example, the aforementioned sulfide-based solid electrolyte, binder and / or solvent, etc. The step of drying the applied solid electrolyte slurry may include, for example, a step of vacuum drying at a temperature of 60 to 80 °C for 3 to 7 hours.

[0091] The step of performing the above isostatic press process may, for example, involve sealing an electrode assembly including the aforementioned negative current collector, non-negative coating layer, solid electrolyte layer, and positive electrode into a pouch, and then performing the isostatic press process on the pouch. A known pouch may be used as the pouch. The isostatic press ensures that a uniform force is applied to all surfaces, for example, by pressure generated by a fluid, and the performance or lifespan characteristics of the battery may be further improved by the isostatic press process. The isostatic press may be a Cold Isostatic Press (CIP) or a Warm Isostatic Press (WIP), and preferably a WIP. The isostatic press process may be performed for 10 to 50 minutes at, for example, 300 to 700 MPa.

[0092] The method for manufacturing an all-solid-state battery according to the present invention may include, in addition to the steps described above, further steps that can be introduced into known all-solid-state battery manufacturing methods, provided that such steps do not impede the purpose of the present invention, but are not limited thereto.

[0093] In the following, the present invention is described in detail with reference to examples to specifically explain the disclosure of the present invention as described above and the intended functions and effects of the present invention. However, the examples may be modified in various different forms, and the scope of this specification is not to be interpreted as being limited only to these examples. It is emphasized that the examples are provided to represent the present invention and to explain it more specifically to those skilled in the art.

[0094] Example 1.

[0095] (cathode)

[0096] 6 g of carbon black (average particle size 41 nm), 2 g of silver (Ag) nanoparticles (average particle size 60 nm), 9.33 g of PVdF solution (solid content 6%), and 7.19 g of NMP solution are placed in a Thinky mixer container and mixed 12 times for 3 minutes at 2000 rpm. Subsequently, an additional 5 g of NMP solution is added, and mixing is performed 5 times for 3 minutes at 2000 rpm to prepare a cathode-free coating layer slurry. Next, using a bar coater, SUS foil (planar surface area 40 cm²) 2 The above slurry was coated onto ), dried in air at 80°C for 20 minutes, and then vacuum dried at 100°C for 10 hours. Through this, a cathode with a non-cathode coating layer formed on a SUS foil was obtained.

[0097] (Solid electrolyte layer / cathode composite)

[0098] A slurry for forming a solid electrolyte layer was prepared by mixing Li6PS5Cl, an Argyrodite-type crystal, SBR (StyreneButadieneRubber), and a process solvent (butyrate) to a solid content of 45 to 60% and using a mixer. The prepared solid electrolyte slurry was applied onto the non-cathode coating layer and coated using a bar coater, and then vacuum dried at a temperature of 70°C for 5 hours.

[0099] (anode)

[0100] LiNi as the positive active material 0.8 Co 0.15 Mn 0.05O2 (NCM), Li6PS5Cl (an argyrodite-type crystal) as the solid electrolyte, polytetrafluoroethylene (Teflon binder, DuPont) as the binder, and carbon nanofiber (CNF) as the conductive agent were prepared. Subsequently, these materials were mixed in a weight ratio of cathode active material : solid electrolyte : conductive agent : binder = 84 : 15 : 0.2 : 1.2, and the mixture was formed into a large sheet to fabricate a cathode sheet. Furthermore, the cathode was fabricated by pressing this cathode sheet onto an 18 µm thick aluminum foil cathode current collector. The initial charge capacity of the cathode (charge capacity at the first cycle) was approximately 20 mAh at a 4.25 V charge. The cathode weight was approximately 110 mg (approx. 203 mAh / g per weight of active material).

[0101] (Solid-state battery)

[0102] An electrode assembly was manufactured by laminating a positive electrode onto the solid electrolyte layer of the above-described solid electrolyte layer / negative electrode composite, and then sealing it in a pouch under vacuum to produce an all-solid-state battery. Here, parts of the positive electrode current collector and the negative electrode current collector were protruded outward from the pouch to maintain the vacuum of the battery. These protrusions served as the positive and negative terminals. Additionally, the all-solid-state battery was placed in an aluminum pouch and vacuum-sealed for at least 40 seconds, followed by hydrostatic treatment at 500 MPa for 30 minutes.

[0103] In an all-solid-state battery manufactured after hydrostatic treatment, the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the SUS foil is 0.25 μm / cm 2 The ratio of the thickness of the solid electrolyte layer to the non-cathode coating layer was 1, and the thickness of the solid electrolyte layer was 10 μm.

[0104] Comparative Example 1.

[0105] In an all-solid-state battery manufactured after hydrostatic treatment, the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the SUS foil is 0.125 μm / cm 2An all-solid-state battery was manufactured in the same manner as in Example 1, except that the ratio of the thickness of the solid electrolyte layer to the non-anode coating layer was 0.5 and the thickness of the solid electrolyte layer was 5 μm.

[0106] Comparative Example 2.

[0107] In an all-solid-state battery manufactured after hydrostatic pressure treatment, the ratio of the thickness of the solid electrolyte layer to the planar area of ​​the SUS foil is 1.25 μm / cm 2 An all-solid-state battery was manufactured in the same manner as in Example 1, except that the ratio of the thickness of the solid electrolyte layer to the non-anode coating layer is 5 and the thickness of the solid electrolyte layer is 50 μm.

[0108] Comparative Example 3.

[0109] An all-solid-state battery was manufactured in the same manner as in Example 1, except that a negative electrode active material layer was formed on a SUS foil instead of a non-negative coating layer as the negative electrode. At this time, the negative electrode active material layer was formed by applying a slurry containing graphite, a solid electrolyte, and a binder in a weight ratio of 75:20:5 onto a SUS foil and drying it. Natural graphite was used as the graphite, Li6PS5Cl as the solid electrolyte, and styrene-butadiene rubber (SBR) as the binder.

[0110] Evaluation Example 1. Evaluation of Output Performance and Cycle Performance

[0111] The above-mentioned all-solid-state battery (11, battery cell) was fastened between the first plate (12) and the second plate (13) of the cell jig (10) as shown in FIG. 4, and the output performance and cycle performance of the battery were evaluated while controlling the battery driving pressure to 10 MPa.

[0112] The all-solid-state batteries (pouch-type monocells) of the above examples and comparative examples were operated under the following charge-discharge conditions at an operating voltage range of 4.25V-3.0V and an operating temperature of 60℃ to evaluate the output characteristics, and the results are shown in Table 1 and Figure 1 below.

[0113] (Charging / Discharging Conditions)

[0114] Charging conditions: 0.1C, 4.25V CC / CV, 0.05C cut-off

[0115] Discharge conditions: 0.1C, 0.1C, 0.33C, 0.5C, or 1C, 3.0V, CC

[0116]

[0117] In addition, the all-solid-state batteries (pouch-type monocells) of the above examples and comparative examples were operated under the following charge-discharge conditions at an operating voltage range of 4.25V-3.0V and an operating temperature of 60℃ to evaluate cycle performance, and the results are shown in Table 2 and Figure 2 below.

[0118] (Charging / Discharging Conditions)

[0119] Charging conditions: 0.33C, 4.25V CC / CV, 0.1C cut-off

[0120] Discharge conditions: 0.33C, 3.0V, CC

[0121]

[0122] (The capacity retention rate (%) at 50 cycles refers to the percentage of the capacity after 50 cycles relative to the capacity after 1 cycle.)

[0123] Evaluation Example 2. Energy density per unit volume

[0124] For the all-solid-state batteries (pouch-type monocells) of the above examples and comparative examples, the energy density per unit volume was calculated in a known manner by considering the cell energy (Nominal voltage * discharge capacity) at an SOC of 30 and the volume of materials and auxiliary materials, and the results are shown in Table 3.

[0125]

Claims

1. An all-solid-state battery using lithium or a lithium alloy as the negative electrode active material, It includes an anode, a solid electrolyte layer, a non-cathode coating layer, and a cathode current collector, The ratio of the thickness of the solid electrolyte layer to the planar area of ​​the above-mentioned cathode current collector is 0.125 μm / cm 2 Exceeding 1.25 µm / cm 2 All-solid-state battery characterized by being less than 2. In Paragraph 1, An all-solid-state battery characterized in that the ratio of the thickness of the solid electrolyte layer to the thickness of the above-mentioned non-cathode coating layer is greater than 0.5 and less than 5.

3. In Paragraph 1, An all-solid-state battery characterized by the thickness of the solid electrolyte layer being 5 to 100 μm.

4. In Paragraph 1, All-solid-state battery characterized in that the above-mentioned non-cathode coating layer comprises amorphous carbon.

5. An all-solid-state battery according to claim 4, characterized in that the amorphous carbon is one or more selected from the group consisting of carbon black, acetylene black, furnace black, Ketjen black, and graphene.

6. An all-solid-state battery according to claim 1, wherein the non-cathode coating layer further comprises a lithium-affinity element that forms an alloy or compound with lithium.

7. An all-solid-state battery according to claim 6, characterized in that the lithium-affinity element is one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn).

8. An all-solid-state battery according to claim 6, characterized in that the non-cathode coating layer contains a lithium-affinity element in a range of 10 to 50 parts by weight per 100 parts by weight of amorphous carbon.

9. An all-solid-state battery according to claim 1, characterized in that the non-cathode coating layer further comprises a binder.

10. The all-solid-state battery according to claim 9, wherein the non-cathode coating layer comprises a binder in a range of 1 to 20 parts by weight per 100 parts by weight of amorphous carbon.

11. An all-solid-state battery according to claim 1, characterized in that the solid electrolyte layer comprises a sulfide-based solid electrolyte.

12. In claim 11, the sulfide-based solid electrolyte is Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, M is one of P, Si, Ge, B, Al, Ga, and In), Li2S-SiS2-P2S5-LiI,Li2S-P2S5,Li2S-P2S5-LiX (X is a halogen element), Li2S-B2S3,Li2S-P2S5-Z m S n (m, n are positive numbers), Z is one of Ge, Zn, or Ga, L i2 S-GeS2,Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2) and Li 7-x PS 6-x I x An all-solid-state battery characterized by being one or more selected from (0≤x≤2).

13. An all-solid-state battery according to claim 1, characterized in that the ratio of the 1C discharge capacity to the 0.1C discharge capacity is 90% or more.

14. An all-solid-state battery according to claim 1, characterized in that the energy density per unit volume is 700 Wh / L or more.

15. A method for manufacturing an all-solid-state battery using lithium or a lithium alloy as a negative electrode active material, wherein A step of forming a non-cathode coating layer on a cathode current collector; A step of forming a solid electrolyte layer on the above-mentioned non-cathode coating layer; Step of stacking an anode on the solid electrolyte layer; and It includes the step of performing a hydrostatic press process, The ratio of the thickness of the solid electrolyte layer to the planar area of ​​the above-mentioned cathode current collector is 0.125 μm / cm 2 Exceeding 1.25 µm / cm 2 A method for manufacturing an all-solid-state battery characterized by being less than 16. In Paragraph 15, A method for manufacturing an all-solid-state battery, characterized in that the step of forming a solid electrolyte layer on the above-mentioned non-cathode coating layer comprises: a step of applying a solid electrolyte slurry on the non-cathode coating layer; and a step of drying the applied solid electrolyte slurry.

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