All-solid-state battery and manufacturing method therefor

Abstract

The present invention relates to an all-solid-state battery comprising: an electrode comprising a current collector layer and an active material layer; a solid electrolyte layer; a first conductive layer between the current collector layer and the active material layer; and a second conductive layer between the active material layer and the solid electrolyte layer. An all-solid-state battery according to one embodiment includes both the first conductive layer and the second conductive layer, and thus ion and electron transfer efficiency is enhanced and an increase in resistance following a battery cycle is mitigated.

Description

All-solid-state battery and manufacturing method thereof

[0001] The present disclosure relates to an all-solid-state battery and a method for manufacturing the same.

[0002] With the recent rapid proliferation of information-related devices such as cameras and mobile phones, as well as communication devices, the development of batteries is becoming increasingly important. Furthermore, the automotive industry is also advancing the development of high-power and high-capacity batteries for electric and hybrid vehicles.

[0003] Current commercially available lithium-ion batteries use electrolytes containing flammable organic solvents. Therefore, safety devices to suppress temperature rise during short circuits and improvements in the structure and materials to prevent short circuits are necessary. In contrast, all-solid-state batteries, which replace the electrolyte with a solid electrolyte layer and solidify the battery, eliminate flammable organic solvents within the battery, simplifying safety devices and improving manufacturing costs and productivity.

[0004] An all-solid-state battery with improved ion and electron transfer efficiency can be provided by one embodiment of the present disclosure.

[0005] Another embodiment of the present disclosure may provide a method for manufacturing the all-solid-state battery.

[0006] One embodiment provides an all-solid-state battery including an electrode including a current collector layer and an active material layer, a solid electrolyte layer, a first conductive layer between the current collector layer and the active material layer, and a second conductive layer between the active material layer and the solid electrolyte layer.

[0007] In one embodiment, the first conductive layer may include at least one compound selected from the group consisting of a lithium-sulfide compound, a lithium-oxide compound, a lithium-hydride compound, and a lithium-halide compound.

[0008] In one embodiment, the first conductive layer may include 70 wt% to 99 wt% of at least one compound selected from the group consisting of lithium-sulfide compounds, lithium-oxide compounds, lithium-hydride compounds, and lithium-halide compounds.

[0009] In one embodiment, the lithium-sulfide compound may include at least one compound selected from the group consisting of lithium phosphorus sulfide (LPS), lithium tin sulfide (LTS), lithium tin phosphorus sulfide (LTPS), lithium germanium phosphorus sulfide (LGPS), lithium phosphorus sulfur halide (LPSHa), and lithium silicon phosphorus sulfur halide (LSiPSHa).

[0010] In one embodiment, the first conductive layer may further include a binder.

[0011] In one embodiment, the first conductive layer may further include a conductive material.

[0012] In one embodiment, the second conductive layer may include at least one compound selected from the group consisting of a lithium-sulfide compound, a lithium-oxide compound, a lithium-hydride compound, and a lithium-halide compound.

[0013] In one embodiment, the second conductive layer may include 70 wt% to 99 wt% of at least one compound selected from the group consisting of lithium-sulfide compounds, lithium-oxide compounds, lithium-hydride compounds, and lithium-halide compounds.

[0014] In one embodiment, the second conductive layer may further include a binder.

[0015] In one embodiment, the second conductive layer may further include a conductive material.

[0016] In one embodiment, the first conductive layer and the second conductive layer may comprise the same lithium-sulfide compound.

[0017] In one embodiment, the first conductive layer and the second conductive layer may each independently include any one of a fluorine-based binder and a rubber-based binder.

[0018] In one embodiment, the first conductive layer and the second conductive layer may each independently include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), or a combination thereof.

[0019] In one embodiment, the first conductive layer and the second conductive layer may comprise the same binder.

[0020] In one embodiment, the first conductive layer and the second conductive layer may each independently include a carbon-based conductive material.

[0021] In one embodiment, the thickness ratio of the first conductive layer and the second conductive layer may be 1:1.0 to 1:5.0.

[0022] In one embodiment, the solid electrolyte layer may include at least one compound selected from the group consisting of a lithium-sulfide compound, a lithium-oxide compound, a lithium-hydride compound, and a lithium-halide compound.

[0023] In one embodiment, the active material layer, the first conductive layer, and the second conductive layer may all include an argyrodite-based compound.

[0024] In one embodiment, both the first conductive layer and the second conductive layer of the solid electrolyte layer may include an argyrodite-based compound.

[0025] In one embodiment, the active material layer may include at least one of a fluorine-based binder and a rubber-based binder.

[0026] In one embodiment, the all-solid-state battery may include a first cathode conductive layer as a first conductive layer, and a second cathode conductive layer as a second conductive layer. That is, the all-solid-state battery may include a cathode including a cathode current collector layer and a cathode active material layer, a solid electrolyte layer, a cathode, a first cathode conductive layer between the cathode current collector layer and the cathode active material layer, and a second cathode conductive layer between the cathode active material layer and the solid electrolyte layer.

[0027] In one embodiment, the negative electrode active material layer may include a rubber-based binder, and the first negative electrode conductive layer and the second negative electrode conductive layer may include a fluorine-based binder.

[0028] In one embodiment, the all-solid-state battery may include a first positive electrode conductive layer as the first conductive layer, and a second positive electrode conductive layer as the second conductive layer. That is, the all-solid-state battery may include a positive electrode including a negative electrode, a solid electrolyte layer, a positive electrode current collector layer, and a positive electrode active material layer, a first positive electrode conductive layer between the positive electrode current collector layer and the positive electrode active material layer, and a second positive electrode conductive layer between the positive electrode active material layer and the solid electrolyte layer.

[0029] In one embodiment, the positive electrode active material layer, the first positive electrode conductive layer, and the second positive electrode conductive layer all include a fluorine-based binder; or the positive electrode active material layer may include a rubber-based binder, and the first positive electrode conductive layer and the second positive electrode conductive layer may include a fluorine-based binder.

[0030] The present disclosure relates to an all-solid-state battery with improved ion and electron transfer efficiency, wherein conductive layers are simultaneously introduced between a current collector and an active material layer, and between an active material layer and a solid electrolyte layer, thereby effectively alleviating an increase in interfacial resistance caused by imperfect interfaces during battery cycle operation. The conductive layers at each interface facilitate the transfer of lithium ions and electrons, and thus, an all-solid-state battery according to an embodiment can realize sufficient charge and discharge capacity to be used as a battery for communication devices or automobiles.

[0031] Figures 1 to 3 schematically illustrate a laminated structure included in an all-solid-state battery according to one embodiment.

[0032] Figure 4 shows a CC-CV charge-discharge graph of an all-solid-state battery manufactured in an example and a comparative example.

[0033] Figure 5 is a graph showing the results of electrochemical impedance spectroscopy (EIS) analysis of all-solid-state batteries manufactured in examples and comparative examples.

[0034] The embodiments described in this specification may be modified in many different forms, and thus the technology according to one implementation is not limited to the embodiments described below. Furthermore, throughout the specification, the terms "comprising," "including," "containing," "includes," or "having" a component do not exclude other components unless specifically stated to the contrary, but rather mean that other components may be included, and do not exclude additional elements, materials, or processes that are not listed.

[0035] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. For example, if the content of a composition is defined as 10% to 80% or 20% to 50%, the numerical ranges of 10% to 50% or 50% to 80% should also be interpreted as being described herein. Unless otherwise specified herein, values ​​outside the numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0036] Unless otherwise specifically defined herein, “about” may be considered a value within 30%, 25%, 20%, 15%, 10%, 5%, 3%, 2%, 1% or 0.5% of the stated value.

[0037] Unless otherwise defined herein, when a part such as a layer, film, thin film, region, plate, etc. is said to be “on” or “over” another part, this includes not only cases where it is “directly on” the other part, but also cases where there are other parts in between.

[0038] Hereinafter, the present disclosure will be described in detail (with reference to the attached drawings). However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0039]

[0040] One embodiment relates to an all-solid-state battery including an electrode including a current collector layer and an active material layer, and a solid electrolyte layer, the all-solid-state battery including a first conductive layer provided between the current collector layer and the active material layer, and a second conductive layer provided between the active material layer and the solid electrolyte layer. The all-solid-state battery according to one embodiment includes both the first conductive layer and the second conductive layer, thereby sufficiently securing an electron transfer path between the current collector layer and the active material layer and an ion transfer path between the active material layer and the solid electrolyte layer, and effectively alleviating resistance at the interface. Through this, the all-solid-state battery according to one embodiment can realize stable charge / discharge efficiency.

[0041] In addition, the solid electrolyte layer used in a high-energy-density all-solid-state battery requires a thickness of approximately 50 μm or less, but short circuits caused by lithium dendrites may occur due to the thin thickness and low physical strength. According to one embodiment, an all-solid-state battery can prevent short circuits caused by dendrite growth occurring at the solid electrolyte grain boundaries by including a conductive layer between the solid electrolyte layer and the active material layer.

[0042] In one embodiment, the first conductive layer and the second conductive layer each independently comprise a conductive material, for example, a solid electrolyte. For example, the conductive layer may comprise a transition metal. The transition metal may comprise one or more of Ti, Zr, Hf, Mn, Co, Ni, Cu, and / or Zn.

[0043] In one embodiment, the first conductive layer may include at least one compound selected from the group consisting of a lithium-sulfide type compound, a lithium-oxide type compound, a lithium-hydride type compound, and a lithium-halide type compound as a solid electrolyte.

[0044] In one embodiment, the first conductive layer may include at least one compound selected from the group consisting of a lithium-sulfide compound, a lithium-oxide compound, a lithium-hydride compound, and a lithium-halide compound, in an amount of 70 wt% to 99 wt%, 80 wt% to 99 wt%, 90 wt% to 99 wt%, 92 wt% to 98 wt%, 94 wt% to 96 wt%, or about 95.5 wt% relative to the weight of the first conductive layer.

[0045] In one embodiment, the first conductive layer may include a lithium-sulfide compound, and specifically, the lithium-sulfide compound may be lithium phosphorus sulfide (LPS) (eg Li3PS4), lithium tin sulfide (LTS) (eg Li4SnS4), lithium tin phosphorus sulfide (LTPS) (eg Li 10 SnP2S 12 ), LGPS(Lithium germanium phosphorus sulfide) (eg Li 10 GeP2S 12 ), LPSHa(Lithium phosphorus sulfur halide) (eg Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS 6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and / or LSiPSHa(Lithium silicon phosphorus sulfur halide) (e.g. Li 6+x2-y1 Si x2 P 1-x2 S 5-y1 Ha 1+y1 (0 <x2<0.4, 0≤y1≤0.5, Ha=F, Cl, Br 또는 I)) 중 어느 1종 이상의 화합물을 포함하는 것일 수 있으며, 더욱 구체적으로 아지로다이트계 화합물(Li6PS5Cl)을 포함할 수 있으나, 이에 제한되지 않는다.

[0046] In one embodiment, the first conductive layer or the slurry for forming the first conductive layer may further include a conductive material. The conductive material may be, for example, a linear conductive material and / or a dot-shaped conductive material, and may include, but is not limited to, a carbon-based conductive material such as graphite, carbon black, carbon nanotubes, carbon nanofibers, carbon fibers, acetylene black, Ketjen black, graphene, vapor-grown carbon fibers (VGCF), and / or a metal-based conductive material including, but not limited to, tin, tin oxide, titanium oxide, LaSrCoO3, and LaSrMnO3.

[0047] Specifically, the first conductive layer may include the conductive material in an amount of 0.1 wt% to 5 wt%, 0.1 wt% to 3 wt%, 0.5 wt% to 3 wt%, 1 wt% to 3 wt%, 1 wt% to 2 wt%, or about 1.5 wt% relative to the weight of the first conductive layer.

[0048] In one embodiment, the first conductive layer or the slurry for forming the first conductive layer may include a binder. The binder may include, for example, a non-aqueous binder and / or an aqueous binder. The binder may include, for example, a fluorinated binder and / or a rubber-based binder. The binder may include, but is not limited to, polyvinylidenefluoride (PVDF), vinylidenefluoride-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), polyacrylonitrile, polymethylmethacrylate, acrylonitrile-butadiene rubber (NBR), polybutadiene rubber (BR), and / or styrene-butadiene rubber (SBR).

[0049] Specifically, the first conductive layer may include the binder in an amount of 1 wt% to 10 wt%, 1 wt% to 6 wt%, 2 wt% to 5 wt%, or about 3 wt% relative to the weight of the first conductive layer.

[0050] In one embodiment, the second conductive layer or the slurry for forming the second conductive layer may include at least one compound selected from the group consisting of a lithium-sulfide type compound, a lithium-oxide type compound, a lithium-hydride type compound, and a lithium-halide type compound as a solid electrolyte.

[0051] In one embodiment, the second conductive layer may include at least one compound selected from the group consisting of a lithium-sulfide compound, a lithium-oxide compound, a lithium-hydride compound, and a lithium-halide compound, in an amount of 70 wt% to 99 wt%, 80 wt% to 99 wt%, 90 wt% to 99 wt%, 92 wt% to 98 wt%, 94 wt% to 96 wt%, or about 95.5 wt%, based on the total weight of the second conductive layer.

[0052] In one embodiment, the second conductive layer or the slurry for forming the second conductive layer may include a lithium-sulfide compound, and specifically, the lithium-sulfide compound may be lithium phosphorus sulfide (LPS) (eg Li3PS4), lithium tin sulfide (LTS) (eg Li4SnS4), lithium tin phosphorus sulfide (LTPS) (eg Li 10 SnP2S 12 ), LGPS(Lithium germanium phosphorus sulfide) (eg Li 10 GeP2S 12 ), LPSHa(Lithium phosphorus sulfur halide) (eg Li6PS5Cl, Li7P2S8ClI, Li 7-x1PS 6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and / or LSiPSHa(Lithium silicon phosphorus sulfur halide) (e.g. Li 6+x2-y1 Si x2 P 1-x2 S 5-y1 Ha 1+y1 (0 <x2<0.4, 0≤y1≤0.5, Ha=F, Cl, Br 또는 I)) 중 어느 1종 이상의 화합물을 포함하는 것일 수 있으며, 더욱 구체적으로 아지로다이트계 화합물(Li6PS5Cl)을 포함할 수 있으나, 이에 제한되지 않는다.

[0053] The first conductive layer and the second conductive layer may include the same or different solid electrolytes, for example, they may include the same solid electrolytes, and specifically, they may include the same lithium-sulfide compound.

[0054] In one embodiment, both the first conductive layer and the second conductive layer may include a lithium-sulfide compound, specifically, lithium phosphorus sulfur halide (LPSHa) (e.g., Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS 6-x1 Ha x1(0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and more specifically, it may include an argyrodite compound (Li6PS5Cl). Here, the particle sizes of the argyrodite compounds included in each layer may be the same or different. In one embodiment, the second conductive layer or the slurry for forming the second conductive layer may further include a conductive material. The conductive material may be, for example, a linear conductive material and / or a dot-shaped conductive material, and may include, but is not limited to, a carbon-based conductive material such as graphite, carbon black, carbon nanotubes, carbon nanofibers, carbon fibers, acetylene black, Ketjen black, graphene, and vapor-grown carbon fibers (VGCF), and / or a metal-based conductive material including a perovskite material such as tin, tin oxide, titanium oxide, LaSrCoO3, and LaSrMnO3.

[0055] Specifically, the second conductive layer may include the conductive material in an amount of 0.1 wt% to 5 wt%, 0.1 wt% to 3 wt%, 0.5 wt% to 3 wt%, 1 wt% to 3 wt%, 1 wt% to 2 wt%, or about 1.5 wt% relative to the weight of the second conductive layer.

[0056] The first conductive layer and the second conductive layer may include the same or different conductive materials, for example, they may include the same conductive materials, and specifically, they may both include carbon-based conductive materials.

[0057] In one embodiment, the second conductive layer or the slurry for forming the second conductive layer may include a binder. The binder may include, for example, a non-aqueous binder and / or an aqueous binder. The binder may include, for example, a fluorinated binder and / or a rubber-based binder. The binder may include, but is not limited to, for example, polyvinylidenefluoride (PVDF), vinylidenefluoride-co-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), polyacrylonitrile, polymethylmethacrylate, acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), and / or styrene-butadiene rubber (SBR). The second conductive layer may include the binder in an amount of 1 wt% to 10 wt%, 1 wt% to 6 wt%, 2 wt% to 5 wt%, or about 3 wt% relative to the weight of the second conductive layer.

[0058] In one embodiment, the first conductive layer and the second conductive layer may include the same or different binders, for example, they may include the same binder, for example, they may both include a fluorinated binder. Specifically, the first conductive layer and the second conductive layer may include polyvinylidenefluoride (PVDF), vinylidenefluoride-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), or a combination thereof.

[0059] In one embodiment, the thickness of the first conductive layer may be from 10 μm to 100 μm, from 10 μm to 80 μm, or from 20 μm to 70 μm. Specifically, the thickness of the first anode conductive layer may be from 10 μm to 50 μm, from 10 μm to 40 μm, from 10 μm to 30 μm, from 20 μm to 30 μm, or about 24 μm, but is not necessarily limited thereto. The thickness of the first cathode conductive layer may be from 40 μm to 100 μm, from 40 μm to 80 μm, from 50 μm to 70 μm, or about 60 μm, but is not necessarily limited thereto.

[0060] In one embodiment, the thickness of the second conductive layer can be from 30 μm to 150 μm, from 30 μm to 120 μm, from 30 μm to 100 μm, from 40 μm to 90 μm, or from 50 μm to 80 μm. Specifically, the thickness of the second anode conductive layer can be from 30 μm to 100 μm, from 40 μm to 80 μm, from 40 μm to 60 μm, from 50 μm to 60 μm, or about 55 μm, but is not necessarily limited thereto. The thickness of the second cathode conductive layer can be from 50 μm to 150 μm, from 50 μm to 100 μm, from 60 μm to 100 μm, from 70 μm to 90 μm, or about 80 μm, but is not necessarily limited thereto.

[0061] In one embodiment, the ratio of the thicknesses of the first conductive layer and the second conductive layer may be 1:1.0 to 1:5.0, 1:1.11 to 1:30, 1:11 to 1:2.5, or 1:1.3 to 1:2.3. Specifically, the ratio of the thicknesses of the first anode conductive layer and the second anode conductive layer may be 1:1.5 to 1:5.0, 1:1.5 to 1:3.0, 1:2.0 to 1:3.0, 1:2.0 to 1:2.5, or about 1:2.3, but is not necessarily limited thereto. The ratio of the thicknesses of the first cathode conductive layer and the second cathode conductive layer may be, but is not necessarily limited to, 1:1.0 to 1:2.0, 1:1.1 to 1:2.0, 1:1.1 to 1:1.5, or about 1:1.3.

[0062] The thickness of the solid electrolyte layer may be 1 μm to 1000 μm, 1 μm to 800 μm, 10 μm to 800 μm, 10 μm to 200 μm, 30 μm to 150 μm, 30 μm to 100 μm, 500 μm to 900 μm, or 600 μm to 700 μm, but is not necessarily limited thereto and may be changed depending on the purpose.

[0063] In one embodiment, the solid electrolyte layer may include an inorganic solid electrolyte.

[0064] The above solid electrolyte layer may include at least one compound selected from the group consisting of lithium-sulfide type compounds, lithium-oxide type compounds, lithium-hydride type compounds, and lithium-halide type compounds.

[0065] Specifically, the solid electrolyte layer may include a lithium-sulfide compound, and specifically, the lithium-sulfide compound may be lithium phosphorus sulfide (LPS) (eg Li3PS4), lithium tin sulfide (LTS) (eg Li4SnS4), lithium tin phosphorus sulfide (LTPS) (eg Li 10 SnP2S 12 ), LGPS(Lithium germanium phosphorus sulfide) (eg Li 10 GeP2S 12 ), LPSHa(Lithium phosphorus sulfur halide) (eg Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS 6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and / or LSiPSHa(Lithium silicon phosphorus sulfur halide) (e.g. Li 6+x2-y1 Si x2 P 1-x2 S 5-y1 Ha 1+y1 (0 <x2<0.4, 0≤y1≤0.5, Ha=F, Cl, Br 또는 I)) 중 어느 1종 이상의 화합물을 포함하는 것일 수 있으며, 더욱 구체적으로 아지로다이트계 화합물(Li6PS5Cl)을 포함할 수 있으나, 이에 제한되지 않는다.

[0066] In one embodiment, the solid electrolyte layer and the electrode may include the same or different solid electrolytes, and specifically, the solid electrolyte layer and the first conductive layer and the second conductive layer may include the same or different solid electrolytes, for example, may include the same solid electrolytes. Here, the solid electrolyte is LPSHa (Lithium phosphorus sulfur halide) (e.g., Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and more specifically, may include an azirodite compound. Here, the particle sizes of the azirodite compound included in each layer may be the same or different.

[0067] In one embodiment, the active material layer may include a solid electrolyte, and may include at least one compound selected from the group consisting of a lithium-sulfide type compound, a lithium-oxide type compound, a lithium-hydride type compound, and a lithium-halide type compound. Specifically, the solid electrolyte may include a lithium-sulfide type compound, and specifically, the lithium-sulfide type compound is selected from the group consisting of lithium phosphorus sulfide (LPS) (eg Li3PS4), lithium tin sulfide (LTS) (eg Li4SnS4), lithium tin phosphorus sulfide (LTPS) (eg Li 10 SnP2S 12 ), LGPS(Lithium germanium phosphorus sulfide) (eg Li 10 GeP2S 12 ), LPSHa(Lithium phosphorus sulfur halide) (eg Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS 6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and / or LSiPSHa(Lithium silicon phosphorus sulfur halide) (e.g. Li 6+x2-y1 Si x2 P 1-x2 S 5-y1 Ha 1+y1(0 <x2<0.4, 0≤y1≤0.5, Ha=F, Cl, Br 또는 I)) 중 어느 1종 이상의 화합물을 포함하는 것일 수 있으며, 더욱 구체적으로 아지로다이트계 화합물(Li6PS5Cl)을 포함할 수 있으나, 이에 제한되지 않는다.

[0068] Specifically, the solid electrolyte layer and the active material layer, first conductive layer, and second conductive layer of the electrode may include the same or different solid electrolytes, and for example, may all include an argyrodite-based compound. Here, the particle sizes of the argyrodite-based compounds included in each layer may be the same or different.

[0069] The active material layer may include a binder, and the binder may include, for example, a non-aqueous binder and / or an aqueous binder. The binder may include, for example, a fluorinated binder and / or a rubber-based binder. The binder may include, but is not limited to, polyvinylidenefluoride (PVDF), vinylidenefluoride-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), polyacrylonitrile, polymethylmethacrylate, acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), and / or styrene-butadiene rubber (SBR).

[0070] In one embodiment, when a structure in which a current collector layer, a first conductive layer, an active material layer, and a second conductive layer are sequentially laminated is referred to as a composite electrode, an all-solid-state battery according to one embodiment may include a composite negative electrode (10) including a negative current collector layer (11), a first negative electrode conductive layer (12), a negative electrode active material layer (13), and a second negative electrode conductive layer (14). Alternatively, an all-solid-state battery according to one embodiment may include a composite positive electrode (30) including a positive current collector layer (31), a first positive electrode conductive layer (32), a positive electrode active material layer (33), and a second positive electrode conductive layer (34).

[0071] An all-solid-state battery according to one embodiment may include a composite negative electrode (10), a solid electrolyte layer (20), a positive electrode current collector layer (31), and a positive electrode active material layer (33), or an all-solid-state battery according to one embodiment may include a negative electrode current collector layer (11), a negative electrode active material layer (13), a solid electrolyte layer (20), and a composite negative electrode (10), or an all-solid-state battery according to one embodiment may include a composite negative electrode (10), a solid electrolyte layer (20), and a composite positive electrode (30).

[0072]

[0073] Another embodiment provides a method for manufacturing an all-solid-state battery according to the above embodiment. In one embodiment, the method for manufacturing an all-solid-state battery includes the steps of: applying a slurry for forming a first conductive layer on a current collector and then forming a first conductive layer; applying a slurry for forming an active material layer on the first conductive layer and then forming an active material layer; and applying a slurry for forming a second conductive layer on the active material layer and then forming a second conductive layer.

[0074]

[0075] Below, an all-solid-state battery according to an implementation example is described.

[0076] [anode]

[0077] The positive electrode may include a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.

[0078] According to one embodiment, the positive electrode (more specifically, the positive electrode active material layer) may include a solid electrolyte, and for example, may include at least one solid electrolyte selected from the group consisting of lithium-sulfide compounds, lithium-oxide compounds, lithium-hydride compounds, and lithium-halide compounds. Specific examples of the solid electrolyte include lithium phosphorus sulfide (LPS) (eg Li3PS4), lithium tin sulfide (LTS) (eg Li4SnS4), and lithium tin phosphorus sulfide (LTPS) (eg Li 10 SnP2S 12 ), LGPS(Lithium germanium phosphorus sulfide) (eg Li 10 GeP2S 12 ), LPSHa(Lithium phosphorus sulfur halide) (eg Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS 6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and / or LSiPSHa(Lithium silicon phosphorus sulfur halide) (e.g. Li 6+x2-y1 Si x2 P 1-x2 S 5-y1 Ha 1+y1 (0 <x2<0.4, 0≤y1≤0.5, Ha=F, Cl, Br 또는 I)) 중 어느 1종 이상의 화합물을 포함하는 것일 수 있으나, 이에 제한되지 않는다. 더욱 구체적으로는 상기 양극(더욱 구체적으로는 양극 활물질층)은 아지로다이트계 화합물을 포함할 수 있다.

[0079] (positive current collector)

[0080] The positive electrode current collector may comprise stainless steel, nickel, aluminum, titanium, or an alloy thereof. The positive electrode current collector may also comprise aluminum or stainless steel surface-treated with carbon, nickel, titanium, or silver. The positive electrode current collector may have a thickness of, but is not limited to, 1 to 50 μm, for example.

[0081] (positive electrode)

[0082] The positive electrode active material layer may include a positive electrode active material. The positive electrode active material may include a compound capable of reversibly intercalating and deintercalating lithium ions.

[0083] According to exemplary embodiments, the positive electrode active material may include a lithium-nickel metal oxide. The lithium-nickel metal oxide may further include at least one of cobalt (Co), manganese (Mn), and aluminum (Al).

[0084] In some embodiments, the positive electrode active material or the lithium-nickel metal oxide may include a layered structure or crystal structure represented by the following chemical formula 1.

[0085] [Chemical Formula 1]

[0086] Li x Ni a M b O 2+z

[0087] In Chemical Formula 1, 0.9≤x≤1.2, 0.6≤a≤0.99, 0.01≤b≤0.4, -0.5≤z≤0.1 may be satisfied. As described above, M may include Co, Mn, and / or Al.

[0088] The chemical structure represented by Chemical Formula 1 represents the bonding relationship included in the layered structure or crystal structure of the positive electrode active material and does not exclude other additional elements. For example, M includes Co and / or Mn, and Co and / or Mn can serve as the main active element of the positive electrode active material together with Ni. Chemical Formula 1 is provided to express the bonding relationship of the above main active elements and should be understood as a formula encompassing the introduction and substitution of additional elements.

[0089] In one embodiment, auxiliary elements may be further included in addition to the main active element to enhance the chemical stability of the positive electrode active material or the layered structure / crystal structure. The auxiliary elements may be incorporated into the layered structure / crystal structure to form bonds, and in this case, it should be understood that they are also included within the chemical structure range represented by Chemical Formula 1.

[0090] The auxiliary element may include, for example, at least one of Na, Mg, Ca, Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, Fe, Cu, Ag, Zn, B, Al, Ga, C, Si, Sn, Sr, Ba, Ra, P, or Zr. The auxiliary element may also act as an auxiliary active element that contributes to the capacity / output activity of the positive electrode active material together with Co or Mn, for example, Al.

[0091] For example, the positive electrode active material or the lithium-nickel metal oxide may include a layered structure or crystal structure represented by the following chemical formula 1-1.

[0092] [Chemical Formula 1-1]

[0093] Li x Ni a M1 b1 M2 b2 O 2+z

[0094] In Chemical Formula 1, M1 may include Co, Mn, and / or Al. M2 may include the auxiliary elements described above. In Chemical Formula 1-1, 0.9≤x≤1.2, 0.6≤a≤0.99, 0.01≤b1+b2≤0.4, -0.5≤z≤0.1 may be satisfied.

[0095] The above-described positive electrode active material may further include a coating element or doping element. For example, elements substantially identical to or similar to the above-described auxiliary elements may be used as the coating element or doping element. For example, the above-described elements may be used singly or in combination of two or more.

[0096] The above coating element or doping element may be present on the surface of the lithium-nickel metal oxide particle, or may penetrate through the surface of the lithium-nickel metal composite oxide particle and be included in the bonding structure represented by the above chemical formula 1 or chemical formula 1-1.

[0097] The above positive electrode active material may include a nickel-cobalt-manganese (NCM) lithium oxide. In this case, an NCM lithium oxide with an increased nickel content may be used.

[0098] Ni can be provided as a transition metal associated with the output and capacity of a lithium secondary battery. Therefore, by employing a high-content (High-Ni) composition as described above in the positive electrode active material, a high-capacity positive electrode and a high-capacity lithium secondary battery can be provided.

[0099] However, as the Ni content increases, the long-term storage stability and lifespan stability of the cathode or secondary battery may relatively deteriorate, and side reactions with the electrolyte may also increase. However, according to exemplary embodiments, the inclusion of Co can maintain electrical conductivity, while improving lifespan stability and capacity retention characteristics through Mn.

[0100] The content of Ni (e.g., the mole fraction of nickel among the total moles of nickel, cobalt, and manganese) in the NCM-based lithium oxide may be 0.6 or more, 0.7 or more, or 0.8 or more. In some embodiments, the content of Ni may be 0.8 to 0.95, 0.82 to 0.95, 0.83 to 0.95, 0.84 to 0.95, 0.85 to 0.95, or 0.88 to 0.95.

[0101] In some embodiments, the positive electrode active material may include a lithium cobalt oxide-based active material, a lithium manganese oxide-based active material, a lithium nickel oxide-based active material, or a lithium iron phosphate (LFP)-based active material (e.g., LiFePO4).

[0102] In some embodiments, the positive electrode active material may include, for example, a Mn-rich active material, an LLO (Li rich layered oxide) / OLO (Over Lithiated Oxide) active material, or a Co-less active material having a chemical structure or crystal structure represented by Chemical Formula 2.

[0103] [Chemical Formula 2]

[0104] p[Li2MnO3]·(1-p)[Li q JO2]

[0105] In chemical formula 2, 0 <p<1이고, 0.9≤q≤1.2이며, J는 Mn, Ni, Co, Fe, Cr, V, Cu, Zn, Ti, Al, Mg 및 B 중 적어도 하나의 원소를 포함할 수 있다.

[0106] (Method of manufacturing positive electrode)

[0107] For example, a slurry for forming a positive electrode active material layer can be prepared by mixing the positive electrode active material in a solvent. The slurry for forming a positive electrode active material layer can be coated on a positive electrode current collector, and then dried and rolled to prepare a positive electrode active material layer. The coating process can be performed by a method such as gravure coating, slot die coating, multilayer simultaneous die coating, imprinting, doctor blade coating, dip coating, bar coating, casting, etc., but is not limited thereto. The positive electrode active material layer can further include a binder and optionally can further include a conductive agent, a thickener, etc. Here, the binder and the conductive agent can be as described above.

[0108] (positive solvent)

[0109] Non-limiting examples of solvents used in the preparation of the above-described positive electrode mixture include N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethylacetamide, N,N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, isobutyl isobutyrate, butyl butyrate, xylene, anisole, and the like.

[0110] (positive binder)

[0111] The above-described positive electrode active material layer may include a binder, and the binder may be the same as or different from the binder used in the first conductive layer and the second conductive layer described above, and specifically, a different binder may be used.

[0112] The binder may include, for example, a non-aqueous binder and / or an aqueous binder. The binder may include, for example, a fluorinated binder and / or a rubber-based binder. The above binder may include polyvinylidene fluoride (PVDF), vinylidene fluoride-co-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), polyacrylonitrile, polymethylmethacrylate, acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), etc. In one embodiment, a rubber-based binder may be used as the positive electrode binder, and specifically, acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), and more specifically, acrylonitrile butadiene rubber (NBR).

[0113] According to one embodiment, the positive electrode active material layer, the first positive electrode conductive layer, and the second positive electrode conductive layer may all include a fluorine-based binder; or the positive electrode active material layer may include a rubber-based binder, and the first positive electrode conductive layer and the second positive electrode conductive layer may include a fluorine-based binder.

[0114] (positive electrode)

[0115] The conductive material may be added to enhance the conductivity of the positive electrode material layer and / or the mobility of lithium ions or electrons. For example, the conductive material may be a linear conductive material and / or a dot-shaped conductive material, and may include, but is not limited to, a carbon-based conductive material such as graphite, carbon black, acetylene black, Ketjen black, graphene, carbon nanotubes, vapor-grown carbon fibers (VGCF), carbon fibers, carbon nanofibers, and / or a metal-based conductive material including a perovskite material such as tin, tin oxide, titanium oxide, LaSrCoO3, and LaSrMnO3.

[0116] (Polar thickener / dispersant)

[0117] If necessary, the positive electrode mixture may further include a thickener and / or a dispersant. In one embodiment, the positive electrode mixture may include a thickener such as carboxymethyl cellulose (CMC).

[0118]

[0119] [cathode]

[0120] The negative electrode may include a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.

[0121] According to one embodiment, the negative electrode (more specifically, the negative electrode active material layer) may include a solid electrolyte, and for example, may include at least one solid electrolyte selected from the group consisting of lithium-sulfide compounds, lithium-oxide compounds, lithium-hydride compounds, and lithium-halide compounds. Specific examples of the solid electrolyte include lithium phosphorus sulfide (LPS) (eg Li3PS4), lithium tin sulfide (LTS) (eg Li4SnS4), and lithium tin phosphorus sulfide (LTPS) (eg Li 10 SnP2S 12), LGPS(Lithium germanium phosphorus sulfide) (eg Li 10 GeP2S 12 ), LPSHa(Lithium phosphorus sulfur halide) (eg Li6PS5Cl, Li7P2S8ClI, Li 7-x1 PS 6-x1 Ha x1 (0.2≤x1≤1.8, Ha=F, Cl, Br or I)), and / or LSiPSHa(Lithium silicon phosphorus sulfur halide) (e.g. Li 6+x2-y1 Si x2 P 1-x2 S 5-y1 Ha 1+y1 (0 <x2<0.4, 0≤y1≤0.5, Ha=F, Cl, Br 또는 I)) 중 어느 1종 이상의 화합물을 포함하는 것일 수 있으나, 이에 제한되지 않는다. 더욱 구체적으로는 상기 음극(더욱 구체적으로는 음극 활물질층)은 아지로다이트계 화합물을 포함할 수 있다.

[0122] (negative current collector)

[0123] Non-limiting examples of the negative electrode current collector include copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, and a polymer substrate coated with a conductive metal. The negative electrode current collector may have a thickness of, but is not limited to, 1 to 50 μm.

[0124] (negative electrode material)

[0125] The negative electrode active material layer may include a negative electrode active material. A material capable of adsorbing and desorbing lithium ions may be used as the negative electrode active material. For example, the negative electrode active material may be a carbon-based material such as crystalline carbon, amorphous carbon, carbon composites, or carbon fiber; lithium metal; lithium alloy; a silicon (Si)-containing material, or a tin (Sn)-containing material.

[0126] Examples of the above amorphous carbon include hard carbon, soft carbon, coke, mesocarbon microbead (MCMB), and mesophase pitch-based carbon fiber (MPCF).

[0127] Examples of the above crystalline carbon include graphite-based carbons such as natural graphite, artificial graphite, graphitized coke, graphitized MCMB, and graphitized MPCF.

[0128] The lithium metal may be pure lithium metal or lithium metal with a protective layer formed thereon for suppressing dendrite growth, etc. In one embodiment, a lithium metal-containing layer deposited or coated on a negative electrode current collector may be used as the negative electrode active material layer. In one embodiment, a lithium thin film layer may be used as the negative electrode active material layer.

[0129] Elements included in the above lithium alloy include aluminum, zinc, bismuth, cadmium, antimony, silicon, lead, tin, gallium, or indium.

[0130] The above silicon-containing material can provide increased capacity characteristics. The above silicon-containing material is Si, SiOx(0 <x<2), 금속 도핑된 SiOx(0<x<2), 실리콘-탄소 복합체 등을 포함할 수 있다. 상기 금속은 리튬 및 / 또는 마그네슘을 포함할 수 있으며, 금속 도핑된 SiOx(0<x<2)는 금속 실리케이트를 포함할 수 있다.

[0131] (Method of manufacturing cathode)

[0132] For example, the negative electrode active material can be mixed in a solvent to prepare a negative electrode slurry. After the negative electrode slurry is coated / deposited on a negative electrode current collector, drying and rolling can be performed to prepare a negative electrode mixture layer. The coating process can be performed by methods such as gravure coating, slot die coating, multilayer simultaneous die coating, imprinting, doctor blade coating, dip coating, bar coating, casting, etc., but is not limited thereto. The negative electrode mixture layer can further include a binder and optionally can further include a conductive material, a thickener, etc.

[0133] In some embodiments, the negative electrode may include a layer of negative active material in the form of lithium metal formed through a deposition / coating process.

[0134] (negative solvent)

[0135] Non-limiting examples of the solvent for the above negative electrode mixture include water, pure water, deionized water, distilled water, ethanol, isopropanol, methanol, acetone, n-propanol, t-butanol, isobutyl isobutyrate, butyl butyrate, xylene, anisole, etc.

[0136] (negative binder / conductive material / thickener)

[0137] The above-described materials that can be used in manufacturing the anode as the binder, conductive agent and thickener can be used.

[0138] In some embodiments, the negative electrode active material layer may include a rubber-based binder, and the first negative electrode conductive layer and the second negative electrode conductive layer may include a fluorine-based binder. In some embodiments, a rubber-based binder such as a styrene-butadiene rubber (SBR)-based binder, carboxymethyl cellulose (CMC), a polyacrylic acid-based binder, a poly(3,4-ethylenedioxythiophene, PEDOT)-based binder, or the like may be used as the negative electrode binder.

[0139]

[0140] [Electrode assembly]

[0141] According to exemplary embodiments, an electrode assembly may be formed by repeatedly arranging a positive electrode, a negative electrode, and a solid electrolyte layer. In some embodiments, the electrode assembly may be of a winding type, a stacking type, a z-folding type, or a stack-folding type. In some embodiments, the electrode assembly may further include a separator as needed.

[0142]

[0143] [Solid electrolyte layer]

[0144] The above solid electrolyte layer may include an inorganic solid electrolyte.

[0145] For example, the solid electrolyte layer may include a lithium-sulfide-based, lithium-oxide-based, lithium-hydride-based, and lithium-halide-based solid electrolyte. As a non-limiting example, the solid electrolyte layer may include at least one compound selected from the group consisting of lithium phosphorus sulfide (LPS), lithium tin sulfide (LTS), lithium tin phosphorus sulfide (LTPS), lithium germanium phosphorus sulfide (LGPS), lithium phosphorus sulfur halide (LPSHa), and lithium silicon phosphorus sulfur halide (LSiPSHa), and more specifically, Li2S-P2S5, Li2S-P2S5-LiCl, Li2S-P2S5-LiBr, Li2S-P2S5-LiCl-LiBr, Li2S-P2S5-Li 2O , Li2S-P2S5-Li 2O -LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z m S n (m, n are positive numbers, Z is Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q , (p, q are positive numbers, M is P, Si, Ge, B, Al, Ga, or In), Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), Li 7-x PS 6-x I x(0≤x≤2) etc. These may be used alone or in combination of two or more. Specifically, the solid electrolyte layer may include an argyrodite compound.

[0146] In one embodiment, the solid electrolyte layer is, for example, Li 2O -B2O3-P2O5, Li 2O -SiO2, Li 2O -B2O3, Li 2O -It may also include an oxide-based amorphous solid electrolyte such as B2O3-ZnO.

[0147] In one embodiment, the solid electrolyte included in the solid electrolyte layer may be the same as or different from the solid electrolyte included in the electrode (positive electrode and / or negative electrode), and specifically, the same solid electrolyte may be used.

[0148] In one embodiment, both the solid electrolyte layer and the electrode may include an argyrodite-based compound. Specifically, both the solid electrolyte layer and the first conductive layer and the second conductive layer of the electrode may include an argyrodite-based compound. More specifically, both the solid electrolyte layer and the active material layer, the first conductive layer, and the second conductive layer of the electrode may include an argyrodite-based compound. Here, the particle sizes of the argyrodite-based compounds included in each layer may be the same or different.

[0149]

[0150] [Cell structure]

[0151] For example, electrode tabs (positive tab and negative tab) may protrude from the positive current collector and negative current collector, respectively, and extend to one side of the case. The electrode tabs may be fused together with the one side of the case and connected to electrode leads (positive lead and negative lead) that extend or are exposed to the outside of the case.

[0152] For example, pouch-shaped cases, square cases, cylindrical cases, coin-shaped cases, etc. can be used.

[0153] Hereinafter, the embodiments will be further described with reference to specific experimental examples. The examples and comparative examples included in the experimental examples are merely illustrative of one implementation and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the examples are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended claims.

[0154]

[0155] <Experimental Method>

[0156] 1. Measurement of charge and discharge capacity

[0157] A constant current was applied at 0.1 C rate at 30 ℃ until the battery voltage reached 4.2 V (vs. Li). When the battery voltage reached 4.2 V, the battery was charged by applying a constant voltage until the current reached 0.01 C rate. During discharge, the battery was discharged at a constant current of 0.1 C rate until the voltage reached 2.5 V (vs. Li).

[0158] 2. Interfacial resistance measurement

[0159] The resistance of the all-solid-state batteries manufactured in the above examples and comparative examples was measured using an electrochemical impedance spectroscopy (EIS, VMP-300 Potentiostat) at room temperature, with an amplitude of 10 mV, and under conditions of 7 MHz to 1 Hz.

[0160]

[0161] <Example>

[0162] A slurry for forming a conductive layer was prepared by adding and mixing a conductive agent (carbon black) into a slurry containing a lithium-sulfide compound (Argyrodite Li6PS5Cl) having a bi-modal particle size distribution and a binder (PVdF-HFP). The weight ratio of the lithium-sulfide compound, binder, and conductive agent was 95.5:3:1.5.

[0163] Li[Ni as a cathode active material 0.8 Co 0.1 Mn 0.1 ]O2, A slurry for forming a cathode active material was prepared by mixing carbon black as a conductive agent, neodymium polybutadiene (NdBR) as a binder, and Argyrodite Li6PS5Cl as a solid electrolyte in a weight ratio of 77:20:1.5:1.5.

[0164] SiC as a negative active material, A slurry for forming a negative electrode active material was prepared by mixing Argyrodite Li6PS5Cl as a solid electrolyte, carbon black as a conductive material, and styrene-butadiene rubber (SBR) as a binder in a weight ratio of 77:19.5:1.5:2.

[0165] A slurry for forming a conductive layer, a slurry for forming a positive electrode active material, and a slurry for forming a conductive layer were sequentially cast on an aluminum positive electrode current collector, and then dried for 6 hours or more to manufacture a composite positive electrode including a positive electrode current collector layer (thickness: about 20 μm), a first positive electrode conductive layer (thickness: about 24 μm), a positive electrode active material layer (thickness: about 115 μm), and a second positive electrode conductive layer (thickness: about 55 μm).

[0166] A slurry for forming a conductive layer, a slurry for forming a negative electrode active material, and a slurry for forming a conductive layer were sequentially cast on a copper negative electrode current collector, and then dried for 6 hours or more to manufacture a composite negative electrode including a negative electrode current collector layer (thickness: about 8 μm), a first negative electrode conductive layer (thickness: about 60 μm), a negative electrode active material layer (thickness: about 50 μm), and a second negative electrode conductive layer (thickness: about 80 μm).

[0167] After solid electrolyte powder (Li6PS5Cl) was injected into the mold, a solid electrolyte layer (approximately 650 μm thick) was formed through pressurization of 1.4 tons, and then the composite cathode and composite anode manufactured above were laminated on top and bottom of the solid electrolyte layer, and then an all-solid-state battery was manufactured through pressurization of 3.4 tons.

[0168]

[0169] <Comparative Example 1>

[0170] In the method for manufacturing an all-solid-state battery according to the above embodiment, an all-solid-state battery was manufactured using the same method except for the step of forming a second positive electrode conductive layer and a second negative electrode conductive layer.

[0171]

[0172] <Comparative Example 2>

[0173] In the method for manufacturing an all-solid-state battery according to the above embodiment, an all-solid-state battery was manufactured using the same method except for the step of forming the first positive electrode conductive layer and the first negative electrode conductive layer.

[0174]

[0175] <Experimental Example>

[0176] According to the above <Experimental Method>, the charge / discharge capacity and interfacial resistance of the all-solid-state batteries manufactured in the above Examples and Comparative Examples were measured, and the results are shown in FIGS. 4 and 5, respectively. Through the EIS analysis results in FIG. 5, it can be confirmed that the impedance is greatly relaxed in the battery according to the Example compared to Comparative Example 2 which does not include the first conductive layer. In addition, through FIG. 4, it can be confirmed that the charge / discharge capacity of the battery according to the Example is significantly increased compared to Comparative Examples 1 and 2. The all-solid-state battery of the Example includes conductive layers between the solid electrolyte layer and the active material layer, and between the current collector layer and the active material layer, thereby simultaneously improving the ion conduction between the solid electrolyte layer and the active material layer and the electron transfer efficiency between the current collector layer and the active material layer, resulting in a significant decrease in the resistance after cycling compared to Comparative Examples 1 and 2, resulting in a significant increase in the charge / discharge capacity.

[0177]

[0178] The above description is merely an example of applying the principles of the present disclosure, and other configurations may be included without departing from the scope of the present disclosure. While one embodiment has been described in detail through examples and experimental examples, the scope of one embodiment is not limited to the specific examples, and should be interpreted in accordance with the appended claims.

[0179] [Description of drawing symbols]

[0180] 10: Composite cathode 11: Cathode current collector layer

[0181] 12: First cathode conductive layer 13: Cathode active material layer

[0182] 14: Second cathode conductive layer 20: Solid electrolyte layer

[0183] 30: Composite anode 31: Anode current collector layer

[0184] 32: First positive electrode conductive layer 33: Positive electrode active material layer

[0185] 34: Second anode conducting layer

Claims

1. An electrode including a current collector layer and an active material layer; solid electrolyte layer; A first conductive layer between the current collector layer and the active material layer; and An all-solid-state battery comprising a second conductive layer between the active material layer and the solid electrolyte layer.

2. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer each independently comprise at least one compound selected from the group consisting of a lithium-sulfide compound, a lithium-oxide compound, a lithium-hydride compound, and a lithium-halide compound.

3. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer each independently contain 70 to 99 wt% of at least one compound selected from the group consisting of lithium-sulfide compounds, lithium-oxide compounds, lithium-hydride compounds, and lithium-halide compounds.

4. In paragraph 2 or 3, An all-solid-state battery, wherein the lithium-sulfide compound comprises at least one compound selected from the group consisting of lithium phosphorus sulfide (LPS), lithium tin sulfide (LTS), lithium tin phosphorus sulfide (LTPS), lithium germanium phosphorus sulfide (LGPS), lithium phosphorus sulfur halide (LPSHa), and lithium silicon phosphorus sulfur halide (LSiPSHa).

5. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer comprise the same lithium-sulfide compound.

6. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer each independently contain at least one of a fluorine-based binder and a rubber-based binder.

7. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer each independently include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer (Poly(vinylidene fluoride-co-hexafluoropropylene, PVDF-HFP), acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR), styrene-butadiene rubber (SBR), or a combination thereof.

8. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer comprise the same binder.

9. In paragraph 1, An all-solid-state battery, wherein the first conductive layer and the second conductive layer each independently contain a carbon-based conductive material.

10. In paragraph 1, An all-solid-state battery, wherein the thickness ratio of the first conductive layer and the second conductive layer is 1:1.0 to 1:5.

0.

11. In paragraph 1, An all-solid-state battery, wherein the solid electrolyte layer comprises at least one compound selected from the group consisting of lithium-sulfide compounds, lithium-oxide compounds, lithium-hydride compounds, and lithium-halide compounds.

12. In paragraph 1, An all-solid-state battery, wherein the active material layer, the first conductive layer, and the second conductive layer all contain an argyrodite-based compound.

13. In paragraph 1, An all-solid-state battery, wherein the solid electrolyte layer, the first conductive layer, and the second conductive layer all contain an argyrodite-based compound.

14. In paragraph 1, An all-solid-state battery, wherein the active material layer comprises at least one of a fluorine-based binder and a rubber-based binder.

15. In paragraph 1, A negative electrode comprising a negative electrode current collector layer and a negative electrode active material layer; solid electrolyte layer; anode; A first negative electrode conductive layer between the negative electrode current collector layer and the negative electrode active material layer; and An all-solid-state battery, comprising a second negative electrode conductive layer between the negative electrode active material layer and the solid electrolyte layer.

16. In paragraph 15, The above negative active material layer includes a rubber-based binder, An all-solid-state battery, wherein the first cathode conductive layer and the second cathode conductive layer include a fluorine-based binder.

17. In paragraph 1, cathode; solid electrolyte layer; A cathode comprising a cathode current collector layer and a cathode active material layer; A first positive electrode conductive layer between the positive electrode current collector layer and the positive electrode active material layer; and An all-solid-state battery, comprising a second positive electrode conductive layer between the positive electrode active material layer and the solid electrolyte layer.

18. In paragraph 17, The above positive electrode active material layer, the first positive electrode conductive layer, and the second positive electrode conductive layer all contain a fluorine-based binder; An all-solid-state battery, wherein the above-mentioned positive electrode active material layer includes a rubber-based binder, and the first positive electrode conductive layer and the second positive electrode conductive layer include a fluorine-based binder.

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