Positive electrode paste for all-solid-state battery, method for manufacturing same, and all-solid-state battery manufactured using same

Abstract

A positive electrode slurry for an all-solid-state battery, a method for manufacturing the same, and an all-solid-state battery are provided. The positive electrode slurry comprises a positive electrode active material, a conductive material, a binder, a sulfide solid electrolyte, a triphenylphosphine additive and a solvent.

Description

[0001] This application claims priority and benefit to Korean Patent Application No. 10-2024-0154225, filed on November 4, 2024, with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference. Technical Field

[0002] One or more embodiments of this disclosure relate to positive electrode slurries for all-solid-state batteries, methods for manufacturing the same, and all-solid-state batteries manufactured using the same. Background Technology

[0003] In response to growing industrial demands, there has been a proactive pursuit of developing batteries with high energy density and enhanced safety. For example, lithium-ion batteries have been commercialized not only in information-related and communication devices but also in the automotive industry (e.g., automobiles). Given that user safety and / or well-being are critical concerns in the automotive industry, battery safety is of paramount importance.

[0004] Recently, all-solid-state batteries have been proposed, in which the liquid electrolyte (solution) is replaced by a solid electrolyte. Because these batteries do not use flammable organic solvents as a dispersion medium, the risk of fire or explosion is significantly reduced, even in the event of a short circuit. Therefore, all-solid-state batteries offer significantly improved safety compared to lithium-ion batteries that utilize liquid electrolytes. Summary of the Invention

[0005] One or more aspects of this disclosure relate to a positive electrode paste having improved adhesion properties and a method for manufacturing the positive electrode paste.

[0006] One or more aspects of this disclosure relate to a positive electrode for an all-solid-state battery having excellent or suitable performance, and an all-solid-state battery including the positive electrode.

[0007] Additional aspects will be set forth in part in the description which follows, and will also be apparent in part from the description, or may be learned by practice of the disclosed embodiments presented.

[0008] According to one or more embodiments of this disclosure, the positive electrode slurry for all-solid-state batteries includes a positive electrode active material, a conductive material, a binder, a sulfide-based solid electrolyte, a phosphine additive represented by Formula 1, and a solvent.

[0009] Formula 1

[0010] In Equation 1, n1 to n3 can all be independently 0 to 5, and R1 to R3 can each be independently hydrogen, halogen, nitrile, nitro, amino, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted C5 to C14 heteroaryl.

[0011] According to one or more embodiments of the present disclosure, a method for manufacturing a positive electrode slurry for an all-solid-state battery includes mixing a positive electrode active material, a conductive material, a binder, a sulfide-based solid electrolyte, a phosphine additive represented by Formula 1, and a solvent.

[0012] Formula 1

[0013] In Equation 1, n1 to n3 can all be independently 0 to 5, and R1 to R3 can each be independently hydrogen, halogen, nitrile, nitro, amino, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted C5 to C14 heteroaryl.

[0014] According to one or more embodiments of this disclosure, an all-solid-state battery includes a positive electrode, a negative electrode, and a solid electrolyte layer between the positive and negative electrodes, wherein the positive electrode may include a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector. The positive electrode active material layer may be formed using a positive electrode slurry manufactured according to the method of this disclosure. Attached Figure Description

[0015] The accompanying drawings are included to provide a further understanding of this disclosure, and are incorporated in and constitute a part of this disclosure. The drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain the principles of the disclosure. The above and other aspects, features, and advantages of certain embodiments of the present disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings. In the drawings: Figure 1 This is a cross-sectional view of an all-solid-state battery according to one or more embodiments of the present disclosure; Figure 2 This is a cross-sectional view of an all-solid-state battery according to one or more embodiments of the present disclosure; Figure 3 and Figure 4 These are plan views and cross-sectional views of an all-solid-state battery according to one or more embodiments of the present disclosure; Figure 5 This is a cross-sectional view of an all-solid-state battery according to one or more embodiments of the present disclosure; Figure 6This is a cross-sectional view of an all-solid-state battery including a gasket structure according to one or more embodiments of the present disclosure; Figure 7 This is an enlarged view showing the positive electrode active material layer according to one or more embodiments of the present disclosure; and Figure 8 and Figures 9A to 9C The results are an evaluation of the bending strength and load level of the positive electrode according to the examples and comparative examples of this disclosure. Detailed Implementation

[0016] To fully understand the structure and effects of the invention, one or more embodiments of the invention will be described in more detail with reference to the accompanying drawings. However, this disclosure may be practiced in one or more suitable forms and should not be construed as limited to the embodiments set forth herein, and one or more suitable changes and modifications may be made. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of this disclosure to those skilled in the art.

[0017] In this disclosure, it will be understood that if (e.g., when) an element is referred to as being on another element, then the element may be directly on said other element, or one or more intervening elements may exist between them. Conversely, if (e.g., when) an element is referred to as being "directly on" another element, then no intervening element exists. In the accompanying drawings, the thickness of components may be exaggerated for the purpose of effectively explaining the technical content. Throughout the disclosure, the same reference numerals or symbols denote the same elements, and for the sake of brevity, their repeated descriptions may be omitted.

[0018] The embodiments described herein will be explained with reference to cross-sectional views and / or plan views, which serve as ideal or simplified illustrations of this disclosure. In the drawings, the thickness of the films and regions may be exaggerated for the purpose of effectively explaining the technical content. Therefore, the regions shown in the drawings are schematic, and the shapes of the regions shown in the drawings are intended to illustrate the specific shapes of the regions of the device and not to limit the scope of the disclosure. In one or more embodiments of this disclosure, terms such as “first,” “second,” and “third” are used to describe one or more suitable components, but these components should not be limited by these terms. These terms are used only to distinguish one component from another. Therefore, a first element discussed herein may be referred to as a second element without departing from the scope of the disclosure. The embodiments described and shown herein also include their complementary embodiments.

[0019] The terminology used herein is for describing embodiments and is not intended to limit this disclosure. In this disclosure, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise. For example, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms “comprising / including” and / or variations thereof as used in this disclosure do not exclude the presence or addition of one or more other components. Additionally, the terms “comprising / including,” variations thereof, or other similar terms include or support the terms “consisting of” and “substantially consisting of,” which indicate the presence of the stated features, numbers, steps, operations, elements, parts, and / or components, while other features, numbers, steps, operations, elements, parts, components, and / or groups thereof are absent or substantially absent. Furthermore, when describing embodiments of this disclosure, the use of “may” refers to “one or more embodiments of this disclosure.”

[0020] In this disclosure, “combinations thereof” can refer to mixtures, stacks, complexes, copolymers, alloys, blends and reaction products of the components.

[0021] Unless otherwise defined in this disclosure, particle size / particle size can refer to average particle size / average particle size. Furthermore, particle size / particle size refers to average particle size / average particle size (D...). 50 D), which refers to the diameter / size of particles whose cumulative volume is approximately 50 vol% in the particle size distribution. In other words, D 50 In a particle size distribution (e.g., cumulative distribution), the average diameter (or average size) of the particles corresponding to 50 vol% of the cumulative volume is the value corresponding to 50% of the particle size, starting from the smallest particle in a cumulative distribution curve from smallest to largest particle size, when the total number of particles is 100%. Average particle size / average particle size (D 50 The average particle size / average particle size can be measured using methods well known to those skilled in the art, for example, by a particle size analyzer (e.g., the HORIBA LA-950 laser particle size analyzer), or by using transmission electron microscopy (TEM) images or scanning electron microscopy (SEM) images. In one or more embodiments, the average particle size / average particle size is measured using a dynamic light scattering measuring device, wherein the number of particles in each particle size range is counted by performing data analysis, and the average particle size / average particle size (D) can then be calculated from this. 50The average particle size / average particle size can also be measured using laser diffraction. Specifically, when measuring by laser diffraction, after dispersing the particles to be measured in a dispersion medium, the dispersion medium is introduced into a commercially available laser diffraction particle size analyzer (e.g., Microtrac MT 3000) and irradiated with ultrasound at approximately 28 kHz with an output of approximately 60 W. The average particle size / average particle size (Dsize) can then be calculated based on approximately 50% of the particle size distribution in the analyzer. 50 In this disclosure, when the particles are spherical, "diameter / size" refers to the average particle diameter / average particle size, and when the particles are non-spherical, "diameter / size" refers to the average major axis length of the particles.

[0022] Figure 1 This is a cross-sectional view of an all-solid-state battery 10 according to one or more embodiments of the present disclosure.

[0023] Reference Figure 1 The all-solid-state battery 10 according to one or more embodiments may include a positive electrode layer 100, a negative electrode layer 200 opposite to the positive electrode layer 100, and a solid electrolyte layer 300 disposed between the positive electrode layer 100 and the negative electrode layer 200 (e.g., disposed between the positive electrode layer 100 and the negative electrode layer 200). However, embodiments of this disclosure are not limited thereto. For example, in one or more embodiments, the all-solid-state battery 10 may further include additional functional layers (e.g., adhesion improvement layers) disposed between the positive electrode layer 100 and the solid electrolyte layer 300 and / or between the negative electrode layer 200 and the solid electrolyte layer 300.

[0024] According to one or more embodiments, the positive electrode layer 100 may include a positive electrode current collector 110 and a positive electrode active material layer 120 disposed on the positive electrode current collector 110 (e.g., disposed on the positive electrode current collector 110). The positive electrode active material layer 120 may include a positive electrode active material, a sulfide-based solid electrolyte, a conductive material, a binder, and a phosphine-based additive.

[0025] The positive electrode current collector 110 can provide a reference surface on which the positive electrode active material layer 120 is disposed. The positive electrode current collector 110 may include a plate or foil containing indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or alloys thereof.

[0026] In one or more embodiments, the positive electrode current collector 110 may not be provided. In one or more embodiments, a carbon layer with a thickness of about 0.1 micrometers (μm) to about 4 μm may be further disposed between the positive electrode current collector 110 and the positive electrode active material layer 120 to improve the adhesion between the positive electrode current collector 110 and the positive electrode active material layer 120.

[0027] The positive electrode layer 100 of the all-solid-state battery 10 according to one or more embodiments can be manufactured using the positive electrode slurry of this disclosure, which will be described later. The positive electrode layer 100 can be manufactured using conventional techniques for manufacturing electrodes, and the method is not particularly limited. For example, the positive electrode slurry, described later, can be applied to the positive electrode current collector 110 using a doctor blade with spraying, bar coating, slot coating, etc., dried, and then pressed to manufacture the electrode. The positive electrode active material layer 120 can be formed from the positive electrode slurry.

[0028] Please refer to later Figure 7 The positive electrode active material layer 120 is described in more detail.

[0029] Reference Figure 1 The negative electrode layer 200 may include a negative electrode current collector 210 and a coating layer 220 disposed on the negative electrode current collector 210 (e.g., disposed on the negative electrode current collector 210). The coating layer 220 may include a negative electrode active material and a binder.

[0030] The negative electrode current collector 210 can provide a reference surface on which the coating layer 220 is disposed. For example, the negative electrode current collector 210 may comprise a material that does not react with lithium (i.e., a material that does not form an alloy or compound with lithium). The materials constituting the negative electrode current collector 210 may include, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), etc., but the embodiments of this disclosure are not limited thereto, and any material used as an electrode current collector may be used. The negative electrode current collector 210 may have a thickness of about 1 μm to about 20 μm, for example, about 5 μm to about 15 μm, and for example, about 7 μm to about 10 μm.

[0031] The negative electrode current collector 210 may include one of the metals described above, or may include an alloy or covering material (e.g., a layered material) of two or more of the metals described above. The negative electrode current collector 210 may be in the form of, for example, a plate or foil. In one or more embodiments, the negative electrode current collector 210 may not be provided.

[0032] If (for example, when) the all-solid-state battery 10 is charged, the coating layer 220 can cause lithium metal to grow between the coating layer 220 and the negative electrode current collector 210. The coating layer 220 can serve as a protective layer for the lithium metal, while also inhibiting or reducing the deposition and growth of lithium dendrites.

[0033] The coating layer 220 may include metals and carbon. For example, in one or more embodiments, the coating layer 220 may include at least one metal 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). The coating layer 220 may include at least one carbon selected from the group consisting of carbon black, acetylene black, furnace black, Ketjen black, and graphene. In one or more embodiments, the coating layer 220 may include a mixture of carbon black and silver (Ag).

[0034] In one or more embodiments, in addition to metals and carbon, coating layer 220 may also include additives. Coating layer 220 may also include at least one additive selected from the group consisting of, for example, binders, fillers, coating agents, dispersants, and ion-conducting auxiliary materials.

[0035] The thickness of the coating layer 220 can be less than the thickness of the positive electrode active material layer 120. The thickness of the coating layer 220 can be, for example, about 50% or less, about 40% or less, about 30% or less, about 20% or less, about 10% or less, or about 5% or less of the thickness of the positive electrode active material layer 120. The thickness of the coating layer 220 can be, for example, about 1 μm to about 20 μm, about 2 μm to about 10 μm, or about 3 μm to about 7 μm. If the thickness of the coating layer 220 is too small, lithium dendrites formed between the coating layer 220 and the negative electrode current collector 210 may cause the coating layer 220 to collapse, thus degrading the cycle characteristics of the all-solid-state battery 10. If the thickness of the coating layer 220 is too large, the energy density of the all-solid-state battery 10 will decrease, and the internal resistance of the all-solid-state battery 10 may increase due to the coating layer 220, thereby degrading the cycle characteristics of the all-solid-state battery 10.

[0036] In one or more embodiments, a carbon layer may be further included to improve the adhesion between the coating layer 220 and the solid electrolyte layer 300.

[0037] Reference Figure 1The solid electrolyte layer 300 may be disposed between the positive electrode layer 100 and the negative electrode layer 200, and may include a sulfide-based solid electrolyte with excellent or suitable lithium-ion conductivity. The solid electrolyte included in the solid electrolyte layer 300 may be the same as or different from any of the solid electrolytes that may be included in the positive electrode active material layer 120, as will be described in more detail later.

[0038] The solid electrolyte layer 300 according to one or more embodiments may include a solid electrolyte. The solid electrolyte can be manufactured by processing initial raw materials (such as Li₂S and P₂S₅) using a melt quenching method, a mechanical grinding method, or the like. Additionally, heat treatment may be performed after processing. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. Furthermore, the solid electrolyte may include sulfur (S), phosphorus (P), and lithium (Li) as at least constituent elements of the aforementioned sulfide-based solid electrolyte material. For example, in one or more embodiments, the sulfide-based solid electrolyte may be a material containing Li₂S-P₂S₅. In embodiments using a material containing Li₂S-P₂S₅ as the sulfide-based solid electrolyte material forming the solid electrolyte, the molar ratio of Li₂S:P₂S₅ is, for example, in the range of about 50:50 to about 90:10.

[0039] In one or more embodiments, the sulfide-based solid electrolyte may be containing Li 7-a M a PS 6-c X c (0≤a≤2 and 0≤c≤2) sulfogermanium-type (e.g., sulfogermanium-type compounds). Here, X can be F, Br, Cl, I, or a combination thereof. M can be scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or combinations thereof.

[0040] Sulfide solid electrolytes can include those derived from Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Brx (0≤x≤2) and Li 7-x PS 6-x I x One or more of the following compounds are selected from (0≤x≤2): silver-germanium sulfide type (or similar) compounds. In one or more embodiments, the sulfide solid electrolyte may be one or more of the following compounds: silver-germanium sulfide type (or similar) compounds selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0041] The sulfide-germanium ore-type (or similar) solid electrolyte (e.g., sulfide-germanium ore solid electrolyte) can have a density of about 1.5 g / cc to about 2.0 g / cc. Because the density of the sulfide-germanium ore-type (or similar) solid electrolyte is about 1.5 g / cc or greater, the internal resistance of the all-solid-state battery can be reduced, and defects caused by lithium dendrite formation (such as penetration and short circuits of the solid electrolyte film) can be prevented or reduced. The solid electrolyte can have an elastic modulus of, for example, about 15 GPa to about 35 GPa.

[0042] In one or more embodiments, the solid electrolyte layer 300 may further include a binder. The binder included in the solid electrolyte layer 300 may include, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but the embodiments of this disclosure are not limited thereto. The binder of the solid electrolyte layer 300 may be the same as or different from the binder included in the positive electrode active material layer 120 or the binder included in the coating layer 220.

[0043] Figure 2 This is a cross-sectional view of an all-solid-state battery 10 according to one or more embodiments of the present invention.

[0044] Reference Figure 2 In one or more embodiments, the solid electrolyte layer 300 may include a first solid electrolyte layer 310 and a second solid electrolyte layer 320. The first solid electrolyte layer 310 may be adjacent to the positive electrode layer 100, and the second solid electrolyte layer 320 may be adjacent to the negative electrode layer 200.

[0045] The first solid electrolyte layer 310 and the second solid electrolyte layer 320 may have different thicknesses. The first solid electrolyte layer 310 may have a first thickness TK1, and the second solid electrolyte layer 320 may have a second thickness TK2. The first thickness TK1 may be greater than the second thickness TK2. For example, the first thickness TK1 may be about 2 to about 100 times the second thickness TK2.

[0046] Figure 3 This is a plan view of an all-solid-state battery 10 according to one or more embodiments of the present disclosure. Figure 4 According to one or more embodiments Figure 3 A cross-sectional view along line A-A'. In these embodiments, for the sake of brevity, a view with reference to... Figure 1 and Figure 2 The described technical features are repeated in detail, and the differences will be described in more detail.

[0047] Reference Figure 3 and Figure 4 The area of ​​the positive electrode layer 100 may differ from the area of ​​the negative electrode layer 200. For example, the area of ​​the negative electrode layer 200 may be larger than the area of ​​the positive electrode layer 100. The positive electrode layer 100 may completely overlap with the negative electrode layer 200 inwards. For example, the positive electrode layer 100 may completely overlap with the negative electrode layer 200 in a planar view.

[0048] According to one or more embodiments of this disclosure, the first solid electrolyte layer 310 may have an area substantially the same as that of the positive electrode layer 100. The second solid electrolyte layer 320 may have an area substantially the same as that of the negative electrode layer 200.

[0049] For example, the first solid electrolyte layer 310 may have a first width WI1 in the first direction D1. The second solid electrolyte layer 320 may have a second width WI2 in the first direction D1. The first width WI1 may be smaller than the second width WI2. The first solid electrolyte layer 310 may have a third width WI3 in the second direction D2, which intersects (e.g., is orthogonal to) the first direction D1. The second solid electrolyte layer 320 may have a fourth width WI4 in the second direction D2. The third width WI3 may be smaller than the fourth width WI4.

[0050] The all-solid-state battery 10 according to one or more embodiments can be manufactured by forming a first stack of a positive electrode layer 100 and a first solid electrolyte layer 310 and forming a second stack of a negative electrode layer 200 and a second solid electrolyte layer 320, and then stacking the first stack and the second stack.

[0051] Figure 5 It is based on Figure 3 Line A-A' shows a cross-sectional view of an all-solid-state battery according to one or more embodiments of the present disclosure.

[0052] Reference Figure 5In one or more embodiments, the negative electrode layer 200 of the all-solid-state battery 10 may further include a lithium metal layer 400 between the negative electrode current collector 210 and the coating layer 220. The thickness of the lithium metal layer 400 may be further increased if (e.g., when) the all-solid-state battery 10 is charged. The coating layer 220 may serve as a protective layer for the lithium metal layer 400, while also suppressing or reducing the growth of lithium dendrites from the lithium metal layer 400.

[0053] The lithium metal layer 400 may be a thin metal film comprising lithium or a lithium alloy. 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 embodiments of this disclosure are not limited thereto, and any alloy used as a lithium alloy may be used. In one or more embodiments, the lithium metal layer 400 may comprise one of these alloys or lithium. In one or more embodiments, the lithium metal layer 400 may comprise one or more suitable types (classes) of alloys.

[0054] The lithium metal layer 400 may have a fifth width WI5 in the first direction D1. The fifth width WI5 may be equal to or greater than the first width WI1. The fifth width WI5 may be equal to or less than the second width WI2. For example, in one or more embodiments, the fifth width WI5 may be greater than the first width WI1 and less than the second width WI2.

[0055] Figure 6 This is a cross-sectional view of an all-solid-state battery 10 according to one or more embodiments of the present disclosure.

[0056] Reference Figure 6 In one or more embodiments, the all-solid-state battery 10 may include a gasket structure 500. The gasket structure 500 may fill steps on the side surface of the all-solid-state battery 10 caused by area differences between the first stack and the second stack.

[0057] Reference Figure 6 The gasket structure 500 can surround the side surface of the first stack of the all-solid-state battery 10 in the first direction D1 and the second direction D2. For example, the thickness of the gasket structure 500 can be substantially equal to the thickness of the first stack. Therefore, even if the first and second stacks with different areas are stacked and pressed, damage to the steps on the side surface of the all-solid-state battery can be prevented or reduced. "Substantially equal thickness" can be defined as the thickness that is sufficient to prevent or reduce damage to the steps on the side surface of the all-solid-state battery even if the first and second stacks with different areas are stacked and pressed.

[0058] Positive electrode active material layer Figure 7 This illustrates the positive electrode active material layer 120 according to one or more embodiments of the present disclosure (see...). Figure 1 An enlarged sectional view of a portion of ( ). Figure 7 This illustrates one or more embodiments. Figure 1 A magnified view of region M.

[0059] Reference Figure 7 The positive electrode active material layer 120 according to this disclosure may include (e.g., in particulate form) a positive electrode active material CAM, a conductive material CDM, a binder BID, (e.g., in particulate form) a sulfide solid electrolyte SEL, a phosphine additive PHA, and a binder-modified material BMD. The positive electrode active material layer 120 may be manufactured by applying a positive electrode slurry, described later, onto the positive electrode current collector 110.

[0060] The positive electrode active material (CAM) can be a material capable of reversibly adsorbing and desorbing lithium ions. The positive electrode active material (CAM) can include, 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 iron phosphate, etc.), nickel sulfide, copper sulfide, lithium sulfide, iron oxide, vanadium oxide, etc., but the embodiments of this disclosure are not limited to these. The positive electrode active material can be a single material or a mixture of two or more of these materials.

[0061] Lithium transition metal oxides can be derived from, for example, Li a A 1-b B b D2 (0.90≤a≤1 and 0≤b≤0.5), Li a E 1- b B b O 2-c D c (0.90≤a≤1, 0≤b≤0.5 and 0≤c≤0.05), LiE 2-b B b O 4-c D c (0≤b≤0.5 and 0≤c≤0.05), Li a Ni 1-b-c Co b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05 and 0<α<2), Li a Ni 1-b-c Co b B c O 2-α Fα (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05 and 0<α<2), Li a Ni 1-b-c Mn b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05 and 0<α≤2), Li a Ni 1-b-c Mn b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05 and 0<α<2), Li a Ni b E c G d O2 (0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5 and 0.001≤d≤0.1), Li a Ni b Co c Mn d G e O2 (0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5 and 0.001≤e≤0.1), Li a NiG b O2 (0.9≤a≤1 and 0.001≤b≤0.1), Li a CoG b O2 (0.90≤a≤1 and 0.001≤b≤0.1), Li a MnG b O2 (0.90≤a≤1 and 0.001≤b≤0.1), Li a Mn2G b O4 (0.90≤a≤1 and 0.001≤b≤0.1), QO2, QS2, LiQS2, V2O5, LiV2O5, LiIO2, LiNiVO4, Li 3-f J2(PO4)3 (0≤f≤2), Li 3-fA compound represented by any one selected from Fe2(PO4)3 (0 ≤ f ≤ 2) and LiFePO4. Among these compounds, the capital letter "A" can be nickel (Ni), cobalt (Co), manganese (Mn), or a combination thereof, the capital letter "B" can be aluminum (Al), Ni, Co, Mn, chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth elements, or a combination thereof, the capital letter "D" can be oxygen (O), fluorine (F), sulfur (S), phosphorus (P), or a combination thereof, the capital letter "E" can be Co, Mn, or a combination thereof, the capital letter "F" can be fluorine (F), sulfur (S), phosphorus (P), or a combination thereof, the capital letter "G" can be Al, Cr, Mn, Fe, Mg, lanthanum (La), cerium (Ce), Sr, V, or a combination thereof, the capital letter "Q" can be titanium (Ti), Mo, Mn, or a combination thereof, the capital letter "I" can be Cr, V, Fe, scandium (Sc), yttrium (Y), or a combination thereof, and the capital letter "J" can be V, Cr, Mn, Co, Ni, copper (Cu), or a combination thereof.

[0062] For example, in one or more embodiments, the positive electrode active material CAM may include a lithium salt of a transition metal oxide having a layered rock salt-type (like) structure among the above lithium transition metal oxides. The "layered rock salt-type (like) structure" can be, for example, a cubic rock salt-type (like) structure, in which oxygen atom layers and metal atom layers are alternately and regularly arranged in the <111> direction, and thus each atom layer forms a two-dimensional plane. The "cubic rock salt-type (like) structure" can have a sodium chloride-type (like) (NaCl-type (like)) structure as a kind of (like) crystal structure. For example, it can have a structure in which face-centered cubic lattices (fcc) formed by positive ions and negative ions respectively are arranged to shift by 1 / 2 of the ridge of the unit lattice with respect to each other. The lithium transition metal oxide having this layered rock salt-type (like) structure can be a ternary lithium transition metal oxide, such as LiNi x Co y Al z O2 (NCA), LiNi x Co y Mn z O2 (NCM) (0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1), etc. In an embodiment where the positive electrode active material CAM includes a ternary lithium transition metal oxide having a layered rock salt-type (like) structure, the all-solid-state battery 10 can have an increased energy density and improved thermal stability.

[0063] The compounds included in the positive electrode active material CAM can be coated with a capping layer. For example, the compounds included in the positive electrode active material CAM can be in particulate form, and each particulate can be coated with a capping layer. In the positive electrode active material CAM, the compounds in particulate form can be mixed and used with added compounds constituting the capping layer. In one or more embodiments, the capping layer added to the surface of the positive electrode active material CAM can include, for example, oxides, hydroxides, hydroxyoxides, oxycarbonates, or hydroxycarbonates of the coating element. The compounds constituting the capping layer can be amorphous or crystalline. The coating element included in the capping layer can include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. In one or more embodiments, the capping layer can include, for example, Li2O-ZrO2 (LZO). The method of forming the capping layer can be selected within a range that does not adversely affect the properties of the positive electrode active material CAM. The method of forming the capping layer can include, for example, spraying, dipping, etc.

[0064] If (for example, when) the positive electrode active material CAM includes nickel (Ni) as a transition metal element in ternary lithium transition metal oxides (e.g., NCA, NCM, etc.), the capacity density of the all-solid-state battery 10 can be increased, thus reducing the elution of metals from the positive electrode active material CAM during charging. Therefore, the cycle characteristics of the all-solid-state battery 10 during charging can be improved. Meanwhile, "cycle characteristics" refers to the characteristics representing the degree of degradation of the all-solid-state battery 10 caused by charging / discharging, and an all-solid-state battery 10 with high cycle characteristics can have a low degree of degradation due to charging / discharging, while an all-solid-state battery 10 with low cycle characteristics can have a high degree of degradation due to charging / discharging.

[0065] The shape of the positive electrode active material CAM can include, for example, spherical, elliptical, or other particle shapes. There are no particular limitations on the particle size and content (e.g., amount) of the positive electrode active material CAM.

[0066] The positive electrode active material layer 120 may include a positive electrode active material CAM, based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM and the binder BID, wherein the amount of the positive electrode active material CAM is about 75 parts by weight to about 95 parts by weight.

[0067] The positive electrode active material layer 120 may include a conductive material CDM. The conductive material CDM may be conductive (e.g., electrically conductive) without causing chemical changes in the all-solid-state battery 10, thus increasing the conductivity (e.g., electrically conductive) of the positive electrode active material CAM and the sulfide-based solid electrolyte SEL.

[0068] Conductive material CDM can include carbon-based materials. Conductive material CDM can include one or more selected from, for example, graphite (e.g., natural graphite and artificial graphite), carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanofiber, and carbon nanotube.

[0069] The positive electrode active material layer 120 may include a conductive material CDM, based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM and the binder BID, wherein the amount of the conductive material CDM is from about 0.05 parts by weight to about 5 parts by weight.

[0070] The positive electrode active material layer 120 may include a sulfide solid electrolyte (SEL).

[0071] Sulfide solid electrolytes (SELs) can have a particulate shape (e.g., in granular form). Sulfide solid electrolytes (SELs) can be dispersed between the positive electrode active material (CAM). Sulfide solid electrolytes (SELs) with excellent or suitable lithium-ion conductivity can include, for example, Li₂S-P₂S₅, Li₂S-P₂S₅-LiX (where X is a halogen element), Li₂S-P₂S₅-Li₂O, Li₂S-P₂S₅-Li₂O-LiI, Li₂S-SiS₂, Li₂S-SiS₂-LiI, Li₂S-SiS₂-LiBr, Li₂S-SiS₂-LiCl, Li₂S-SiS₂-B₂S₃-LiI, Li₂S-SiS₂-P₂S₅-LiI, Li₂S-B₂S₃, and Li₂S-P₂S₅-Z. m S n (where m and n are both positive numbers, and the uppercase letter "Z" is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (Both p and q are positive numbers, and the uppercase letter "M" is one of 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) and Li 7-x PS 6-xI x At least one of the following (0≤x≤2).

[0072] In one or more embodiments, the sulfide-based solid electrolyte (SEL) may be composed of compounds derived from 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 One or more of the following compounds are selected from (0≤x≤2): silver-germanium sulfide type (or similar) compounds. In one or more embodiments, the sulfide solid electrolyte may be one or more of the following compounds: silver-germanium sulfide type (or similar) compounds selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0073] In one or more embodiments, the sulfide-based solid electrolyte (SEL) may be including Li 7-a M a PS 6-c X c A sulfide-silver-germanium mineral (or similar) compound (0 ≤ a ≤ 2 and (0 ≤ c ≤ 2)). Here, X can be F, Br, Cl, or a combination thereof. M can be scandium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof.

[0074] The sulfide-germanium ore-type (quasi-)solid electrolyte can have a density of about 1.5 g / cc to about 2.0 g / cc. Because the density of the sulfide-germanium ore-type (quasi-)solid electrolyte is about 1.5 g / cc or greater, the internal resistance of the all-solid-state battery 10 can be reduced, and defects caused by the formation of lithium dendrites (such as penetration and short circuits of the solid electrolyte film) can be prevented or reduced.

[0075] In one or more embodiments, the sulfide-based solid electrolyte (SEL) may have an elastic modulus of, for example, from about 15 GPa to about 35 GPa. The sulfide-based solid electrolyte (SEL) may be the same as the solid electrolyte contained in the solid electrolyte layer 300 described above.

[0076] The sulfide-based solid electrolyte (SEL) included in the positive electrode active material layer 120 can have a more moderate average particle size (D) than the solid electrolyte included in the solid electrolyte layer 300. 50 Small medium-sized average particle size (D) 50 For example, the medium average particle size (D) of sulfide-based solid electrolytes (SELs) included in the positive electrode active material layer 120. 50 ) can be the medium-sized average particle size (D) of the solid electrolyte included in the solid electrolyte layer 300. 50 The proportions are approximately 90% or less, approximately 80% or less, approximately 70% or less, approximately 60% or less, approximately 50% or less, approximately 40% or less, approximately 30% or less, or approximately 20% or less. In one or more embodiments, the average particle size (D) is moderate. 50 The median diameter can be measured using a laser diffraction particle size analyzer.

[0077] The average particle size (D) of sulfide solid electrolytes (SELs) 50 The particle size can be about 1 μm or smaller, about 0.9 μm or smaller, about 0.5 μm or smaller, or about 0.1 μm or smaller. In one or more embodiments, the average particle size (D) of the solid electrolyte SEL is... 50 The size can be, for example, about 10 nm to about 1 μm, about 10 nm to about 0.9 μm, or about 10 nm to about 0.1 μm.

[0078] The positive electrode active material layer 120 may include a sulfide solid electrolyte SEL, with the amount of the sulfide solid electrolyte SEL being about 5 parts by weight to about 25 parts by weight, based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM and the binder BID.

[0079] The positive electrode active material layer 120 may include an adhesive BID. The adhesive BID may include materials for bonding positive electrode active materials CAM, sulfide solid electrolyte SEL, conductive materials CDM, etc. included in the positive electrode active material layer 120, and for improving adhesion to the positive electrode current collector 110.

[0080] In one or more embodiments, the adhesive BID may include a fluoride adhesive.

[0081] Fluoride adhesives may include at least one of the following: polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP), polyvinylidene fluoride-co-trichloroethylene, polyvinylidene fluoride-co-tetrafluoroethylene, polyvinylidene fluoride-co-trifluoroethylene, polyvinylidene fluoride-co-trifluorochloroethylene, polyvinylidene fluoride-co-fluoroethylene-hexafluoropropylene, or polyvinylidene fluoride-co-trichloroethylene.

[0082] The positive electrode active material layer 120 may include a binder BID, with the amount of binder BID ranging from about 0.5 parts by weight to about 5 parts by weight, based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM, and the binder BID. If (for example, when) the amount of binder BID is below the above range, the dispersion effect of the binder BID may be reduced. If (for example, when) the amount of binder BID is greater than the above range, clogging of the binder BID may lead to a decrease in the stability of the slurry phase.

[0083] Meanwhile, fluoride binders are excellent or suitable as binders for integrating materials, but they have poor adhesion to current collector metals (such as copper). Therefore, in all-solid-state batteries 10 with electrodes using fluoride binders, repeated charging and discharging may cause materials such as active materials to separate from the current collector, thereby reducing battery capacity, which is a problem that reduces the cycle life of all-solid-state batteries.

[0084] To address this issue, the positive electrode active material layer 120 according to this disclosure may include a phosphine additive, PHA.

[0085] Phosphorus additive PHA can improve the processability, stability and performance of all-solid-state batteries.

[0086] Phosphine additives (PHA) may include compounds represented by Formula 1: Formula 1

[0087] In Equation 1, n1 to n3 can all be independently 0 to 5, and R1 to R3 can each be independently hydrogen, halogen, nitrile, nitro, amino, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted C5 to C14 heteroaryl.

[0088] For example, in one or more embodiments, the phosphine additive PHA may include at least one selected from the group consisting of triphenylphosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, tris(4-chlorophenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(o-tolyl)phosphine, diphenyl(p-tolyl)phosphine, and combinations thereof.

[0089] For example, as a phosphine additive, PHA can be used in combination with polysulfides (S... x Triphenylphosphine reacts with .

[0090] The positive electrode active material layer 120 may include a phosphine additive PHA, with the amount of PHA ranging from approximately 0.01 parts by weight to approximately 3 parts by weight based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM, and the binder BID. If (for example) the amount of phosphine additive PHA is excessive, the resistance of the electrode plate will increase, causing the battery performance to deteriorate. If (for example) the amount falls within the aforementioned value range, the positive electrode active material layer 120 can exhibit an overall improvement in performance (such as processability, stability, and capacity in production).

[0091] The weight ratio of the phosphine additive PHA to the sulfide solid electrolyte SEL can be from about 0.2 to about 25. For example, in one or more embodiments, the weight ratio of the phosphine additive PHA to the sulfide solid electrolyte SEL can be from about 0.3 to about 24, from about 0.4 to about 23, or from about 0.45 to about 22.5. If the weight ratio is too low, falling outside the above range, it may be difficult to obtain the product generated by the reaction with the sulfide solid electrolyte SEL, and if the weight ratio is too high, excessive unreacted material may remain in the positive electrode active material layer 120. In addition, during the manufacture of the electrode plate, slurry gelation may cause a large number of defects (scattering).

[0092] Because the sulfide solid electrolyte SEL and the phosphine additive PHA have the above weight ratio, a sufficient amount of the binder-modified material BMD, which will be described later, can be ensured in the positive electrode active material layer 120.

[0093] The positive electrode active material layer 120 according to one or more embodiments may include a binder-modified material (BMD).

[0094] Binder-modified material (BMD) can be obtained by reacting a phosphine additive (PHA) with the elution material of a sulfide solid electrolyte (SEL).

[0095] Because the phosphine additive PHA is included in the positive electrode active material layer 120 in a specific content (e.g., amount) range, the phosphine additive PHA can react optimally with the elution material of the sulfide solid electrolyte SEL to obtain the binder modified material BMD.

[0096] Sulfide-based solid electrolytes (SELs) can be dissolved in polar solvents during wet processes, allowing alkali metals and sulfides, among the components of the SEL, to be released from its surface as eluent. Then, the phosphine additive PHA according to this disclosure can react with the sulfides in the eluent of the SEL that are unstable in air and polar solvents, thereby generating a binder-modified material (BMD).

[0097] Binder modified material (BMD) generated by reacting phosphine additive PHA with the elution material of sulfide solid electrolyte (SEL) can be a sulfide material.

[0098] For example, in one or more embodiments, the binder-modified material BMD may include a mixture of substituted or unsubstituted triphenylphosphine sulfide (e.g., C... 18 H 15 At least one selected from the group consisting of PS, phosphorus sulfide, lithium sulfide (Li2S), or combinations thereof.

[0099] The positive electrode active material layer 120 may include a binder-modified material BMD, based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM and the binder BID, wherein the amount of the binder-modified material BMD is from about 0.0001 parts by weight to about 1 part by weight.

[0100] During the process of generating the binder-modified material BMD through the reaction of the phosphine additive PHA with the elution material of the sulfide solid electrolyte SEL, free radicals can be generated. These free radicals can interact with the binder BMD to modify the structure of the fluoride binder, thereby improving its adhesive properties. Therefore, the modified fluoride binder can possess strong adhesiveness and can firmly bond the positive electrode active material to the metal current collector (i.e., the positive electrode current collector).

[0101] In addition to the aforementioned positive electrode active material CAM, conductive material CDM, binder BID, sulfide solid electrolyte SEL, phosphine additive PHA, and binder-modified material BMD, the positive electrode active material layer 120 may also include additives such as fillers, coating agents, dispersants, and ion conduction auxiliary materials.

[0102] For example, in one or more embodiments, the positive electrode active material layer 120 can be manufactured by providing a mixture of materials included in the positive electrode active material layer 120 dispersed therein onto the positive electrode current collector 110. Because the materials included in the positive electrode active material layer 120 include the binder BID and the phosphine additive PHA, stable dispersion can be achieved, and the adhesion of the positive electrode active material layer 120 can be improved.

[0103] According to one or more embodiments, because the positive electrode active material layer 120 includes a phosphine additive PHA that can cause structural deformation / modification in the binder BID, the adhesion characteristics between the positive electrode active material layer 120 and the positive electrode current collector 110 can be improved, thereby improving the output characteristics and capacity of the all-solid-state battery 10.

[0104] In the following, a positive electrode paste according to one or more embodiments of the present disclosure and a method for manufacturing the positive electrode paste will be described.

[0105] Positive electrode paste and method for manufacturing the positive electrode paste The following describes a method for manufacturing a positive electrode slurry for all-solid-state batteries according to one or more embodiments.

[0106] A method for manufacturing a positive electrode slurry for an all-solid-state battery according to one or more embodiments of the present disclosure may include mixing a positive electrode active material CAM, a conductive material CDM, a binder BID, a sulfide solid electrolyte SEL, a phosphine additive PHA, and a solvent.

[0107] The positive electrode active material CAM, conductive material CDM, binder BID, sulfide solid electrolyte SEL, phosphine additive PHA and solvent are added to a container and mixed to prepare the positive electrode slurry.

[0108] For hybrid methods, any method that can be used by those skilled in the art (such as wet or dry methods) can be used, without being limited to a specific method.

[0109] For example, in one or more embodiments, mixing can be performed using a mixer or kneader. According to one or more embodiments of this disclosure, mixing can be performed at about 20°C to about 60°C for about 10 minutes to about 90 minutes using a planetary disperser mixer (PD mixer), a planetary mixer, a paddle mixer, a screw mixer, a twin-shaft mixer, a high-speed impeller mixer, or a propeller mixer for about 10 minutes to about 90 minutes.

[0110] According to one or more embodiments of this disclosure, mixing can be performed using a PD mixer. When mixing is performed using a PD mixer, the RPM speed can be from about 60 to about 150.

[0111] In the method for manufacturing positive electrode slurry, the previously described materials can be used, respectively, as positive electrode active material CAM, conductive material CDM, binder BID, sulfide solid electrolyte SEL, and phosphine additive PHA.

[0112] The positive electrode active material CAM according to one or more embodiments can be (e.g., in particulate form) a powder-type (or similar) positive electrode active material. The positive electrode active material may include, 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 iron phosphate, etc.), nickel sulfide, copper sulfide, lithium sulfide, iron oxide, vanadium oxide, etc., but the embodiments of this disclosure are not necessarily limited thereto. The positive electrode active material CAM can be a single material or a mixture of two or more of these materials.

[0113] The conductive material CDM may include carbon-based materials. In one or more embodiments, the conductive material CDM may include one or more selected from, for example, graphite (e.g., natural and artificial graphite), carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanofibers, and carbon nanotubes.

[0114] Binders (BIDs) may include materials used to improve the bonding and dispersibility of the positive electrode active material (CAM) and the sulfide-based solid electrolyte (SEL).

[0115] The adhesive BID according to one or more embodiments may include a fluoride adhesive. The fluoride adhesive may be one or more selected, for example, from polyvinylidene fluoride, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP), polyvinylidene fluoride-co-trichloroethylene, polyvinylidene fluoride-co-tetrafluoroethylene, polyvinylidene fluoride-co-trifluoroethylene, polyvinylidene fluoride-co-trifluorochloroethylene, polyvinylidene fluoride-co-fluoroethylene-hexafluoropropylene, and / or polyvinylidene fluoride-co-trichloroethylene.

[0116] According to one or more embodiments, the sulfide-based solid electrolyte (SEL) can be (e.g., in granular form) a powder-type (or sulfide-like) solid electrolyte. The sulfide-based solid electrolyte (SEL) can include, for example, Li... 7-x PS 6- x Cl x (0≤x≤2), Li 7-x PS 6-x Brx (0≤x≤2) and Li 7-x PS 6-x I x One or more of the following compounds are selected from (0≤x≤2): silver-germanium sulfide (or similar) compounds. In one or more embodiments, the solid electrolyte may be one or more of the following compounds: silver-germanium sulfide (or similar) compounds selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0117] Based on a total of 100 parts by weight of positive electrode active material CAM, conductive material CDM and binder BID, the amount of sulfide solid electrolyte SEL in the positive electrode slurry can be from about 5 parts by weight to about 25 parts by weight.

[0118] In the method for manufacturing a positive electrode slurry according to one or more embodiments, a phosphine additive PHA may be added. Because the phosphine additive PHA is the same as previously described, its detailed description will be simplified.

[0119] According to one or more embodiments, the phosphine additive PHA can be a compound represented by Formula 1: Formula 1

[0120] In Equation 1, n1 to n3 can all be independently 0 to 5, and R1 to R3 can each be independently hydrogen, halogen, nitrile, nitro, amino, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted C5 to C14 heteroaryl.

[0121] For example, a phosphine additive PHA may include at least one selected from the group consisting of triphenylphosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, tris(4-chlorophenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(o-tolyl)phosphine, diphenyl(p-tolyl)phosphine, and combinations thereof.

[0122] Based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM, and the binder BID, the amount of the phosphine additive PHA in the positive electrode slurry can be from about 0.01 parts by weight to about 3 parts by weight.

[0123] The solvent may include one or more solvents selected from the group consisting of ethyl acetate, hexyl butyrate, water (H2O), alcohol, formic acid, acetic acid, tetrahydrofuran, dimethylformamide, acetonitrile, dimethyl sulfoxide, acetone, dimethoxyethane, 1,3-dioxolane, N-methylpyrrolidone, N-methylformamide, diethyl carbonate, methyl ethyl carbonate and dimethyl carbonate.

[0124] Based on a total of 100 parts by weight of the positive electrode active material CAM, the conductive material CDM, and the binder BID, the amount of solvent in the positive electrode slurry can be from about 15 parts by weight to about 50 parts by weight.

[0125] In one or more embodiments, the solvent may include ethyl acetate, which promotes surface elution of sulfide-based solid electrolytes (SELs), or hexyl butyrate, which has a vapor pressure suitable for or appropriate for slurry processes.

[0126] The mixing ratio of the phosphine additive PHA to the sulfide solid electrolyte SEL in the positive electrode slurry can be from about 0.2 to about 25 by weight. For example, in one or more embodiments, the weight ratio of the phosphine additive PHA to the sulfide solid electrolyte SEL can be from about 0.3 to about 24, from about 0.4 to about 23, or from about 0.45 to about 22.5.

[0127] The positive electrode slurry may also include products generated by the reaction of a phosphine-based additive (PHA) with the elution material of a sulfide-based solid electrolyte (SEL). These products may include a binder-modified material (BMD).

[0128] "Product" refers to the intermediate reaction product obtained during the mixing process between the solvent, the sulfide solid electrolyte SEL, and the phosphine additive PHA.

[0129] Binder modifiers (BMDs) can modify the structure of fluoride adhesives to improve their adhesion properties.

[0130] For example, binder-modified materials (BMDs) may include those derived from substituted or unsubstituted triphenylphosphine sulfide (e.g., C450). 18 H 15 At least one selected from the group consisting of PS, phosphorus sulfide, lithium sulfide (Li2S), or combinations thereof.

[0131] Based on a total of 100 parts by weight of positive electrode active material CAM, conductive material CDM and binder BID, the amount of binder-modified material BMD in the positive electrode slurry can be from about 0.0001 parts by weight to about 1 part by weight.

[0132] After the positive electrode slurry manufactured in the above manufacturing method is applied to the positive electrode current collector 110 and dried, it can be rolled to form the positive electrode active material layer 120. In one or more embodiments, the thickness of the positive electrode active material layer 120 can be about 10 μm to about 30 μm, about 5 μm to about 30 μm, about 10 μm to about 20 μm, about 10 μm to about 40 μm, about 20 μm to about 50 μm, or about 40 μm to about 50 μm.

[0133] Because the phosphine additive PHA is added to the positive electrode slurry according to one or more embodiments, the problem of material separation, such as the active material, from the current collector during the manufacture of the positive electrode can be solved.

[0134] Therefore, the positive electrode slurry according to one or more embodiments can have electrical properties and improved dispersibility and adhesion. Thus, all-solid-state batteries fabricated using the positive electrode slurry of this disclosure can have excellent or suitable performance.

[0135] The present disclosure will be described in more detail below with reference to examples. However, these examples are for illustrative purposes only, and the scope of the disclosure is not limited thereto.

[0136] Manufacturing of positive electrode paste Example 1 Sulfide solid electrolyte (Li6PS5Cl) 0.5 Br 0.5 A mixture was prepared by adding a phosphine additive (triphenylphosphine, PPh3) to a solvent (ethyl acetate). In the mixture, the phosphine additive was present at a content (e.g., by weight) of about 0.45% by weight of the sulfide solid electrolyte.

[0137] The mixture was dispersed in a total of 100 parts by weight of positive electrode active material (LiNi). 0.94 Co 0.04 Al 0.02 The positive electrode slurry is ultimately manufactured using O2, a binder (PVdF-HFP), and a conductive material (carbon nanotubes). Based on a total of 100 parts by weight of the positive electrode active material, conductive material, and binder, the amount of phosphine additives is from 0.01 parts by weight to 3 parts by weight, the amount of sulfide solid electrolyte is from 5 parts by weight to 25 parts by weight, and the amount of solvent is from 15 parts by weight to 50 parts by weight.

[0138] The prepared positive electrode slurry is applied to an aluminum foil used as the positive electrode current collector and then dried at a temperature of about 150°C for about 2 hours to produce the positive electrode.

[0139] Example 2 Except for changing the content (e.g., by weight) ratio of phosphine additives to sulfide solid electrolytes to about 2.31%, the positive electrode slurry and positive electrode are manufactured in essentially the same manner as in Example 1.

[0140] Example 3 Except for changing the content (e.g., by weight) ratio of phosphine additives to sulfide solid electrolytes to about 6.92%, the positive electrode slurry and positive electrode are manufactured in a manner substantially the same as in Example 1.

[0141] Example 4 Except for changing the content (e.g., by weight) ratio of phosphine additives to sulfide solid electrolytes to about 22.32%, the positive electrode slurry and positive electrode are manufactured in a manner substantially the same as in Example 1.

[0142] Comparison Example 1 The positive electrode slurry and positive electrode are manufactured in essentially the same manner as in Example 1, except that no phosphine additives are added.

[0143] Comparison Example 2 Except for changing the content (e.g., by weight) ratio of phosphine additives to sulfide solid electrolytes to about 37.20%, the positive electrode slurry and positive electrode are manufactured in a manner substantially the same as in Example 1.

[0144] The composition of the positive electrode slurry prepared according to the example and comparative examples is detailed in Table 1.

[0145] Table 1

[0146] In this specification, the weight ratio (%) of phosphine additives to sulfide solid electrolytes is calculated as (weight of phosphine additives / weight of sulfide solid electrolytes) × 100.

[0147] Evaluation Example 1: Adhesion force of the positive electrode The adhesion force between the positive electrode active material layer and the positive electrode current collector of each positive electrode manufactured according to the example and comparative examples was measured, and the results are listed in Table 2.

[0148] Specifically, the positive electrode manufactured according to the examples and comparative examples is cut to a size of approximately 150 mm in length and approximately 20 mm in width, and the surface of the positive electrode is attached along its length to a glass slide approximately 75 mm in length and approximately 25 mm in width using double-sided adhesive tape. For example, the glass slide is attached to a region corresponding to half the length of the positive electrode.

[0149] Then, the roller is rubbed 10 times to ensure uniform (e.g., substantially uniform) adhesion of the double-sided adhesive tape, and evaluation samples are prepared from it. Next, the slide area of ​​the evaluation sample is fixed to the sample stage of a universal testing machine (UTM, product name: LS5, manufacturer: LLOYD), and the half of the positive electrode not attached to the slide is connected to the load sensor of the UTM machine. The load sensor is moved upward to about 50 mm by applying a force at about 90° and at a speed of about 100 mm / min, and the weight applied to the load sensor is measured. At this time, during the movement interval, the average weight measured in the interval from about 20 mm to about 40 mm is calculated, and the calculation is repeated 5 times to obtain its average value, and the obtained value is evaluated as the positive electrode adhesion force (gf / mm) for each sample.

[0150] Evaluation Example 2: Peel Strength The peel strength of the positive electrodes manufactured according to the examples and comparative examples was evaluated. Specifically, the peel strength was measured using a Surface and Interface Cutting Analysis System (SAICAS) machine by cutting the positive electrode with a blade to separate the lower part (positive electrode current collector) and the upper part (positive electrode active material layer). The evaluation results of the measured peel strength are listed in Table 2.

[0151] Evaluation Example 3: Bending Strength The bending strength of each positive electrode plate manufactured according to the example and comparative examples was measured using a method equivalent to ASTM D790 (3-point bending test).

[0152] Specifically, positive electrode plates manufactured according to the examples and comparative examples were cut into dimensions of approximately 15 mm × approximately 20 mm to prepare samples. In the three-point bending method, the samples were arranged at approximately 10 mm intervals between the first and second points, and a probe was used to press the center of the sample (the third point) at a regular speed in the thickness direction to perform a bending performance test. The force applied to the third point when moving at a speed of approximately 5 mm / min in the thickness direction was measured. The measurement results are shown in Table 2 and... Figure 8 The maximum bending strength (or maximum bending force) is the maximum force applied to the sample based on the distance the probe travels.

[0153] Table 2

[0154] As shown in Table 2, compared with the positive electrode according to the comparative example, the positive electrodes according to the examples all exhibit increased adhesion and peel strength. The maximum flexural strength values ​​of the positive electrodes according to the examples are all higher than those of the positive electrodes according to the comparative example.

[0155] Additionally, as shown in Table 2 and Figure 8As shown, the maximum bending strength values ​​of the positive electrodes according to the examples are all higher than the maximum bending strength values ​​of the positive electrodes according to the comparative examples.

[0156] Therefore, it can be seen that, compared with the positive electrode according to the comparative example, the positive electrode according to the example has a significantly improved adhesion between the positive electrode active material layer and the positive electrode current collector.

[0157] Evaluation Example 4: Positive Electrode Loading Level (L / L, mg / cm³) 2 ) Correspondingly, the loading level (mg / cm²) of the positive electrodes manufactured according to Example 1 and Comparative Example 1 was measured. 2 The results are shown in Figure 9A and Figure 9B middle.

[0158] Specifically, a positive electrode coated with positive electrode active material and a positive electrode current collector without active material coating are each punched through a circular punch with a diameter of approximately 16 mm, and then their weights are measured. The weight of the positive electrode current collector without active material coating is subtracted from the weight of the positive electrode coated with positive electrode active material to measure the weight of the active material loaded onto the electrode. This measured weight is then divided by the area coated with active material to measure the amount of positive electrode active material applied per unit area (load level, mg / cm²). 2 ).

[0159] Next, the bending strength of the positive electrodes manufactured according to Example 1 and Comparative Example 1 will be slowly increased, and the corresponding phenomena will be observed. The results are shown in... Figure 9C middle.

[0160] like Figures 9A to 9C As shown, the loading level of the positive electrode according to the example is approximately 30 mg / cm². 2 Approximately 45 mg / cm 2 Furthermore, under the same bending strength, the positive electrode according to the comparative example has cracks in the active material layer, but the positive electrode according to the example does not have cracks in the active material layer.

[0161] Therefore, it can be seen that the positive electrode according to the example has improved flexibility compared to the positive electrode according to the comparative example.

[0162] Evaluation Example 5: Lifetime Characteristics of All-Solid-State Batteries The positive electrodes fabricated according to the example and comparative examples are applied to the corresponding all-solid-state batteries. In this evaluation example, to evaluate the battery life of the all-solid-state battery, charging and discharging are performed using a charge and discharge tester with a constant current method.

[0163] The fabricated all-solid-state rechargeable battery was charged at approximately 25°C with a constant current at a rate of approximately 0.1C until the voltage reached approximately 3.63V (vs. Li-In), and then cut off in constant voltage mode while maintaining approximately 3.63V with a current at a rate of approximately 0.05C. Next, the battery was discharged at a constant current at a rate of approximately 0.1C until the voltage reached approximately 1.88V (vs. Li-In) (cycle 1). This cycle was repeated 50 times under substantially the same conditions.

[0164] In all charge and discharge cycles, the cells were allowed to rest for approximately 10 minutes after each charge / discharge cycle. Test results for charge and discharge at room temperature are listed in Table 3. Capacity retention is defined by Equation 1.

[0165] Equation 1 Capacity retention [%] = [Discharge capacity at 50th cycle / Discharge capacity at 1st cycle] × 100 Table 3

[0166] As shown in Table 3, it can be seen that all solid-state batteries using the positive electrode of the examples according to this disclosure have improved cycle characteristics and lifespan compared to the cycle characteristics and lifespan of the comparative examples.

[0167] Therefore, compared to the all-solid-state battery of the comparative example, the all-solid-state battery coated with the positive electrode slurry described in the claims of this disclosure has improved discharge capacity due to the improved adhesion between the positive electrode current collector and the positive electrode active material layer. Furthermore, even during repeated charging and discharging during cycling, the positive electrode current collector and the positive electrode active material layer remain in stable contact with each other without separation or delamination, thus improving capacity retention. These improvements are achieved, for example, by incorporating phosphine-based additives (such as triphenylphosphine (PPh3)) into the slurry formulation. The additive chemically interacts with the sulfide-based solid electrolyte to form a binder-modified material that enhances the compatibility between the active material and the binder matrix. This chemical interaction reduces interfacial resistance and improves mechanical cohesion, thereby maintaining contact integrity during electrochemical cycling.

[0168] A method for manufacturing a positive electrode slurry for all-solid-state batteries according to one or more embodiments of this disclosure can provide a positive electrode slurry with improved adhesion properties. This can be achieved by incorporating phosphine-based additives that interact with sulfide-based solid electrolytes to enhance the cohesion and mechanical robustness of the electrode structure. The resulting slurry not only facilitates uniform coating and high loading levels but also contributes to the long-term durability of the electrode during battery operation. For example, as shown in Examples 1 through 4, the concentration of the additives is carefully tuned to balance the chemical reactivity and mechanical flexibility of the electrode. At a desired specific gravity (or proportion) (e.g., 6.92 wt% in Example 3), the additives significantly improve adhesion and flexural strength without compromising electrochemical performance. This enhancement should result in a slurry that can be processed using relevant techniques while providing excellent electrode performance.

[0169] By applying the previously described positive electrode slurry, this disclosure provides positive electrodes with excellent or suitable electrochemical and mechanical properties. The resulting all-solid-state batteries exhibit enhanced safety, cycle life, and energy density, making them particularly suitable for demanding applications such as electric vehicles, aerospace systems, and / or grid-scale energy storage. For example, the synergistic effect of phosphine-based additives and sulfide-based solid electrolytes not only improves the mechanical integrity of the electrode but also contributes to a more uniform ion transport path. This results in reduced internal resistance and more stable cycling behavior, which is advantageous for the practical deployment of all-solid-state batteries in high-performance applications.

[0170] In this disclosure, when expressions such as “at least one of…”, “one of…”, and “selected from…” are placed before or after a list of elements, they modify the entire list of elements, not individual elements within that list. For example, “at least one of a, b, or c”, “at least one selected from a, b, and c”, “at least one selected from a to c”, etc., can indicate only a, only b, only c, both a and b (e.g., simultaneously), both a and c (e.g., simultaneously), both b and c (e.g., simultaneously), all of a, b, and c, or variations thereof. Depending on the context, the “ / ” used herein can be interpreted as “and” or “or”.

[0171] In the context of this disclosure and unless otherwise defined, the term “use” and its variations may be considered synonymous with the term “utilize” and its variations, respectively.

[0172] In this disclosure, the term "group" as used herein refers to a group in the periodic table of elements according to the group 1 to group 18 system of the International Union of Pure and Applied Chemistry ("IUPAC").

[0173] As used herein, the terms “approximately,” “about,” and similar terms are used as approximate terms rather than terms of degree, and are intended to account for the inherent biases of measured or calculated values ​​that would be recognized by one of ordinary skill in the art. Taking into account the measurements discussed and the errors associated with the measurement of a particular quantity (i.e., the limitations of the measurement system), “about” or “approximately” as used herein also includes the stated value and means within an acceptable range of deviation for a particular value as determined by one of ordinary skill in the art. For example, “about” may mean within one or more standard deviations, or within ±30%, ±20%, ±10%, or ±5% of the stated value.

[0174] Any numerical range described herein is intended to include all subranges with the same numerical precision contained within the described range. For example, the range "1.0 to 10.0" is intended to include all subranges between the described minimum value of 1.0 and the described maximum value of 10.0 (and including both the described minimum value of 1.0 and the described maximum value of 10.0), i.e., a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as 2.4 to 7.6. Any maximum numerical limit described herein is intended to include all lower numerical limits contained therein, and any minimum numerical limit described in this specification is intended to include all higher numerical limits contained therein. Therefore, the applicant reserves the right to amend this specification (including the claims) to expressly describe any subranges contained within the range expressly described herein.

[0175] The apparatus and / or any other related means or components for manufacturing dry electrodes according to embodiments of the invention described herein can be further implemented using any suitable hardware, firmware (e.g., application-specific integrated circuits), software, or a combination of software, firmware, and hardware. For example, various components of the apparatus can be formed on an integrated circuit (IC) chip or a separate IC chip. Furthermore, various components of the apparatus can be implemented on a flexible printed circuit film, a tape-on-a-package (TCP), a printed circuit board (PCB), or formed on a substrate. Additionally, various components of the apparatus can be processes or threads running on one or more processors in one or more computing devices, executing computer program instructions and interacting with other system components to perform the various functions described herein. The computer program instructions are stored in memory, which can be implemented in a computing device using standard memory devices (such as random access memory (RAM) for example). The computer program instructions can also be stored in other non-transitory computer-readable media (such as CD-ROMs, flash drives, etc.). Furthermore, those skilled in the art will recognize that, without departing from the scope of this disclosure, the functions of various computing devices can be combined or integrated into a single computing device, or the functions of a particular computing device can be distributed across one or more other computing devices.

[0176] It will be understood by those skilled in the art that, in view of the entirety of this disclosure, each suitable feature of the various embodiments of this disclosure may be combined or integrated with each other in part or in whole, and may be technically interlocked and operated in various suitable ways, and each embodiment may be implemented independently or in combination with each other in any suitable manner, unless otherwise stated or implied.

[0177] Although one or more embodiments of this disclosure have been described with reference to the accompanying drawings, it is understood that this disclosure may be implemented in other specific forms without altering the technical concept or essential characteristics of the disclosure. Therefore, the above embodiments should be understood in all respects as illustrative rather than restrictive. Consequently, the scope of the disclosure is not intended to be limited to what is set forth in the detailed description thereof, but rather to be defined by the appended claims and their equivalents.

Claims

1. A positive electrode paste, the positive electrode paste comprising: Positive electrode active material; Conductive materials; Adhesive; Sulfide solid electrolytes; Phosphine additives represented by Formula 1; as well as Solvent, Formula 1 ， In Equation 1, n1 to n3 are all independently 0 to 5, and R1 to R3 are each independently hydrogen, halogen, nitrile, nitro, amino, substituted or unsubstituted C1 to C10 alkyl, substituted or unsubstituted C1 to C10 alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted C5 to C14 heteroaryl, and The positive electrode slurry is a positive electrode slurry used in all-solid-state batteries.

2. The positive electrode paste according to claim 1, wherein, The phosphine additives include at least one selected from the group consisting of triphenylphosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, tris(4-chlorophenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(o-tolyl)phosphine, diphenyl(p-tolyl)phosphine, and combinations thereof.

3. The positive electrode paste according to claim 1, wherein, Based on a total of 100 parts by weight of the positive electrode active material, the conductive material, and the binder, the amount of the phosphine additive is from 0.01 parts by weight to 3 parts by weight.

4. The positive electrode paste according to claim 1, wherein, Based on a total of 100 parts by weight of the positive electrode active material, the conductive material, and the binder, the amount of the sulfide-based solid electrolyte is from 5 to 25 parts by weight.

5. The positive electrode paste according to claim 1, wherein, Based on a total of 100 parts by weight of the positive electrode active material, the conductive material, and the binder, the amount of the solvent is from 15 to 50 parts by weight.

6. The positive electrode paste according to claim 1, wherein, The weight ratio of the phosphine additive to the sulfide solid electrolyte is 0.2% to 25%.

7. The positive electrode paste according to claim 1, wherein, The positive electrode active material includes a compound represented by Formula 2: Formula 2 Li a Ni x Co y Mr z X c O 2-b , In Equation 2, 0.8≤a≤1.2, 0.8≤x≤1.0, 0≤y≤0.1, 0≤z≤0.1, 0≤c≤0.1, 0≤b≤0.05, and x+y+z+c=1, and X is at least one element selected from the group consisting of Al, Ti, Mg, Zr, Mo and Nb.

8. The positive electrode paste according to claim 1, wherein, The adhesive includes fluoride adhesives.

9. The positive electrode paste according to claim 1, wherein, The conductive material includes at least one selected from the group consisting of natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, carbon nanofiber, carbon nanotube, and combinations thereof.

10. The positive electrode paste according to claim 1, wherein, The sulfide-based solid electrolyte includes Li 7- a M a PS 6-c X c sulfoargillite-type compounds, wherein 0 ≤ a ≤ 2 and 0 ≤ c ≤ 2, X is F, Br, Cl, I, or a combination thereof, and M is scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, or combinations thereof.

11. A method, the method comprising: The positive electrode active material, conductive material, binder, sulfide solid electrolyte, phosphine additive represented by Formula 1, and solvent are mixed: Formula 1 ， In Equation 1, n1 to n3 are all independently 0 to 5. R1 to R3 are each independently a hydrogen atom, a halogen group, a nitrile group, a nitro group, an amino group, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted C5 to C14 heteroaryl group. The method described herein is a method for manufacturing a positive electrode slurry for all-solid-state batteries.

12. The method according to claim 11, wherein, The phosphine additives include at least one selected from the group consisting of triphenylphosphine, tris(4-trifluoromethylphenyl)phosphine, tris(4-fluorophenyl)phosphine, tris[3,5-bis(trifluoromethyl)phenyl]phosphine, tris(4-chlorophenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)phosphine, tris(o-tolyl)phosphine, diphenyl(p-tolyl)phosphine, and combinations thereof.

13. The method according to claim 11, wherein, The adhesive includes fluoride adhesives, and The sulfide-based solid electrolyte includes Li 7-a M a PS 6-c X c sulfoargillite-type compounds, wherein 0 ≤ a ≤ 2 and 0 ≤ c ≤ 2, X is F, Br, Cl, I, or a combination thereof, and M is scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, silicon, germanium, tin, lead, arsenic, antimony, bismuth, or combinations thereof.

14. The method according to claim 11, wherein, Based on a total of 100 parts by weight of the positive electrode active material, the conductive material, and the binder, the amount of the phosphine additive is from 0.01 parts by weight to 3 parts by weight.

15. The method according to claim 11, wherein, Based on a total of 100 parts by weight of the positive electrode active material, the conductive material, and the binder, the amount of the sulfide-based solid electrolyte is from 5 to 25 parts by weight.

16. The method according to claim 11, wherein, The weight ratio of the phosphine additive to the sulfide solid electrolyte is 0.2 to 25.

17. An all-solid-state battery, the all-solid-state battery comprising: Positive electrode; negative electrode; And a solid electrolyte layer, between the positive electrode and the negative electrode. The positive electrode includes a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector. The positive electrode active material layer is formed using the positive electrode slurry according to any one of claims 1 to 10.

18. The all-solid-state battery according to claim 17, wherein, The positive electrode active material layer includes a binder-modified material produced by the reaction between the elution material of the sulfide-based solid electrolyte and the phosphine-based additive.

19. The all-solid-state battery according to claim 18, wherein, The binder-modifying material includes at least one selected from the group consisting of substituted or unsubstituted triphenylphosphine sulfide, phosphorus sulfide, lithium sulfide, and combinations thereof.

20. The all-solid-state battery according to claim 18, wherein, Based on a total of 100 parts by weight of the positive electrode active material, the conductive material, and the binder, the amount of the binder-modified material is from 0.0001 parts by weight to 1 part by weight.

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