Positive electrode and all-solid-state battery comprising same

Abstract

Disclosed are a positive electrode and an all-solid-state battery comprising same, the positive electrode including a positive electrode active material layer which comprises a positive electrode active material and a solid electrolyte. The positive electrode active material comprises an Li2S-containing composite which comprises Li2S, a lithium salt compound, a boron group metal halide salt, and an electron conductive material, wherein the amounts of Li2S, the lithium salt compound, the boron group metal halide salt, and the electron conductive material are controlled.

Description

Anode and all-solid-state battery including the same

[0001] This relates to a positive electrode and an all-solid-state battery containing the same.

[0002] Recently, driven by industrial demands, the development of batteries with high energy density and safety is actively underway. For example, lithium batteries are being put into practical use not only in information and communication equipment sectors but also in the automotive sector. In the automotive field, safety is considered particularly important because it is directly related to human life.

[0003] All-solid-state batteries using a solid electrolyte instead of a liquid electrolyte are being proposed.

[0004] By not using flammable organic solvents, all-solid-state batteries can significantly reduce the likelihood of fire or explosion in the event of a short circuit. These batteries can greatly enhance safety compared to lithium batteries that use liquid electrolytes.

[0005] Secondary batteries use sulfur-based materials as cathode active materials to increase capacity. Using sulfur-based materials allows for a higher theoretical energy capacity compared to lithium-ion batteries, and the low cost of sulfur-based materials can lower the manufacturing cost of secondary batteries.

[0006] One aspect is to provide an anode that possesses thin-film characteristics while simultaneously having excellent capacity.

[0007] Another aspect is to provide all-solid-state batteries with improved energy density.

[0008] According to one embodiment, it comprises a positive active material layer including a positive active material and a solid electrolyte; The above positive active material comprises a Li2S-containing composite, wherein the Li2S-containing composite comprises Li2S, a lithium salt compound, a boron group metal halide salt, and an electronically conductive material, wherein the content of Li2S is 40 to 60 parts by weight per 100 parts by weight of the entire positive active material layer, the content of the lithium salt compound is 5 to 15 parts by weight per 100 parts by weight of the entire positive active material layer, the content of the boron group metal halide salt is 15 to 25 parts by weight per 100 parts by weight of the entire positive active material layer, the content of the electronically conductive material is 5 to 15 parts by weight per 100 parts by weight of the entire positive active material layer, the content of the positive active material is 75 to 85 parts by weight per 100 parts by weight of the entire positive active material layer, and the content of the solid electrolyte is 15 to 25 parts by weight per 100 parts by weight of the entire positive active material layer. A positive electrode is provided.

[0009] According to another embodiment, an all-solid-state battery is provided, comprising the aforementioned anode; cathode layer; and a solid electrolyte layer disposed between the anode and the cathode layer; wherein the cathode layer comprises a cathode current collector and a cathode coating layer on the cathode current collector.

[0010] According to one aspect, it is possible to provide an all-solid-state battery with improved energy density by employing a thin-film cathode with controlled composition and content of the cathode active material layer.

[0011] FIG. 1 is a cross-sectional view of an all-solid-state battery according to an exemplary embodiment.

[0012] Figure 2 is an enlarged schematic diagram showing area A of Figure 1 enlarged.

[0013] Figure 3 is an enlarged schematic diagram showing area B of Figure 2 enlarged.

[0014] FIG. 4 is a cross-sectional view of an all-solid-state battery according to another exemplary embodiment.

[0015] FIG. 5 is a cross-sectional view of an all-solid-state battery according to another exemplary embodiment.

[0016] The present inventive concept described below is subject to various modifications and may have various embodiments, and specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present inventive concept to specific embodiments and should be understood to include all modifications, equivalents, or substitutions that fall within the scope of the description of the present inventive concept.

[0017] The terms used below are used merely to describe specific embodiments and are not intended to limit the creative concept. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the following, terms such as “comprising” or “having” are intended to indicate the existence of the features, numbers, steps, actions, components, parts, components, materials, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, components, materials, or combinations thereof. The “ / ” used below may be interpreted as “and” or “or” depending on the context.

[0018] In the drawings, thicknesses have been enlarged or reduced to clearly represent various layers and regions. Throughout the specification, the same reference numerals have been used for similar parts. Throughout the specification, when a part such as a layer, film, region, or plate is described as being “on” or “above” another part, this includes not only cases where it is directly above another part but also cases where there is another part in between. Throughout the specification, terms such as “first,” “second,” etc., may be used to describe various components, but the components should not be limited by these terms. In this specification and drawings, components having substantially the same functional configuration are referred to by the same reference numerals to avoid redundant descriptions.

[0019] In the present disclosure, the “size” of a particle is, for example, the “particle diameter” of the particle. The “particle diameter” of the particle represents the average diameter when the particle is spherical and represents the average major axis length when the particle is non-spherical. The particle diameter of the particle can be measured using a particle size analyzer (PSA). The “particle diameter” of the particle is, for example, the average particle diameter. The average particle diameter is, for example, the median particle diameter (D50). The median particle diameter (D50) is the particle size corresponding to the 50% cumulative volume calculated from the side of the particle having a small particle size in the particle size distribution measured, for example by laser diffraction.

[0020] In the present disclosure, D50 is the particle size corresponding to 50% of the cumulative volume calculated from the side of the particle having a small particle size in the particle size distribution measured by laser diffraction.

[0021] In the present disclosure, D90 is the particle size corresponding to the 90% cumulative volume calculated from the side of the particle having a small particle size in the particle size distribution measured by laser diffraction.

[0022] In the present disclosure, D10 is the particle size corresponding to 10% cumulative volume calculated from the side of the particle having a small particle size in the particle size distribution measured by laser diffraction.

[0023] In the present disclosure, “metal” includes both metals and metalloids such as silicon and germanium in an elemental or ionic state.

[0024] In this disclosure, “alloy” means a mixture of two or more metals.

[0025] In the present disclosure, “anode active material” refers to an anode material capable of undergoing lithiation and delithiation.

[0026] In the present disclosure, “anode active material” refers to an anode material capable of undergoing lithiation and delithiation.

[0027] In the present disclosure, “lithiation” and “to lithiate” refer to the process of adding lithium to a positive electrode active material or a negative electrode active material.

[0028] In the present disclosure, “delithiation” and “to delithiate” refer to the process of removing lithium from a positive electrode active material or a negative electrode active material.

[0029] In this disclosure, “charge” and “to charge” refer to the process of providing electrochemical energy to a battery.

[0030] In this disclosure, “anode” and “cathode” refer to electrodes where electrochemical reduction and lithiation occur during the discharge process.

[0031] In this disclosure, “cathode” and “anode” refer to electrodes where electrochemical oxidation and delithiation occur during the discharge process.

[0032] In the present disclosure, each of the phrases such as “A or B”, “at least one of A and B”, “at least one of A or B”, “A, B or C”, “at least one of A, B and C”, and “at least one of A, B, or C” may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0033] A positive electrode and an all-solid-state battery including the same according to exemplary embodiments will be described in more detail below.

[0034] Referring to FIG. 1, an anode (100) according to one embodiment of the present disclosure may include an anode current collector (110) and an anode active material layer (120) on the anode current collector (110).

[0035] The positive current collector (110) may provide a reference surface on which the positive active material layer (120) is disposed. The positive current collector (110) may include, for example, a plate or foil comprising indium (In), copper (Cu), magnesium (Mg), stainless steel (SUS), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof. The thickness of the positive current collector (110) may be, for example, 5 μm to 100 μm, 5 μm to 50 μm, or 8 μm to 25 μm. In another embodiment, the positive current collector (110) may be omitted. Although not illustrated, a carbon layer with a thickness of 10 nm to 4 μm may be further disposed between the positive current collector (110) and the positive active material layer (120) to increase the bonding strength between the positive current collector and the positive active material layer (120). The carbon layer may include amorphous carbon, crystalline carbon, etc.

[0036] Referring to FIGS. 1 and 2, a positive active material layer (120) according to one embodiment of the present disclosure may include a positive active material (10) and a solid electrolyte (20). Within the positive active material layer (120), the positive active material (10) stores energy through the insertion and release of lithium ions, thereby determining the capacity and energy density of the battery. Within the positive active material layer (120), the solid electrolyte (20) provides a path for the movement of lithium ions, thereby determining the lifespan characteristics of the battery.

[0037] The positive electrode active material (10) may include a lithium-containing sulfide-based positive electrode active material. The lithium-containing sulfide-based positive electrode active material may include, for example, Li2S, a Li2S-containing composite, or a combination thereof. The positive electrode active material (10) according to one embodiment of the present disclosure may include a Li2S-containing composite. By including Li2S, a Li2S-containing composite, or a combination thereof having high capacity as the lithium-containing sulfide-based positive electrode active material, the use of lithium metal may be omitted during the manufacture of a secondary battery. Since lithium metal has high reactivity and large ductility, it may reduce mass production efficiency during battery manufacturing. Therefore, if the use of lithium metal is omitted during the manufacture of a secondary battery, the mass production efficiency of the secondary battery may be improved.

[0038] The Li2S-containing composite is, for example, a composite of Li2S (1) and a conductive material. The conductive material is, for example, an ion-conducting material (2, 3), an electron-conducting material (4), or a combination thereof.

[0039] The ionic conductivity of an ion-conducting material is, for example, 1.0 × 10⁻⁶ at 25°C. -5 S / m or greater, 1.0×10 -4 S / m or more, or 1.0×10 -3It is greater than S / m. The ion-conducting material may have pores. By having pores, Li2S (1) can be contained within the pores, thereby increasing the contact area between Li2S (1) and the ion-conducting material and increasing the specific surface area of ​​Li2S (1). The form of the ion-conducting material may be, for example, a particulate ion-conducting material, a plate-shaped ion-conducting material, a rod-shaped ion-conducting material, or a combination thereof, but is not necessarily limited to these.

[0040] An ion-conducting material according to one embodiment may include, for example, a metal salt compound. The metal salt compound may include a lithium salt compound (2). The lithium salt compound (2) may include, for example, at least one of LiF, LiCl, LiBr, or LiI. According to one embodiment, a Li2S-containing composite including the lithium salt compound (2) may include, for example, Li2S-LiF, Li2S-LiCl, Li2S-LiBr, Li2S-LiI, or a combination thereof. The metal salt compound may further include a boron group metal halide salt (3). The boron group metal halide salt (3) may include, for example, at least one of AlF3, AlCl3, AlBr3, AlI3, GaF3, GaCl3, GaBr3, GaI3InF3, InCl3, InBr3, InI3T1F3, T1Cl3, T1Br3, or T1I3. According to one embodiment, a Li2S-containing composite further comprising a boron group metal halide salt (3) is, for example, Li2S-LiF-AlF3, Li2S-LiF-AlCl3, Li2S-LiF-AlBr3, Li2S-LiF-AlI3, Li2S-LiF-GaF3, Li2S-LiF-GaCl3, Li2S-LiF-GaBr3, Li2S-LiF-GaI3, Li2S-LiF-InF3, Li2S-LiF-InCl3, Li2S-LiF-InBr3, Li2S-LiF-InI3, Li2S-LiF-TlF3, Li2S-LiF-TlCl3, Li2S-LiF-TlBr3, Li2S-LiF-TlI3, Li2S-LiCl-AlF3, Li2S-LiCl-AlCl3, Li2S-LiCl-AlBr3, Li2S-LiCl-AlI3, Li2S-LiCl-GaF3, Li2S-LiCl-GaCl3, Li2S-LiCl-GaBr3, Li2S-LiCl-GaI3, Li2S-LiCl-InF3, Li2S-LiCl-InCl3, Li2S-LiCl-InBr3, Li2S-LiCl-InI3, Li2S-LiCl-TlF3, Li2S-LiCl-TlCl3, Li2S-LiCl-TlBr3, Li2S-LiCl-TlI3,Li2S-LiBr-AlF3, Li2S-LiBr-AlCl3, Li2S-LiBr-AlBr3, Li2S-LiBr-AlI3, Li2S-LiBr-GaF3, Li2S-LiBr-GaCl3, Li2S-LiBr-GaBr3, Li2S-LiBr-GaI3, Li2S-LiBr-InF3, Li2S-LiBr-InCl3, Li2S-LiBr-InBr3, Li2S-LiBr-InI3, Li2S-LiBr-TlF3, Li2S-LiBr-TlCl3, Li2S-LiBr-TlBr3, Li2S-LiBr-TlI3, Li2S-LiI-AlF3, Li2S-LiI-AlCl3, Li2S-LiI-AlBr3, Li2S-LiI-AlI3, Li2S-LiI-GaF3, Li2S-LiI-GaCl3, It may include Li2S-LiI-GaBr3, Li2S-LiI-GaI3, Li2S-LiI-InF3, Li2S-LiI-InCl3, Li2S-LiI-InBr3, Li2S-LiI-InI3, Li2S-LiI-TlF3, Li2S-LiI-TlCl3, Li2S-LiI-TlBr3, Li2S-LiI-TlI3 or a combination thereof.

[0041] The electronic conductivity of the electronically conductive material (4) is, for example, 1.0×10 at 25°C. 3 S / m or greater, 1.0×10 4 S / m or more, or 1.0×10 5It is S / m or greater. The form of the electronic conductive material (4) is, for example, a particulate electronic conductive material, a plate-shaped electronic conductive material, a rod-shaped electronic conductive material, or a combination thereof, but is not necessarily limited to these. The electronic conductive material (4) may be, for example, carbon, metal powder, metal compound, etc. When carbon is included as the electronic conductive material (4), a secondary battery having a high energy density per unit mass can be realized because carbon has high electronic conductivity and is light. The electronic conductive material (4) may have pores. By having pores in the electronic conductive material (4), Li2S can be contained within the pores, thereby increasing the contact area between Li2S and the electronic conductive material and increasing the specific surface area of ​​Li2S. The pore capacity is, for example, 0.1 cc / g to 20.0 cc / g, 0.5 cc / g to 10 cc / g, or 0.5 cc / g to 5 cc / g. The average pore diameter is, for example, 1 nm to 100 nm, 1 nm to 50 nm, or 1 nm to 20 nm. The BET specific surface area of ​​the electron-conducting material (4) having pores is 200 m² when the average pore diameter is 15 nm or less. 2 / g to 4500 m 2 / g, and if the average pore diameter is greater than 15 nm, 100 m 2 / g to 2500 m 2 It is / g. BET specific surface area, pore diameter, pore capacity, and average pore diameter can be obtained, for example, using the nitrogen adsorption method.

[0042] The electronically conductive material (4) according to one embodiment may include, for example, carbon. Carbon may be any material containing carbon atoms, for example, used as a conductive material in the art. Carbon may be, for example, crystalline carbon, amorphous carbon, or a combination thereof. Carbon may be, for example, a calcined product of a carbon precursor. Carbon may be, for example, a carbon nanostructure. The carbon nanostructure may be, for example, a one-dimensional carbon nanostructure, a two-dimensional carbon nanostructure, a three-dimensional carbon nanostructure, or a combination thereof. The carbon nanostructure may be, for example, a carbon nanotube (CNT), a carbon nanofiber (CNF), a carbon nanobelt, a carbon nanorod, graphene, graphene oxide (GO), reduced graphene oxide (rGO), a graphene ball (GB), or a combination thereof. The electronically conductive material (4) according to one embodiment may include, for example, at least one of a carbon nanotube (CNT) or a carbon nanofiber (CNF). Carbon may be, for example, porous carbon or non-porous carbon. Porous carbon may include, for example, periodic and regular two-dimensional or three-dimensional pores. Porous carbon may be, for example, carbon black such as Ketjen black, acetylene black, Denka black, thermal black, or channel black; graphite, activated carbon, or a combination thereof. The form of carbon may be, for example, particle form, sheet form, flake form, etc., but is not limited thereto; any form used as carbon in the relevant technical field is possible. The method for manufacturing a composite of Li2S or a Li2S-containing composite and carbon may be a dry method, a wet method, or a combination thereof, but is not limited thereto; and the method for manufacturing a composite of Li2S, a Li2S-containing composite and carbon in the relevant technical field may be, for example, milling, heat treatment, deposition, etc., but is not necessarily limited thereto; any method used in the relevant technical field is possible.According to one embodiment, a carbon-containing Li2S-containing composite may include, for example, Li2S-CNT, Li2S-CNF, or a combination thereof.

[0043] According to one embodiment, a Li2S-containing composite comprising a composite of Li2S (1), an ion-conducting material and an electron-conducting material (4) is, for example, Li2S-LiF-CNT, Li2S-LiCl-CNT, Li2S-LiBr-CNT, Li2S-LiI-CNT, Li2S-LiF-CNF, Li2S-LiCl-CNF, Li2S-LiBr-CNF, Li2S-LiI-CNF, Li2S-LiF-AlF3-CNT, Li2S-LiF-AlCl3-CNT, Li2S-LiF-AlBr3-CNT, Li2S-LiF-AlI3-CNT, Li2S-LiF-GaF3-CNT, Li2S-LiF-GaCl3-CNT, Li2S-LiF-GaBr3-CNT, Li2S-LiF-GaI3-CNT, Li2S-LiF-InF3-CNT, Li2S-LiF-InCl3-CNT, Li2S-LiF-InBr3-CNT, Li2S-LiF-InI3-CNT, Li2S-LiF-TlF3-CNT, Li2S-LiF-TlCl3-CNT, Li2S-LiF-TlBr3-CNT, Li2S-LiF-TlI3-CNT, Li2S-LiCl-AlF3-CNT, Li2S-LiCl-AlCl3-CNT, Li2S-LiCl-AlBr3-CNT, Li2S-LiCl-AlI3-CNT, Li2S-LiCl-GaF3-CNT, Li2S-LiCl-GaCl3-CNT, Li2S-LiCl-GaBr3-CNT, Li2S-LiCl-GaI3-CNT, Li2S-LiCl-InF3-CNT, Li2S-LiCl-InCl3-CNT, Li2S-LiCl-InBr3-CNT, Li2S-LiCl-InI3-CNT, Li2S-LiCl-TlF3-CNT, Li2S-LiCl-TlCl3-CNT, Li2S-LiCl-TlBr3-CNT, Li2S-LiCl-TlI3-CNT, Li2S-LiBr-AlF3-CNT, Li2S-LiBr-AlCl3-CNT, Li2S-LiBr-AlBr3-CNT, Li2S-LiBr-AlI3-CNT, Li2S-LiBr-GaF3-CNT, Li2S-LiBr-GaCl3-CNT, Li2S-LiBr-GaBr3-CNT, Li2S-LiBr-GaI3-CNT,Li2S-LiBr-InF3-CNT, Li2S-LiBr-InCl3-CNT, Li2S-LiBr-InBr3-CNT, Li2S-LiBr-InI3-CNT, Li2S-LiBr-TlF3-CNT, Li2S-LiBr-TlCl3-CNT, Li2S-LiBr-TlBr3-CNT, Li2S-LiBr-TlI3-CNT, Li2S-LiI-AlF3-CNT, Li2S-LiI-AlCl3-CNT, Li2S-LiI-AlBr3-CNT, Li2S-LiI-AlI3-CNT, Li2S-LiI-GaF3-CNT, Li2S-LiI-GaCl3-CNT, Li2S-LiI-GaBr3-CNT, Li2S-LiI-GaI3-CNT, Li2S-LiI-InF3-CNT, Li2S-LiI-InCl3-CNT, Li2S-LiI-InBr3-CNT, Li2S-LiI-InI3-CNT, Li2S-LiI-TlF3-CNT, Li2S-LiI-TlCl3-CNT, Li2S-LiI-TlBr3-CNT, Li2S-LiI-TlI3-CNT, Li2S-LiF-AlF3-CNF, Li2S-LiF-AlCl3-CNF, Li2S-LiF-AlBr3-CNF, Li2S-LiF-AlI3-CNF, Li2S-LiF-GaF3-CNF, Li2S-LiF-GaCl3-CNF, Li2S-LiF-GaBr3-CNF, Li2S-LiF-GaI3-CNF, Li2S-LiF-InF3-CNF, Li2S-LiF-InCl3-CNF, Li2S-LiF-InBr3-CNF, Li2S-LiF-InI3-CNF, Li2S-LiF-TlF3-CNF, Li2S-LiF-TlCl3-CNF, Li2S-LiF-TlBr3-CNF, Li2S-LiF-TlI3-CNF, Li2S-LiCl-AlF3-CNF, Li2S-LiCl-AlCl3-CNF, Li2S-LiCl-AlBr3-CNF, Li2S-LiCl-AlI3-CNF, Li2S-LiCl-GaF3-CNF, Li2S-LiCl-GaCl3-CNF, Li2S-LiCl-GaBr3-CNF, Li2S-LiCl-GaI3-CNF, Li2S-LiCl-InF3-CNF, Li2S-LiCl-InCl3-CNF,Li2S-LiCl-InBr3-CNF, Li2S-LiCl-InI3-CNF, Li2S-LiCl-TlF3-CNF, Li2S-LiCl-TlCl3-CNF, Li2S-LiCl-TlBr3-CNF, Li2S-LiCl-TlI3-CNF, Li2S-LiBr-AlF3-CNF, Li2S-LiBr-AlCl3-CNF, Li2S-LiBr-AlBr3-CNF, Li2S-LiBr-AlI3-CNF, Li2S-LiBr-GaF3-CNF, Li2S-LiBr-GaCl3-CNF, Li2S-LiBr-GaBr3-CNF, Li2S-LiBr-GaI3-CNF, Li2S-LiBr-InF3-CNF, Li2S-LiBr-InCl3-CNF, Li2S-LiBr-InBr3-CNF, Li2S-LiBr-InI3-CNF, Li2S-LiBr-TlF3-CNF, Li2S-LiBr-TlCl3-CNF, Li2S-LiBr-TlBr3-CNF, Li2S-LiBr-TlI3-CNF, Li2S-LiI-AlF3-CNF, Li2S-LiI-AlCl3-CNF, Li2S-LiI-AlBr3-CNF, Li2S-LiI-AlI3-CNF, Li2S-LiI-GaF3-CNF, Li2S-LiI-GaCl3-CNF, Li2S-LiI-GaBr3-CNF, Li2S-LiI-GaI3-CNF, Li2S-LiI-InF3-CNF, Li2S-LiI-InCl3-CNF, Li2S-LiI-InBr3-CNF, Li2S-LiI-InI3-CNF, Li2S-LiI-TlF3-CNF, Li2S-LiI-TlCl3-CNF, Li2S-LiI-TlBr3-CNF, 또는 Li2S-LiI-TlI3-CNF, 또는 이들의 임의의 조합을 포함할 수 있다.,

[0044] The size of the crystallites of Li2S obtained from the XRD spectrum of a Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electronic-conducting material (4) according to one embodiment may be, for example, 20 nm or less, 15 nm or less. The size of the crystallites of Li2S obtained from the XRD spectrum of the Li2S-containing composite may be, for example, 1 to 20 nm, 1 to 15 nm, or 3 to 14.5 nm. As the size of the crystallites of Li2S decreases, the contact area between Li2S and the lithium salt may be further increased. As the contact area between Li2S and the lithium salt is further increased, the ion conductivity of the composite of Li2S and the lithium salt may be further increased.

[0045] The ionic conductivity of the Li2S-containing composite comprising the composite of Li2S, the ionic conductive material, and the electronic conductive material (4) is, for example, 1×10⁻⁶ at 45°C. -6 S / cm or more, 2×10 -6 S / cm or more, 5×10 -6 It can be greater than S / cm. The ionic conductivity of the Li2S-containing composite is, for example, 5×10⁻⁶ at 45 ℃. -2 S / cm or less, 1×10 -2 S / cm or less, 7.5×10 -3 It may be less than S / cm. Ionic conductivity can be measured using, for example, electrochemical impedance spectrometry, DC polarization method, etc. As the Li2S-containing composite comprising a composite of Li2S, an ionic conductive material and an electronic conductive material (4) has an ionic conductivity in this range, the internal resistance of the positive active material layer (120) comprising the Li2S-containing composite comprising a composite of Li2S, an ionic conductive material and an electronic conductive material (4) can be further reduced.

[0046] The electronic conductivity of the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electronic-conducting material (4) is, for example, 1×10⁻⁶ at 45 °C. -3 S / cm or more, 5×10 -3 S / cm or greater, 7.5×10 -3 It can be greater than S / cm. The electronic conductivity of the Li2S-containing composite is, for example, 7.5×10⁻⁶ at 45 °C. -3 S / cm or less, 1×10 -2 S / cm or less, 1.5×10 -2 It may be less than S / cm. Electronic conductivity can be measured using, for example, electrochemical impedance spectrometry, DC polarization method, etc. As the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material and an electronically conductive material (4) has electronic conductivity in this range, the internal resistance of the positive active material layer (120) comprising the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material and an electronically conductive material (4) can be further reduced.

[0047] The lattice constant of the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electron-conducting material (4) according to one embodiment may be 5 Å or more, 5.5 Å or more, or 5.76 Å or more. It can be confirmed that a solid solution is formed by satisfying the above ranges for the lattice constant of the Li2S-containing composite. The lattice constant of the Li2S-containing composite may be 10 nm or less. The lattice constant was derived from the first peak for the (111) crystal plane appearing at a diffraction angle 2θ = 27˚ ± 2.0˚ in the XRD spectrum.

[0048] D10 of the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electronically conductive material (4) according to one embodiment may be 1.5 μm to 2.5 μm. D50 of the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electronically conductive material (4) according to one embodiment may be 6 μm to 7 μm. D90 of the Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electronically conductive material (4) according to one embodiment may be 20 μm to 36 μm. By having the Li2S-containing composite particles within this range of sizes, they can be more easily placed in the voids between the sulfide-based solid electrolytes, the formation of pinholes within the positive active material layer (120) is suppressed, and the internal resistance of the positive active material layer (120) can be reduced.

[0049] The modulus of a Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electron-conducting material (4) according to one embodiment may be 25 GPa or less. For example, the modulus may be measured through nanoindentation, dynamic mechanical analysis, atomic force microscopy, acoustic resonance, etc., but is not necessarily limited thereto. As the modulus of the Li2S-containing composite satisfies the above range, contact stability with the solid electrolyte within the positive electrode active material layer (120) may be improved.

[0050] Referring to FIG. 3, the Li2S-containing composite may comprise Li2S (1), an ion-conducting material (2, 3), and an electron-conducting material (4). A Li2S-containing composite according to one embodiment of the present disclosure may comprise Li2S (1), a lithium salt compound (2), and a boron group metal halide salt (3). The compositional ratio of each component forming the Li2S-containing composite is an important consideration in the cell design of a lithium-sulfur battery. For example, increasing the content of Li2S within the Li2S-containing composite may improve the capacity characteristics of the lithium-sulfur battery, but this may lead to a decrease in the ion conductivity and / or electron conductivity of the cathode (100). Conversely, decreasing the content of Li2S may result in a decrease in capacity characteristics. Therefore, in the design of a lithium-sulfur battery containing a Li2S-containing composite, it is important to design it so that the compositional ratio of Li2S and the conductive material is balanced.

[0051] According to one embodiment of the present disclosure, the content of Li2S (1) in the positive active material layer (120) may be 40 to 60 parts by weight or 45 to 50 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the energy density of the all-solid-state battery (10) may be improved.

[0052] According to one embodiment of the present disclosure, the content of the ion-conducting material (2, 3) in the positive active material layer (120) may be 20 to 40 parts by weight or 20 to 25 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the ion conductivity of the all-solid-state battery (10) can be improved. Consequently, a positive active material layer (120) with good lifespan characteristics can be manufactured even if a relatively small amount of solid electrolyte (20) is included. As a result, the content of the positive active material (10) included in the positive active material layer (120) can be increased, thereby providing an all-solid-state battery (10) with excellent capacity characteristics.

[0053] An ion-conducting material (2, 3) according to one embodiment of the present disclosure may include a lithium salt compound (2) and a boron group metal halide salt (3). Since the above description of the lithium salt compound (2) and the boron group metal halide salt (3) can be applied as is, a detailed description thereof will be omitted below.

[0054] According to one embodiment of the present disclosure, the content of the lithium salt compound (2) in the positive active material layer (120) may be 5 to 15 parts by weight, 4 to 10 parts by weight, or 5 to 6 parts by weight, based on 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the ion conductivity of the positive active material layer (120) can be improved. Consequently, a positive active material layer (120) with good lifespan characteristics can be manufactured even if a relatively small amount of solid electrolyte (20) is included. As a result, the content of the positive active material (10) included in the positive active material layer (120) can be increased, thereby providing an all-solid-state battery (10) with excellent capacity characteristics.

[0055] According to one embodiment of the present disclosure, the content of the boron group metal halide salt (3) in the positive active material layer (120) may be 15 to 25 parts by weight per 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the morphological characteristics of the Li2S-containing composite of the positive active material layer (120) are improved, thereby improving structural stability. Consequently, a positive active material layer (120) with good lifespan characteristics can be manufactured even if a relatively small amount of solid electrolyte (20) is included. As a result, the content of the positive active material (10) included in the positive active material layer (120) can be increased, thereby providing an all-solid-state battery (10) with excellent capacity characteristics.

[0056] According to one embodiment of the present disclosure, the content of the electronically conductive material (4) in the positive active material layer (120) may be 5 to 15 parts by weight or 10 to 12 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the electronic conductivity of the all-solid-state battery (10) may be improved. Consequently, the lifespan characteristics of the all-solid-state battery (10) may be improved.

[0057] According to one embodiment of the present disclosure, the content of the positive active material in the positive active material layer (120) may be 75 to 85 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). According to one embodiment of the present disclosure, the content of the positive active material may be greater than 70 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). According to one embodiment of the present disclosure, the content of the positive active material may be less than 90% by weight with respect to 100 parts by weight of the total positive active material layer (120). By satisfying the above ranges for the content of the positive active material, the all-solid-state battery (10) may have a high energy density.

[0058] A solid electrolyte according to one embodiment of the present disclosure may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics.

[0059] Sulfide-based solid electrolytes are, for example, Li3PO4-Li2SO4, 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, Li2S-P2S5-Z m S n (In the above formula, m and n are positive numbers, and Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (In the above formula, p and q are positive numbers, and M is one of P, Si, Ge, B, Al, Ga, and In), Li + 12-n-x A n+ X 2- 6-x Y - x (In the above formula, A is one of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, or Ta, X is one of S, Se, or Te, Y is Cl, Br, I, F, CN, OCN, SCN, or N3, and 1≤n≤5, 0≤x≤2) Li 7-m M m PS 6-n X n(In the above formula, M is one of Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, Sc, Y, Ti, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Ru, Os, Hs, Co, Rh, Ir, Mt, Ni, Pd, Pt, Ds, Au, Rg, Cd, Hg, or Cn, X is one of F, Cl, Br, or I, 0 <n≤2, 0<x≤2), 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 It may include (0≤x≤2) or a combination thereof.

[0060] Sulfide-based solid electrolytes can be manufactured by processing starting materials, such as Li2S or P2S5, using methods such as melt quenching or mechanical milling. Additionally, heat treatment may be performed after such processing. Sulfide-based solid electrolytes may be amorphous, crystalline, or a mixture thereof. Sulfide-based solid electrolytes may, for example, contain at least sulfur (S), phosphorus (P), and lithium (Li) as constituent elements. Sulfide-based solid electrolytes may, for example, contain Li2S-P2S5. When using a material containing Li2S-P2S5 as a sulfide-based solid electrolyte, the molar ratio of Li2S and P2S5 is, for example, in the range of Li2S : P2S5 = 20 : 80 to 90 : 10, 25 : 75 to 90 : 10, 30 : 70 to 70 : 30, and 40 : 60 to 60 : 40.

[0061] The sulfide-based solid electrolyte may be, for example, an argyrodite-type solid electrolyte. The density of the argyrodite-type solid electrolyte may be 1.5 to 2.0 g / cc. Since the argyrodite-type solid electrolyte has a density of 1.5 g / cc or higher, the internal resistance of the all-solid-state battery is reduced, and penetration of the solid electrolyte separator by lithium can be suppressed more effectively.

[0062] According to one embodiment of the present disclosure, the content of the solid electrolyte in the positive active material layer (120) may be 15 to 25 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). According to one embodiment of the present disclosure, the content of the positive active material may be greater than 15 parts by weight with respect to 100 parts by weight of the total positive active material layer (120). According to one embodiment of the present disclosure, the content of the positive active material may be less than 25 parts by weight with respect to the total weight of the positive active material layer (120). By satisfying the above ranges for the content of the positive active material, the all-solid-state battery (10) may have a high energy density.

[0063] A positive active material layer (120) according to one embodiment of the present disclosure may further include a binder. The binder included in the positive active material layer (120) may include, for example, at least one of styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), or polyethylene (PE).

[0064] According to one embodiment of the present disclosure, the content of the binder in the positive active material layer (120) may be 0.1 to 5 parts by weight or 0.5 to 2 parts by weight per 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the lifespan characteristics of the all-solid-state battery (10) may be further improved.

[0065] A positive active material layer (120) according to one embodiment of the present disclosure may further include a positive additive. The positive additive included in the positive active material layer (120) may include a composite electrolyte comprising a polymer and a lithium salt and a lithium-containing sulfide-based material.

[0066] The polymer of the above composite electrolyte may include, for example, polyoxyethylene (Mw = ~ 500), polyoxyalkylene, polyalkylene oxide (Mw = ~ 500), polyethylene glycol (Mw = ~ 500), polyethylene glycol dimethyl ether (PEGDME, Mw = ~ 500), or a combination thereof.

[0067] The lithium salt of the above composite electrolyte may include, for example, lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO₄), lithium tetrafluoroborate (LiBF4), lithium difluoro(oxalato)borate (LiDFOB), or a combination thereof.

[0068] In the above composite electrolyte, the mixing weight ratio of the polymer and the lithium salt may be, for example, 6:1 to 1:6 or 3:1 to 1:3 or 2:1 to 1:2.

[0069] The above lithium-containing sulfide-based material may include Li2S or lithium polysulfide. The lithium polysulfide may include Li2S2, Li2S3, Li2S4, Li2S6, Li2S8, or a combination thereof.

[0070] The weight ratio of the composite electrolyte and the lithium-containing sulfide-based material in the above anode additive may be, for example, 99:1 to 90:10 or 97:3 to 92:8 or 96:4 to 93:7.

[0071] According to one embodiment of the present disclosure, the positive active material layer (120) may further improve the ionic conductivity of the positive active material layer (120) by further including a positive additive. As a result, even if a relatively small amount of solid electrolyte (20) is included, the lifespan characteristics are good, and the content of the positive active material (10) included in the positive active material layer (120) can be increased to provide an all-solid-state battery (10) with excellent capacity characteristics.

[0072] According to one embodiment of the present disclosure, the content of the positive additive of the positive active material layer (120) may include 0.01 to 1 part by weight or 0.1 to 0.5 parts by weight per 100 parts by weight of the total positive active material layer (120). By satisfying the above range, the lifespan characteristics of the all-solid-state battery (10) may be further improved.

[0073] According to one embodiment of the present disclosure, the porosity of the positive active material layer (120) may be 0.1 to 35%. By satisfying the above range, the positive electrode is thinned and the energy density can be further improved. Consequently, the capacity of the all-solid-state battery (10) can be further improved. In this specification, the porosity of the positive active material layer (120) may be measured, for example, by a method of calculating the pore area from a mapping image of the cross-section of the positive active material layer (120) through ultrasonic analysis, or by a method of calculating the pore area from an electron microscope image of the cross-section of the positive active material layer (120).

[0074] The positive energy density of the positive active material layer (120) according to one embodiment of the present disclosure is 1 mAh / cm² 2 Up to 10 mAh / cm 2 It may be. In this specification, the positive energy density is the charge capacity that can be stored per unit area of ​​the positive active material layer (120), and can be measured through an electrochemical charge-discharge test. For example, a cell can be constructed by assembling the positive (100) with a reference electrode (e.g., lithium metal), and the discharge capacity can be measured by performing a charge-discharge test within a set voltage range and then dividing by the area of ​​the positive (100). The positive energy density can be set by adjusting the amount of the positive active material layer loaded onto the positive current collector (110).

[0075] A positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 2 mAh / cm² 2 Up to 4 mAh / cm 2 When this occurs, the thickness of the positive active material layer (120) may be 50 μm or less. The positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 3 mAh / cm² 2In this case, the thickness of the positive active material layer (120) may be 10 μm to 50 μm. The positive active material layer (120) according to one embodiment of the present disclosure may contain a relatively small amount of solid electrolyte by including a positive active material having excellent ion conductivity. In addition, the positive active material (10) included in the positive active material layer (120) according to one embodiment of the present disclosure has physical properties that facilitate thin film formation due to the characteristic of having low hardness (Vickers hardness or nano-indentation hardness). Accordingly, the positive energy density is approximately 3 mAh / cm² 2 Even at the level of the positive active material layer (120), thinning of the positive active material layer is possible.

[0076] A positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 4 mAh / cm² 2 Up to 6 mAh / cm² 2 When this occurs, the thickness of the positive active material layer (120) may be 90 μm or less. The positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 5 mAh / cm² 2 In this case, the thickness of the positive active material layer (120) may be 10 μm to 90 μm or 10 μm to 70 μm. The positive active material layer (120) according to one embodiment of the present disclosure may contain a relatively small amount of solid electrolyte by including a positive active material having excellent ion conductivity. In addition, the positive active material (10) included in the positive active material layer (120) according to one embodiment of the present disclosure has physical properties that facilitate thin film formation due to its low hardness (Vickers hardness or nano-indentation hardness). Accordingly, the positive energy density is approximately 5 mAh / cm² 2 Even at the level of the positive active material layer (120), thinning of the positive active material layer is possible.

[0077] A positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 5 mAh / cm² 2 Up to 7 mAh / cm² 2In this case, the thickness of the positive active material layer (120) may be 100 μm or less. The positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 6 mAh / cm² 2 When this occurs, the thickness of the positive active material layer (120) may be 10 μm to 100 μm or 10 μm to 90 μm. The positive active material layer (120) according to one embodiment of the present disclosure may contain a relatively small amount of solid electrolyte by including a positive active material having excellent ion conductivity. In addition, the positive active material (10) included in the positive active material layer (120) according to one embodiment of the present disclosure has physical properties that facilitate thin film formation due to its low hardness (Vickers hardness or nano-indentation hardness). Accordingly, the positive energy density is approximately 6 mAh / cm² 2 Even at the level of the positive active material layer (120), thinning of the positive active material layer is possible.

[0078] A positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 6 mAh / cm² 2 Up to 8 mAh / cm² 2 When this occurs, the thickness of the positive active material layer (120) may be 130 μm or less. The positive active material layer (120) according to one embodiment of the present disclosure has a positive energy density of 7 mAh / cm² 2 When this occurs, the thickness of the positive active material layer (120) may be 10 μm to 120 μm or 10 μm to 115 μm. The positive active material layer (120) according to one embodiment of the present disclosure may contain a relatively small amount of solid electrolyte by including a positive active material having excellent ion conductivity. In addition, the positive active material (10) included in the positive active material layer (120) according to one embodiment of the present disclosure has physical properties that facilitate thin film formation due to its low hardness (Vickers hardness or nano-indentation hardness). Accordingly, the positive energy density is approximately 9 mAh / cm² 2 Even at the level of the positive active material layer (120), thinning of the positive active material layer is possible.

[0079] Referring to FIG. 4, an all-solid-state battery (10) according to another embodiment of the present disclosure comprises a positive electrode (100); a negative electrode layer (200); and a solid electrolyte layer (300) disposed between the positive electrode (100) and the negative electrode layer (200); wherein the negative electrode layer (200) comprises a negative electrode current collector (210) and a negative electrode coating layer (220) on the negative electrode current collector (210).

[0080] Since the details regarding the anode (100) can be applied as described above, a detailed explanation will be omitted below.

[0081] A solid electrolyte layer (300) may be disposed between the positive electrode (100) and the negative electrode layer (200). The solid electrolyte layer (300) may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. The solid electrolyte included in the solid electrolyte layer (300) may be the same as or different from any one of the materials that may be included in the solid electrolyte included in the aforementioned positive electrode active material layer (120).

[0082] The negative current collector (210) may provide a reference surface on which a lithium metal layer (230) or a negative coating layer (220) is disposed. The negative current collector (210) may include, for example, a material that does not react with lithium, that is, does not form any alloys or compounds with lithium. The material constituting the negative current collector (210) may include at least one metal selected from the group consisting of, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni). The thickness of the negative current collector (210) may be 1 to 20 μm, for example, 5 to 15 μm, for example, 7 to 12 μm. The negative current collector (210) may be composed of one of the metals described above, or may include an alloy or coating material of two or more metals. The negative current collector (210) is, for example, in the form of a plate or foil. In other embodiments, the negative current collector (210) may be omitted.

[0083] The cathode coating layer (220) may include a mixture of first particles containing a lithium-affinity metal and second particles containing a carbon element.

[0084] The lithium-affinity metal contained in the first particle is a material that can be lithiated and delithiated. The cathode coating layer (220) can be formed by introducing the lithium-affinity metal onto the cathode current collector (210) through nanoparticle casting. Nanoparticle casting can be performed, for example, by applying a slurry (dispersion) in which the first particle and the second particle are mixed and dispersed in a solvent onto the cathode current collector (210) using a doctor blade. When the cathode coating layer (220) is introduced onto the cathode current collector (210) through nanoparticle casting, lithium ions can pass through the cathode coating layer (220), and lithium metal can be formed between the cathode coating layer (220) and the cathode current collector (210). The first particle included in the cathode coating layer (220) may be a nanoparticle of the lithium-affinity metal. The average particle size of the first particle may be, for example, 10 nm to 4 µm, 10 nm to 1 µm, 10 nm to 500 nm, 10 nm to 100 nm, or 20 nm to 80 nm. Since the first particle has an average particle size within this range, reversible plating and / or dissolution of lithium during charging and discharging may be facilitated. Additionally, as the first particle has a nano-size, lithium ions may pass through the negative electrode coating layer (220) containing the first particle, and lithium metal may be deposited between the negative electrode current collector (210) and the negative electrode coating layer (220). The average particle size of the first particle is, for example, a median diameter (D50) measured using a laser particle size distribution meter.

[0085] Lithium-affinity metals may include, for example, at least one of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), or zinc (Zn), or any combination thereof.

[0086] The second particle can uniformly coat the first particle onto the negative current collector (210). The second particle containing a carbon element can uniformly coat the first particle onto the negative current collector (210), thereby uniformly coating the first particle onto the negative current collector (210). The uniformly coated first particle can uniformly precipitate lithium metal onto the negative current collector (210) to prevent the formation of lithium dendrites.

[0087] The second particle may include, for example, at least one of amorphous carbon or crystalline carbon, or any combination thereof.

[0088] Amorphous carbon may include, for example, at least one of carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, or carbon nanotubes (CNT), or any combination thereof. Amorphous carbon can be distinguished from crystalline carbon or graphite-based carbon as carbon that does not have crystallinity or has very low crystallinity.

[0089] The negative electrode coating layer (220) comprises, for example, a mixture of a first particle containing a lithium-affinity metal and a second particle containing a carbon element, so that the first particle is uniformly coated on the negative electrode current collector (210) through the second particle, and the first particle can uniformly deposit lithium metal between the negative electrode coating layer (220) and the negative electrode current collector (210). Accordingly, the formation of lithium dendrites is suppressed, and the lifespan characteristics of the all-solid-state battery (10) can be improved.

[0090] The mixing ratio of the mixture of the first particle and the second particle included in the cathode coating layer (220) may be, for example, 10:1 to 1:10, 1:1 to 1:10, 1:2 to 1:10, 1:1 to 1:5, or 1:2 to 1:5 by weight.

[0091] The cathode coating layer (220) may further include a binder. The binder included in the cathode coating layer (220) may be, for example, polyacrylic acid, carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, etc., but is not necessarily limited to these, and any binder used in the relevant technical field is possible. The binder may be composed of a single binder or a plurality of different binders. The content of the binder included in the cathode coating layer (220) may be, for example, 55 weight% or less, 0.1 to 50 weight%, 0.1 to 20 weight%, or 0.1 to 10 weight% with respect to the total weight of the cathode coating layer (220).

[0092] The thickness of the negative electrode coating layer (220) may be, for example, 0.1 μm to 5 μm, 0.1 μm to 3 μm, or 0.5 μm to 5 μm, 0.5 μm to 3 μm, or 0.5 μm to 2 μm. If the thickness of the negative electrode coating layer (220) is less than the above range, lithium dendrites formed between the negative electrode coating layer (220) and the negative electrode current collector (210) may cause the negative electrode coating layer (220) to collapse, thereby degrading the cycle characteristics of the all-solid-state battery (10). If the thickness of the negative electrode coating layer (220) exceeds the above range, the energy density of the all-solid-state battery (10) may decrease.

[0093] Referring to FIG. 5, a negative electrode layer (200) according to another embodiment of the present disclosure may further include a lithium metal layer (230) disposed between a negative electrode current collector (210) and a negative electrode coating layer (220).

[0094] The lithium metal layer (230) may include lithium or a lithium alloy. Since the lithium metal layer (230) is a metal layer containing lithium, it may function as, for example, a lithium reservoir. 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, but is not limited to these; any alloy used as a lithium alloy in the relevant technical field may be possible. The lithium metal layer (230) may be composed of one of these alloys or lithium, or may be composed of various types of alloys. The lithium metal layer (230) may be, for example, a plated layer. The lithium metal layer (230) may be deposited between the negative electrode coating layer (220) and the negative electrode current collector (210) during the charging process of the all-solid-state battery (10), for example.

[0095]

[0096] The creative idea is explained in more detail through the following examples and comparative examples. However, the examples are intended to illustrate the creative idea and do not limit the scope of the creative idea to these examples alone.

[0097] Example 1 (Li2S-LiI-AlI3-CNF : SE = 80:20)

[0098] (Manufacturing of the anode layer)

[0099] A Li2S-LiI-AlI3-CNF composite was prepared as a cathode active material. The Li2S-LiI-AlI3-CNF composite was prepared as follows. Li2S, LiI, and AlI3 were mixed in a weight ratio of 45.71:5.71:17.14. The mixture was mechanically milled using a ball mill to prepare the Li2S-LiI-AlI3 composite. The milling conditions were 25 ℃ at 450 rpm for 10 hours. The milling energy applied to the sample during milling was 20 G. The Li2S-LiI-AlI3 composite thus prepared was mixed with carbon nanofiber (CNF) in a weight ratio of 68.56:11.44. The mixture was mechanically milled using a ball mill to prepare the Li2S-LiI-AlI3-CNF composite. The milling conditions were 25 ℃ at 450 rpm for 10 hours. The milling energy applied to the sample during milling was 20 G.

[0100] As a solid electrolyte, Li6PS5Cl solid electrolyte (D50 = 1.0 μm, crystalline), which is an argyrodite-type crystal, was prepared.

[0101] PTFE was prepared as the anode binder.

[0102] The cathode additive was prepared by mixing the composite electrolyte and a lithium-containing sulfide-based material (Li2S) in a weight ratio of 95:5. The composite electrolyte was prepared by mixing Polyethylene glycol dimethyl ether (PEGDME, Mw = ~500) as the polymer and LiTFSI as the lithium salt. The mixing weight ratio of the polymer and the lithium salt in the composite electrolyte was 1:1.

[0103] The prepared positive electrode active material and solid electrolyte were dry-mixed using a RAM mixer. A positive electrode binder and a positive electrode additive were mixed into the mixture of the positive electrode active material and solid electrolyte to prepare a mixture. The mixture was prepared in a weight ratio of positive electrode active material : solid electrolyte : positive electrode binder : positive electrode additive = 80 : 20 : 0.72 : 0.48. The positive electrode mixture was placed on one side of a positive electrode current collector made of aluminum foil coated with carbon on one side. The positive electrode mixture ultimately has a positive electrode energy density of 3 mAh / cm² 2 The layers were stacked as follows. An anode layer was prepared by plate pressing the anode current collector / anode composite laminate at a pressure of 200 MPa for 10 minutes. The thickness of the anode layer was approximately 65 μm. The thickness of the anode active material layer was approximately 45 μm, and the thickness of the carbon-coated aluminum foil was approximately 20 μm.

[0104] (Preparation of solid electrolyte layer)

[0105] A mixture was prepared by adding 1.5 parts by weight of an acrylic binder to 98.5 parts by weight of an argyrodite-type crystal Li6PS5Cl solid electrolyte (D50 = 3.0 μm, crystalline) to the solid electrolyte. A slurry was prepared by stirring while adding octyl acetate to the prepared mixture. The prepared slurry was applied using a bar coater onto a 15 μm thick nonwoven fabric placed on a 75 μm thick PET substrate, and dried in air at 80°C for 10 minutes to obtain a laminate. The obtained laminate was vacuum dried at 80°C for 2 hours. A solid electrolyte layer was prepared by the above process.

[0106] (Cathode layer manufacturing)

[0107] A SUS foil with a thickness of 10 μm was prepared as a cathode current collector. In addition, carbon black (CB) with a primary particle size of about 30 nm and silver (Ag) particles with an average particle diameter of about 60 nm were prepared as the composition of the cathode coating layer.

[0108] 4 g of a mixed powder, prepared by mixing carbon black (CB) and silver (Ag) particles in a weight ratio of 3:1, was placed in a container, and 4 g of an NMP solution containing 7 wt% of PVDF binder (Kureha # 9300) was added to prepare a mixed solution. A slurry was prepared by stirring the mixed solution while gradually adding NMP (N-methyl-2-pyrrolidone) to it. The prepared slurry was applied to a SUS sheet using a bar coater and dried in air at 80°C for 10 minutes to prepare a laminate. The prepared laminate was vacuum dried at 40°C for 10 hours. The dried laminate was cold-roll-pressed to flatten the surface of the cathode coating layer, thereby fabricating the cathode layer. The thickness of the cathode coating layer was approximately 15 μm.

[0109] (Manufacturing of all-solid-state batteries)

[0110] A cathode layer / solid electrolyte layer was arranged so that a cathode coating layer on the cathode layer contacted the solid electrolyte layer, and a cathode layer / solid electrolyte layer laminate was prepared by heat and pressure.

[0111] An electrode assembly comprising a cathode layer / solid electrolyte layer / anode layer was prepared by arranging the anode layer such that the solid electrolyte layer contacts one surface of the anode layer.

[0112] The prepared electrode assembly was subjected to plate press treatment. This pressurization process sintered the solid electrolyte layer, thereby improving battery characteristics. The thickness of the sintered solid electrolyte layer was approximately 45 μm. The sintered electrode assembly was placed in a pouch and sealed to prepare a sealed electrode assembly. Parts of the positive electrode current collector and the negative electrode current collector were protruded outside the sealed electrode assembly to be used as the positive layer terminal and the negative layer terminal.

[0113] An all-solid-state battery was manufactured by placing an electrode assembly between two pressure plates (not shown) and fastening the two pressure plates with screws, thereby applying constant pressure to both sides of the electrode assembly.

[0114] Example 2 (Li2S-LiI-AlI3-CNF : SE = 80:20)

[0115] The cathode composite ultimately has a cathode energy density of 5 mAh / cm² 2 An all-solid-state battery was manufactured using the same method as in Example 1, except that the layers were stacked to form a solid-state battery. The thickness of the manufactured positive electrode layer was approximately 89 μm. The thickness of the positive electrode active material layer was approximately 69 μm, and the thickness of the carbon-coated aluminum foil was approximately 20 μm.

[0116] Example 3 (Li2S-LiI-AlI3-CNF : SE = 80:20)

[0117] The cathode composite ultimately has a cathode energy density of 6 mAh / cm² 2An all-solid-state battery was manufactured in the same manner as in Example 1, except that the layers were stacked to form a solid-state battery. The thickness of the manufactured positive electrode layer was approximately 107 μm. The thickness of the positive electrode active material layer was approximately 87 μm, and the thickness of the carbon-coated aluminum foil was approximately 20 μm.

[0118] Example 4 (Li2S-LiI-AlI3-CNF : SE = 80:20)

[0119] The cathode composite ultimately has a cathode energy density of 7 mAh / cm² 2 An all-solid-state battery was manufactured using the same method as in Example 1, except that the layers were stacked to form a solid-state battery. The thickness of the manufactured positive electrode layer was approximately 134 μm. The thickness of the positive electrode active material layer was approximately 114 μm, and the thickness of the carbon-coated aluminum foil was approximately 20 μm.

[0120] Comparative Example 1 (Li2S-LiI-CNF : SE = 70:30)

[0121] A Li2S-LiI-CNF composite was prepared as a cathode active material. The Li2S-LiI-CNF composite was prepared as follows. Li2S and LiI were mixed in a weight ratio of 40:20. The mixture was mechanically milled using a ball mill to prepare the Li2S-LiI composite. The milling conditions were 25 ℃ at 450 rpm for 10 hours. The milling energy applied to the sample during milling was 20 G. The Li2S-LiI composite thus prepared was mixed with carbon nanofiber (CNF) in a weight ratio of 60:10. The mixture was mechanically milled using a ball mill to prepare the Li2S-LiI-CNF composite. The milling conditions were 25 ℃ at 450 rpm for 10 hours. The milling energy applied to the sample during milling was 20 G.

[0122] The prepared positive electrode active material and solid electrolyte were dry-mixed using a RAM mixer. A positive electrode binder was mixed into the mixture of the positive electrode active material and solid electrolyte to prepare a mixture. The same solid electrolyte and positive electrode binder prepared in Example 1 were used. The mixture was prepared in a weight ratio of positive electrode active material : solid electrolyte : positive electrode binder = 70 : 30 : 1.2.

[0123] The anode composite was placed on one side of an anode current collector made of aluminum foil carbon-coated on one side. The anode composite ultimately has an anode energy density of 3 mAh / cm² 2 The layers were stacked to form a positive current collector / positive composite laminate. The positive layer was prepared by plate pressing the positive current collector / positive composite laminate at a pressure of 200 MPa for 10 minutes. The thickness of the positive layer was approximately 104 μm. The thickness of the positive active material layer was approximately 84 μm, and the thickness of the carbon-coated aluminum foil was approximately 20 μm. An all-solid-state battery was manufactured using the same method as in Example 1, except that the positive layer prepared in this way was applied.

[0124] Comparative Example 2 (Li2S-LiI-CNF : SE = 80:20)

[0125] An all-solid-state battery was manufactured using the same method as in Comparative Example 1, except that the cathode composite layer was prepared by mixing the cathode active material, solid electrolyte, and cathode binder in a weight ratio of 80:20:1.2. The cathode composite ultimately had a cathode energy density of 3 mAh / cm². 2 It was stacked so as to be, and the thickness of the anode layer was about 88 μm. The thickness of the anode active material layer was about 68 μm, and the thickness of the carbon-coated aluminum foil was about 20 μm.

[0126] Comparative Example 3 (Li2S-LiI-CNF : SE = 90:10)

[0127] An all-solid-state battery was manufactured using the same method as in Comparative Example 1, except that the cathode composite layer was prepared by mixing the cathode active material, solid electrolyte, and cathode binder in a weight ratio of 90:10:1.2. The cathode composite ultimately had a cathode energy density of 3 mAh / cm². 2 It was stacked so as to be, and the thickness of the anode layer was about 79 μm. The thickness of the anode active material layer was about 59 μm, and the thickness of the carbon-coated aluminum foil was about 20 μm.

[0128] Comparative Example 4 (Li2S-LiI-AlI3-CNF : SE = 70:30)

[0129] An all-solid-state battery was manufactured using the same method as in Example 1, except that the cathode composite layer was prepared by mixing the cathode active material, solid electrolyte, and cathode binder in a weight ratio of 70:30:1.2. The cathode composite ultimately had a cathode energy density of 3 mAh / cm². 2 It was stacked so as to be, and the thickness of the anode layer was about 85 μm. The thickness of the anode active material layer was about 65 μm, and the thickness of the carbon-coated aluminum foil was about 20 μm.

[0130] Comparative Example 5 (Li2S-LiI-AlI3-CNF : SE = 90:10)

[0131] An all-solid-state battery was manufactured using the same method as in Example 1, except that the cathode composite layer was prepared by mixing the cathode active material, solid electrolyte, and cathode binder in a weight ratio of 90:10:1.2. The cathode composite ultimately has a cathode energy density of 3 mAh / cm². 2 It was stacked so as to be, and the thickness of the anode layer was about 67 μm. The thickness of the anode active material layer was about 47 μm, and the thickness of the carbon-coated aluminum foil was about 20 μm.

[0132] Evaluation Example 1: Evaluation of Anode Capacity and Measurement of Mechanical Properties

[0133] The initial electrode capacity, positive active material layer thickness, and positive energy density of all-solid-state batteries prepared according to Examples 1 to 4 and Comparative Examples 1 to 5 were measured and / or calculated and summarized in Table 1 below.

[0134] The initial electrode capacity was calculated by dividing the mass of the loaded positive active material by the discharge capacity of the first cycle, and the positive energy density was set in advance during the loading stage and the positive active material layer was applied accordingly.

[0135] The thickness of the positive active material layer was measured as the average thickness between the interface of the positive active material layer (120) and the solid electrolyte layer (300) from the positive current collector (110).

[0136] The porosity was calculated by determining the area of ​​the pores from a mapping image of the cross-section of the positive active material layer (120) through ultrasonic analysis.

[0137] Initial electrode capacity (mAh / g 양극 ) Anode active material layer thickness (㎛) Anode energy density (mAh / cm²) 2 ) Anode active material layer porosity (%) Example 1 38945332 Example 2 40169531 Example 3 36887629 Example 4 349114727 Comparative Example 1 32684336 Comparative Example 2 33468342 Comparative Example 3 34159348 Comparative Example 4 32765338 Comparative Example 5 34047349

[0138] Referring to Table 1, although Example 1 was designed to have the same anode energy density as Comparative Examples 1 to 5, Example 1 had a relatively superior electrode capacity and a thinner anode active material layer compared to Comparative Examples 1 to 5. Examples 1 to 4 had a relatively lower anode active material layer porosity (%) compared to Comparative Examples 1 to 5. As a result, it was easy to realize an anode active material layer having a high anode energy density.

[0139] Evaluation Example 2: Evaluation of Life and Rate Characteristics

[0140] Charge and discharge tests of the all-solid-state batteries prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were conducted in the following manner. Measurements were performed by placing the batteries in a constant temperature bath at 45°C. In the first cycle, the batteries were charged with a constant current of 0.05 C until the battery voltage reached 2.8 V, and discharged with a constant current of 0.05 C until the battery voltage reached 1 V to measure the initial charge capacity and initial discharge capacity. In the second cycle, the batteries were charged with a constant current of 0.05 C until the battery voltage reached 2.65 V, and discharged with a constant current of 0.05 C until the battery voltage reached 1.4 V to measure the capacity. From the third cycle onwards, the batteries were charged with a constant current of 0.1 C until the battery voltage reached 2.65 V, and discharged with a constant current of 0.1 C until the battery voltage reached 1.4 V to measure the capacity. The third cycle discharge capacity divided by the second cycle discharge capacity and expressed as a percentage is defined as the rate characteristic and is shown in Table 2 below.

[0141] Afterwards, the charge-discharge test as described above was repeated, and the charge-discharge cycle was repeated until the discharge capacity compared to the initial discharge capacity of the battery reached 80% (SOH 80%). The life characteristics measured in this way are shown in Table 2 below.

[0142] Lifespan Characteristics (@SOH 80%, Cycles) Rate Characteristics (%) Example 1: 14094.4 Example 2: 15094.2 Example 3: 6791.2 Example 4: 4190.7 Comparative Example 1: 2188.0 Comparative Example 2: 1786.1 Comparative Example 3: 3880.7 Comparative Example 4: 2889.3 Comparative Example 5: 1985.2

[0143] Examples 1 to 4 realize a positive electrode having good lifespan and rate characteristics, a thin thickness, and excellent capacity characteristics, and an all-solid-state battery including the same. Although exemplary embodiments have been described in detail above with reference to the attached drawings, the present creative idea is not limited to such examples. It is obvious that a person skilled in the art to which the present creative idea belongs can derive various modified or altered examples within the scope of the technical idea described in the patent claims, and these also naturally fall within the technical scope of the present creative idea.

Claims

1. A positive active material layer comprising a positive active material and a solid electrolyte, wherein; The above positive active material includes a Li2S-containing complex, and The above Li2S-containing composite comprises Li2S, a lithium salt compound, a boron group metal halide salt, and an electronically conductive material, wherein The content of the above Li2S is 40 to 60 parts by weight per 100 parts by weight of the entire anode active material layer, and The content of the lithium salt compound is 5 to 15 parts by weight per 100 parts by weight of the entire positive electrode active material layer, and The content of the above boron group metal halide salt is 15 to 25 parts by weight per 100 parts by weight of the entire anode active material layer, and The content of the electronically conductive material is 5 to 15 parts by weight per 100 parts by weight of the entire positive active material layer, and The content of the above positive active material is 75 to 85 parts by weight based on 100 parts by weight of the entire positive active material layer, and An anode having a content of 15 to 25 parts by weight per 100 parts by weight of the entire anode active material layer.

2. In Paragraph 1, The above lithium salt compound comprises at least one of LiF, LiCl, LiBr, or LiI, an anode.

3. In Paragraph 1, The above boron group metal halide salt comprises at least one of AlF3, AlCl3, AlBr3, AlI3, GaF3, GaCl3, GaBr3, GaI3InF3, InCl3, InBr3, InI3TlF3, TlCl3, TlBr3, or TlI3, an anode.

4. In Paragraph 1, The above electronically conductive material is an anode comprising at least one of carbon nanotubes (CNT) or carbon nanofibers (CNF).

5. In Paragraph 1, 상기 Li2S 함유 복합체는, Li2S-LiF-CNT, Li2S-LiCl-CNT, Li2S-LiBr-CNT, Li2S-LiI-CNT, Li2S-LiF-CNF, Li2S-LiCl-CNF, Li2S-LiBr-CNF, Li2S-LiI-CNF, Li2S-LiF-AlF3-CNT, Li2S-LiF-AlCl3-CNT, Li2S-LiF-AlBr3-CNT, Li2S-LiF-AlI3-CNT, Li2S-LiF-GaF3-CNT, Li2S-LiF-GaCl3-CNT, Li2S-LiF-GaBr3-CNT, Li2S-LiF-GaI3-CNT, Li2S-LiF-InF3-CNT, Li2S-LiF-InCl3-CNT, Li2S-LiF-InBr3-CNT, Li2S-LiF-InI3-CNT, Li2S-LiF-TlF3-CNT, Li2S-LiF-TlCl3-CNT, Li2S-LiF-TlBr3-CNT, Li2S-LiF-TlI3-CNT, Li2S-LiCl-AlF3-CNT, Li2S-LiCl-AlCl3-CNT, Li2S-LiCl-AlBr3-CNT, Li2S-LiCl-AlI3-CNT, Li2S-LiCl-GaF3-CNT, Li2S-LiCl-GaCl3-CNT, Li2S-LiCl-GaBr3-CNT, Li2S-LiCl-GaI3-CNT, Li2S-LiCl-InF3-CNT, Li2S-LiCl-InCl3-CNT, Li2S-LiCl-InBr3-CNT, Li2S-LiCl-InI3-CNT, Li2S-LiCl-TlF3-CNT, Li2S-LiCl-TlCl3-CNT, Li2S-LiCl-TlBr3-CNT, Li2S-LiCl-TlI3-CNT, Li2S-LiBr-AlF3-CNT, Li2S-LiBr-AlCl3-CNT, Li2S-LiBr-AlBr3-CNT, Li2S-LiBr-AlI3-CNT, Li2S-LiBr-GaF3-CNT, Li2S-LiBr-GaCl3-CNT, Li2S-LiBr-GaBr3-CNT, Li2S-LiBr-GaI3-CNT, Li2S-LiBr-InF3-CNT, Li2S-LiBr-InCl3-CNT, Li2S-LiBr-InBr3-CNT,Li2S-LiBr-InI3-CNT, Li2S-LiBr-TlF3-CNT, Li2S-LiBr-TlCl3-CNT, Li2S-LiBr-TlBr3-CNT, Li2S-LiBr-TlI3-CNT, Li2S-LiI-AlF3-CNT, Li2S-LiI-AlCl3-CNT, Li2S-LiI-AlBr3-CNT, Li2S-LiI-AlI3-CNT, Li2S-LiI-GaF3-CNT, Li2S-LiI-GaCl3-CNT, Li2S-LiI-GaBr3-CNT, Li2S-LiI-GaI3-CNT, Li2S-LiI-InF3-CNT, Li2S-LiI-InCl3-CNT, Li2S-LiI-InBr3-CNT, Li2S-LiI-InI3-CNT, Li2S-LiI-TlF3-CNT, Li2S-LiI-TlCl3-CNT, Li2S-LiI-TlBr3-CNT, Li2S-LiI-TlI3-CNT, Li2S-LiF-AlF3-CNF, Li2S-LiF-AlCl3-CNF, Li2S-LiF-AlBr3-CNF, Li2S-LiF-AlI3-CNF, Li2S-LiF-GaF3-CNF, Li2S-LiF-GaCl3-CNF, Li2S-LiF-GaBr3-CNF, Li2S-LiF-GaI3-CNF, Li2S-LiF-InF3-CNF, Li2S-LiF-InCl3-CNF, Li2S-LiF-InBr3-CNF, Li2S-LiF-InI3-CNF, Li2S-LiF-TlF3-CNF, Li2S-LiF-TlCl3-CNF, Li2S-LiF-TlBr3-CNF, Li2S-LiF-TlI3-CNF, Li2S-LiCl-AlF3-CNF, Li2S-LiCl-AlCl3-CNF, Li2S-LiCl-AlBr3-CNF, Li2S-LiCl-AlI3-CNF, Li2S-LiCl-GaF3-CNF, Li2S-LiCl-GaCl3-CNF, Li2S-LiCl-GaBr3-CNF, Li2S-LiCl-GaI3-CNF, Li2S-LiCl-InF3-CNF, Li2S-LiCl-InCl3-CNF, Li2S-LiCl-InBr3-CNF, Li2S-LiCl-InI3-CNF, Li2S-LiCl-TlF3-CNF,Li2S-LiCl-TlCl3-CNF, Li2S-LiCl-TlBr3-CNF, Li2S-LiCl-TlI3-CNF, Li2S-LiBr-AlF3-CNF, Li2S-LiBr-AlCl3-CNF, Li2S-LiBr-AlBr3-CNF, Li2S-LiBr-AlI3-CNF, Li2S-LiBr-GaF3-CNF, Li2S-LiBr-GaCl3-CNF, Li2S-LiBr-GaBr3-CNF, Li2S-LiBr-GaI3-CNF, Li2S-LiBr-InF3-CNF, Li2S-LiBr-InCl3-CNF, Li2S-LiBr-InBr3-CNF, Li2S-LiBr-InI3-CNF, Li2S-LiBr-TlF3-CNF, Li2S-LiBr-TlCl3-CNF, Li2S-LiBr-TlBr3-CNF, Li2S-LiBr-TlI3-CNF, Li2S-LiI-AlF3-CNF, Li2S-LiI-AlCl3-CNF, Li2S-LiI-AlBr3-CNF, Li2S-LiI-AlI3-CNF, Li2S-LiI-GaF3-CNF, Li2S-LiI-GaCl3-CNF, Li2S-LiI-GaBr3-CNF, Li2S-LiI-GaI3-CNF, Li2S-LiI-InF3-CNF, Li2S-LiI-InCl3-CNF, Li2S-LiI-InBr3-CNF, Li2S-LiI-InI3-CNF, Li2S-LiI-TlF3-CNF, Li2S-LiI-TlCl3-CNF, Li2S-LiI-TlBr3-CNF, 또는 Li2S-LiI-TlI3-CNF, 또는 이들의 임의의 조합을 포함하는, 양극., 6. In Paragraph 1, The above solid electrolyte is an anode comprising a sulfide-based solid electrolyte.

7. In Paragraph 6, The above sulfide-based solid electrolyte is Li3PO4-Li2SO4, 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, Li2S-P2S5-Z m S n (In the above formula, m and n are positive numbers, and Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (In the above formula, p and q are positive numbers, and M is one of P, Si, Ge, B, Al, Ga, and In), Li + 12-n-x A n+ X 2- 6-x Y - x (In the above formula, A is one of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, or Ta, X is one of S, Se, or Te, Y is Cl, Br, I, F, CN, OCN, SCN, or N3, and 1≤n≤5, 0≤x≤2) Li 7-m M m PS 6-n X n (In the above formula, M is one of Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, Sc, Y, Ti, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Ru, Os, Hs, Co, Rh, Ir, Mt, Ni, Pd, Pt, Ds, Au, Rg, Cd, Hg, or Cn, X is one of F, Cl, Br, or I, 0 <n≤2, 0<x≤2), 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 A positive electrode comprising (0≤x≤2) or a combination thereof.

8. In Paragraph 1, The above positive active material layer further includes a binder, and The above binder comprises at least one of styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), or polyethylene (PE).

9. In Paragraph 8, An anode comprising 0.1 to 5 parts by weight of the binder based on 100 parts by weight of the entire anode active material layer.

10. In Paragraph 1, The above positive active material layer further comprises a positive additive, The above-mentioned anode additive comprises a composite electrolyte comprising a polymer and a lithium salt and a lithium-containing sulfide-based material, and an anode.

11. In Paragraph 10, An anode comprising 0.01 to 1 weight part of the anode additive per 100 weight parts of the entire anode active material layer.

12. In Paragraph 1, An anode having a porosity of 0.1 to 35% in the anode active material layer.

13. In Paragraph 1, The anode energy density is 2 mAh / cm² 2 Up to 4 mAh / cm 2 A positive electrode having a thickness of 50 μm or less when the positive electrode active material layer is at that time.

14. In Paragraph 1, The anode energy density is 4 mAh / cm² 2 Up to 6 mAh / cm² 2 A positive electrode having a thickness of 90 μm or less when the positive electrode active material layer is at that time.

15. In Paragraph 1, The anode energy density is 5 mAh / cm² 2 Up to 7 mAh / cm² 2 A positive electrode having a thickness of 100 μm or less when the positive electrode active material layer is at that time.

16. In Paragraph 1, The anode energy density is 6 mAh / cm² 2 Up to 8 mAh / cm² 2 A positive electrode having a thickness of 130 μm or less when the positive electrode active material layer is at that time.

17. Anode according to paragraph 1; cathode layer; and It includes a solid electrolyte layer disposed between the anode and the cathode layer; The above-mentioned negative electrode layer comprises a negative electrode current collector and a negative electrode coating layer on the negative electrode current collector, in an all-solid-state battery.

18. In Paragraph 17, The above-described negative electrode coating layer comprises a mixture of first particles containing a lithium-affinity metal and second particles containing a carbon element, in an all-solid-state battery.

19. In Paragraph 17, The above solid electrolyte layer comprises a sulfide-based solid electrolyte, in an all-solid-state battery.

20. In Paragraph 17, The above-described negative electrode layer further comprises a lithium metal layer disposed between the negative electrode current collector and the negative electrode coating layer, in an all-solid-state battery.

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