Negative electrode for all-solid-state battery

Abstract

The present invention relates to a negative electrode for an all-solid-state battery and an all-solid-state battery comprising same and, more specifically, to a negative electrode for an all-solid-state battery and an all-solid-state battery comprising same, the negative electrode comprising a negative electrode current collector and a negative electrode coating layer disposed on the negative electrode current collector, wherein the negative electrode coating layer comprises a carbon material coated with metal phthalocyanine, and the carbon material is carbon black.

Description

Negative electrode for all-solid-state batteries

[0001] The invention relates to a negative electrode for an all-solid-state battery and an all-solid-state battery including the same.

[0002]

[0003] Recently, driven by industrial demands, the development of batteries with high energy density and safety is actively underway. For example, lithium-ion batteries are being commercialized not only in the fields of information and communication devices but also in the automotive sector. In the automotive sector, safety is considered particularly important because it is directly related to human life.

[0004] Recently, all-solid-state batteries in which liquid electrolytes are replaced with solid electrolytes have been proposed. By not using flammable organic dispersion media, all-solid-state batteries can significantly reduce the likelihood of fire or explosion in the event of a short circuit. Therefore, these all-solid-state batteries can offer significantly higher safety compared to lithium-ion batteries that use liquid electrolytes.

[0005]

[0006] The problem that the present invention aims to solve is to provide a negative electrode for an all-solid-state battery that promotes the uniform growth of a lithium metal layer during charging and discharging and suppresses the formation of lithium dendrites.

[0007] Another problem that the present invention aims to solve is to provide an all-solid-state battery with improved electrochemical properties.

[0008]

[0009] According to the concept of the present invention, a negative electrode for an all-solid-state battery comprises a negative electrode current collector and a negative electrode coating layer on the negative electrode current collector, wherein the negative electrode coating layer comprises a carbon material coated with metal phthalocyanine, and the carbon material may be carbon black.

[0010] According to another concept of the present invention, a negative electrode for an all-solid-state battery comprises a negative electrode current collector and a negative electrode coating layer on the negative electrode current collector, wherein the negative electrode coating layer may comprise a carbon material coated with zinc (Zn) phthalocyanine.

[0011] According to another concept of the present invention, a negative electrode for an all-solid-state battery comprises a negative electrode current collector and a negative electrode coating layer on the negative electrode current collector, wherein the negative electrode coating layer comprises a carbon material coated with a metal phthalocyanine, and the weight ratio of the metal phthalocyanine to the carbon material may be 5:95 to 50:50.

[0012]

[0013] The negative electrode for an all-solid-state battery according to the present invention may include a coating layer comprising a carbon material coated with a metal phthalocyanine. The carbon material coated with the metal phthalocyanine can improve the mobility of lithium ions during charging and discharging, thereby inducing the uniform formation of a lithium metal layer, and thus the lifespan characteristics of the all-solid-state battery can be improved.

[0014]

[0015] FIG. 1 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention.

[0016] FIG. 2 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention.

[0017] FIGS. 3 and FIGS. 4 are a plan view and a cross-sectional view, respectively, of an all-solid-state battery according to an embodiment of the present invention.

[0018] FIG. 5 is a cross-sectional view of an all-solid-state battery according to one embodiment of the present invention.

[0019] FIG. 6 is a cross-sectional view of an all-solid-state battery including a gasket structure according to one embodiment of the present invention.

[0020] Figures 7a and 7b are enlarged views of the M region of Figure 1.

[0021] Figures 8a and 8b are enlarged views of the M region of Figure 1.

[0022]

[0023] In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention are described with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and various modifications can be made. The description of these embodiments is provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention.

[0024] In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the components are exaggerated for the effective description of the technical content. Throughout the specification, parts indicated by the same reference numeral represent the same components.

[0025] The embodiments described herein will be described with reference to cross-sectional and / or plan views, which are exemplary illustrations of the invention. In the drawings, the thicknesses of films and regions are exaggerated for effective description of the technical content. Accordingly, the regions illustrated in the drawings are schematic in nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific forms of regions of the device and are not intended to limit the scope of the invention. Although terms such as first, second, third, etc., have been used to describe various components in the various embodiments of this specification, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. The embodiments described and illustrated herein also include their complementary embodiments.

[0026] The terms used herein are for describing the embodiments and are not intended to limit the invention. In this specification, the singular form includes the plural form unless specifically stated otherwise in the text. As used herein, 'comprises' and / or 'comprising' do not exclude the presence or addition of one or more other components to the mentioned components.

[0027] In this specification, "combination of these" may mean a mixture of components, a laminate, a composite, a copolymer, an alloy, a blend, and a reaction product, etc.

[0028] In this specification, 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.

[0029] Unless otherwise defined in this specification, the particle size may be the average particle size. Additionally, the particle size refers to the average particle size (D50), which means the diameter of the particle whose cumulative volume in the particle size distribution is 50% by volume. The average particle size (D50) may be measured by methods widely known to those skilled in the art, for example, by measuring with a particle size analyzer, or by measuring with a transmission electron microscope (TEM) image or a scanning electron microscope (SEM) image. Alternatively, the average particle size (D50) value may be obtained by measuring using a measuring device utilizing dynamic light scattering, performing data analysis to count the number of particles for each particle size range, and then calculating from this. Alternatively, it may be measured using a laser diffraction method. When measuring by laser diffraction, more specifically, after dispersing the particles to be measured in a dispersion medium, they are introduced into a commercially available laser diffraction particle size measuring device (e.g., Microtrac MT 3000) and irradiated with ultrasound of about 28 kHz at an output of 60 W, and then the average particle size (D50) at 50% of the particle size distribution in the measuring device can be calculated.

[0030] FIG. 1 is a cross-sectional view of an all-solid-state battery (10) according to one embodiment of the present invention.

[0031] Referring to FIG. 1, an all-solid-state battery (10) according to one embodiment includes a positive electrode layer (100), a negative electrode layer (200) facing the positive electrode layer (100), and a solid electrolyte layer (300) disposed between the positive electrode layer (100) and the negative electrode layer (200). However, the all-solid-state battery (10) may further include an additional functional layer, such as an adhesion-enhancing layer, disposed between the positive electrode layer (100) and the solid electrolyte layer (300) or between the negative electrode layer (200) and the solid electrolyte layer (300).

[0032] An anode layer (100) of one embodiment includes an anode current collector (110) and an anode active material layer (120) disposed on the anode current collector (110). The anode active material layer (120) may include an anode active material, a solid electrolyte, a conductive material, and a binder.

[0033] The positive current collector (110) can provide a reference surface on which the positive active material layer (120) is placed. The positive current collector (110) may include, for example, a plate or foil comprising 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 an alloy thereof.

[0034] Meanwhile, unlike as illustrated in FIG. 1, the positive current collector (110) may be omitted in one embodiment of the present invention. Although not illustrated, a carbon layer with a thickness of 0.1 μm 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 (110) and the positive active material layer (120).

[0035] The positive active material layer (120) may include a positive active material, a solid electrolyte, a conductive material, and a binder.

[0036] The cathode active material is a material capable of reversibly absorbing and desorbing lithium ions. The cathode 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 manganate, and lithium iron phosphate, as well as nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, but is not necessarily limited to these. Each cathode active material may be a single material or a mixture of two or more materials.

[0037] Lithium transition metal oxides are, for example, Li a A 1-b B b D2(0.90≤a≤1, 0≤b≤0.5), Li a E 1-b B b O 2-c D c (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05), LiE 2-b B b O 4-c D c (0≤b≤0.5, 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, 0<α<2), Li a Ni 1-b-c Co b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Mn b B c D α(0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2), Li a Nor 1-b-c Mn b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Nor b E c G d O2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1), Li a Nor b Co c Mn d GeO2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1), Li a NiG b O2(0.9≤a≤1, 0.001≤b≤0.1), Li a CoG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a MnG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a Mn2GbO4(0.90≤a≤1, 0.001≤b≤0.1), QO2, QS2, LiQS2, V2O5, LiV2O5, LiIO2, LiNiVO4, Li 3-f J2(PO4)3(0≤f≤2), Li 3-fIt is a compound represented by any one of Fe2(PO4)3 (0≤f≤2) or LiFePO4. In such compounds, the uppercase “A” is Ni, Co, Mn, or a combination thereof; the uppercase “B” is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; the uppercase “D” is O, F, S, P, or a combination thereof; the uppercase “E” is Co, Mn, or a combination thereof; the uppercase “F” is F, S, P, or a combination thereof; the uppercase “G” is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; the uppercase “Q” is Ti, Mo, Mn, or a combination thereof; the uppercase “I” is Cr, V, Fe, Sc, Y, or a combination thereof; and the uppercase “J” is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

[0038] The cathode active material may include, for example, a lithium salt of a transition metal oxide having a layered rock salt type structure among the lithium transition metal oxides described above. The "layered rock salt type structure" is, for example, a cubic rock salt type structure. <111> It is a structure in which oxygen and metal atomic layers are alternately and regularly arranged in a specific direction, thereby forming a two-dimensional plane for each atomic layer. The "cubic rock salt type structure" represents a sodium chloride (NaCl type) structure, which is a type of crystal structure; specifically, it exhibits a structure in which face-centered cubic lattices (fcc) formed by cations and anions, respectively, are offset from each other by half the ridge of the unit lattice. Lithium transition metal oxides having such a layered rock salt type structure, for example, LiNi x Co y Al z O2(NCA) or LiNi x Co y Mn zO2(NCM) (0 <x<1,0<y<1, 0<z<1, x+y+z=1) 등의 삼원계 리튬전이금속산화물일 수 있다. 양극활물질이 층상암염형 구조를 갖는 삼원계 리튬전이금속산화물을 포함하는 경우, 전고체 전지(10)의 에너지 밀도가 커지고 열안정성이 향상될 수 있다.

[0039] The aforementioned compound contained in the cathode active material may be covered by a coating layer (not shown). The cathode active material may also be a mixture of the aforementioned compound and the compound to which the coating layer is added. Meanwhile, the coating layer added to the surface of the cathode active material may include, for example, oxides, hydroxides, oxyhydroxides, oxycarbonates, or hydroxycarbonates of the following coating elements. The compounds forming this coating layer are amorphous or crystalline. The coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. The coating layer may include, for example, Li2O-ZrO2 (LZO). The method for forming the coating layer is selected within a range that does not adversely affect the physical properties of the cathode active material. The method for forming the coating layer is, for example, spray coating or immersion.

[0040] When the positive electrode active material is a ternary lithium transition metal oxide such as NCA or NCM and contains nickel (Ni), the capacity density of the all-solid-state battery (10) is increased, and the metal leaching of the positive electrode active material in the charged state can be reduced. As a result, the cycle characteristics of the all-solid-state battery (10) in the charged state are improved. Meanwhile, “cycle characteristics” is a characteristic that indicates the degree of deterioration of the all-solid-state battery (10) due to charging and discharging of the all-solid-state battery (10). An all-solid-state battery (10) with high cycle characteristics has a small degree of deterioration due to charging and discharging, while an all-solid-state battery (10) with low cycle characteristics may have a large degree of deterioration due to charging and discharging.

[0041] The shape of the cathode active material may include particle shapes such as spheres or ellipsoids. The particle size and content of the cathode active material are not particularly limited.

[0042] The solid electrolyte may have a particulate form. The solid electrolyte may be dispersed among the cathode active materials. The solid electrolyte may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. Sulfide-based solid electrolytes are, 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 (m, n are positive numbers, uppercase “Z” is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, uppercase “M” is one of P, Si, Ge, B, Al, Ga, 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-x I x It may include at least one selected from (0≤x≤2).

[0043] Sulfide-based solid electrolytes are, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-xI x It may be an argyrodite-type compound comprising one or more selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0044] Alternatively, sulfide-based solid electrolytes are Li 7-a M a PS 6-c X c It may be an argyrodite-type compound containing (0≤a≤2, (0≤c≤2)). Here, X may be F, Br, Cl, or a combination thereof. M may be candium (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.

[0045] Alternatively, the sulfide-based solid electrolyte may be the same as the solid electrolyte included in the solid electrolyte layer (300) described later.

[0046] The density of the azyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. By having a density of 1.5 g / cc or higher for the azyrodite-type solid electrolyte, the internal resistance of the all-solid-state battery is reduced, and defects such as penetration and short circuit of the solid electrolyte film due to lithium dendrite formation can be prevented. The elastic modulus of the solid electrolyte may be, for example, 15 GPa to 35 GPa.

[0047] The solid electrolyte included in the positive electrode active material layer (120) may have a smaller average particle size (D50) compared to the solid electrolyte included in the solid electrolyte layer (300). For example, the average particle size (D50) of the solid electrolyte included in the positive electrode active material layer (120) may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the average particle size (D50) of the solid electrolyte included in the solid electrolyte layer (300). Meanwhile, the average particle size (D50) may be a median diameter measured using a laser particle size distribution meter.

[0048] The positive active material layer (120) may include a conductive material. The conductive material may have conductivity without causing chemical changes in the all-solid-state battery (10), thereby increasing the conductivity of the positive active material and the solid electrolyte.

[0049] The conductive material may include carbon-based materials. The conductive material may include, for example, one or more selected from graphite, carbon black, acetylene black, carbon nanofibers, and carbon nanotubes.

[0050] The positive active material layer (120) may further include a binder. The binder may include a material for bonding the positive active material, solid electrolyte, and conductive material included in the positive active material layer (120), and for improving the bonding strength with the positive current collector (110). The binder may include, for example, polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, and polymethyl methacrylate.

[0051] Based on 100 parts by weight of the total positive active material, solid electrolyte, conductive material, and binder, the positive active material layer (120) may contain 85 parts by weight or more and 92 parts by weight or less of the positive active material. Based on 100 parts by weight of the total positive active material, solid electrolyte, conductive material, and binder, the positive active material layer (120) may contain 0.5 parts by weight or more and 1.5 parts by weight or less of the binder.

[0052] Based on 100 parts by weight of solid electrolyte, the positive active material layer (120) may contain 1 part by weight or more and 50 parts by weight or less of a conductive material. If the conductive material is included in the positive active material layer (120) in an amount less than 1 part by weight based on 100 parts by weight of solid electrolyte, the proportion of the conductive material decreases, and the electrical conductivity of the positive active material layer (120) may decrease. If the conductive material is included in the positive active material layer (120) in an amount exceeding 50 parts by weight based on 100 parts by weight of solid electrolyte, the proportion of the conductive material is excessively high, and a coating layer covering the surface of the solid electrolyte may not be properly formed.

[0053] The positive active material layer (120) may further include additives such as fillers, coating agents, dispersants, and ion conductivity aids in addition to the positive active material, solid electrolyte, conductive material, and binder described above.

[0054]

[0055] Referring to FIG. 1, the cathode layer (200) may include a cathode current collector (210) and a cathode coating layer (220) on the cathode current collector (210).

[0056] The negative current collector (210) may provide a reference surface on which the negative coating layer (220) is placed. 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 be, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni), but is not necessarily limited to these, and any material used as an electrode current collector is possible. The thickness of the negative current collector (210) may be 1 to 20 μm, for example 5 to 15 μm, for example 7 to 10 μm.

[0057] The negative current collector (210) may be composed of one of the metals described above, or may include an alloy of two or more metals or a coating material. The negative current collector (210) is, for example, in the form of a plate or foil. Meanwhile, in one embodiment, the negative current collector (210) may be omitted.

[0058] FIGS. 7a and 7b are drawings for explaining a negative electrode for an all-solid-state battery according to an embodiment of the present invention, and are enlarged views of the M region of FIG. 1. FIGS. 8a and 8b are drawings for explaining a negative electrode for an all-solid-state battery according to a comparative example of the present invention, and are enlarged views of the M region of FIG. 1. Hereinafter, the negative electrode coating layer (220) will be described in detail with reference to FIGS. 7a, 7b, 8a, and 8b.

[0059] Referring to FIGS. 8a and 8b, if the negative electrode coating layer (220) contains only a carbon material (CB), that is, if the carbon material does not contain a metal phthalocyanine coating layer, the carbon material (CB) has a low affinity for lithium ions (LI), so the movement of lithium ions (LI) from the negative electrode may not be smooth. Consequently, during charging and discharging, lithium ions (LI) may not be evenly dispersed and move, and lithium ions (LI) may not be uniformly electrodeposited on the negative electrode current collector. In other words, the lithium metal layer (400) may not be formed evenly, and lithium dendrites may be formed, which may reduce the lifespan of the battery.

[0060] Referring to FIGS. 7a and 7b, the negative electrode for an all-solid-state battery according to the present invention can improve the above problems by coating a carbon material (CB) with metal phthalocyanine (MPC). Metal phthalocyanine (MPC) contains a large number of nitrogen atoms (N) with high lithium affinity, which can improve the lithium affinity of the negative electrode. Furthermore, metal phthalocyanine (MPC) can be uniformly coated on the carbon material (CB) in a solvent through π-π stacking.

[0061] In other words, the negative electrode for an all-solid-state battery according to the present invention can improve the mobility of lithium ions (LI) in the negative electrode by uniformly coating a metal phthalocyanine (MPC) with high lithium affinity onto a carbon material (CB). Accordingly, the lithium ion flux in the negative electrode can be uniformly dispersed during charging and discharging, and the lithium metal layer (400) can be uniformly formed, thereby improving the electrochemical properties of the all-solid-state battery.

[0062] The coated carbon (AM) may have a particle form. The median average particle size (D50) of the coated carbon (AM) having a particle form may be, for example, 4 µm or less, 2 µm or less, 1 µm or less, or 900 nm or less. The median average particle size (D50) of the coated carbon (AM) may be, for example, 10 nm to 4 µm, 10 nm to 2 µm, 10 nm to 900 nm, or 10 nm to 500 nm. As the coated carbon (AM) has a median average particle size (D50) within this range, the reversible absorption and / or desorption of lithium during charging and discharging may be more facilitated. Meanwhile, the median average particle size (D50) may be a median diameter measured using a laser particle size distribution meter.

[0063] The carbon material (CB) included in the cathode coating layer (220) is not particularly limited and may include, for example, crystalline carbon, amorphous carbon, or a combination thereof. Examples of crystalline carbon include graphite such as amorphous, plate-like, flake-like, spherical, or fibrous natural graphite or artificial graphite, and examples of amorphous carbon include carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, etc., but are not necessarily limited to these. Amorphous carbon is carbon that does not have crystallinity or has very low crystallinity and is distinguished from crystalline carbon or graphite-based carbon. In one embodiment, the cathode coating layer may include carbon black. Carbon black has a small particle size and a large BET specific surface area, so the movement of lithium ions may be easy.

[0064] The type of metal included in the metal phthalocyanine (MPC) is not limited and may include, for example, alkali metals, alkaline earth metals, transition metals, post-transition metals, or combinations thereof. Specifically, the metal included in the metal phthalocyanine (MPC) may include at least one selected from the group consisting of lithium (Li), copper (Cu), zinc (Zn), silver (Ag), gold (Au), magnesium (Mg), cobalt (Co), iron (Fe), and tin (Sn). For example, the metal phthalocyanine may be zinc phthalocyanine. Since zinc has a high affinity for lithium, the mobility of lithium ions may be further enhanced when zinc phthalocyanine is used.

[0065] In the coated carbon (AM), the weight ratio of metal phthalocyanine (MPC) to carbon material (CB) may be 1:99 to 50:50. The weight ratio of metal phthalocyanine (MPC) to carbon material (CB) may be 1:99 to 40:60, 5:95 to 40:60, or 5:95 to 20:80.

[0066] If the content of metal phthalocyanine (MPC) is excessively high, the ionic conductivity of the cathode may decrease, whereas if the content of metal phthalocyanine (MPC) is excessively low, the coating may not be sufficiently formed. When the weight ratio of metal phthalocyanine (MPC) to carbon material (CB) satisfies the range described above, the cathode can have excellent electrical conductivity and excellent lithium ion mobility.

[0067] The cathode coating layer (220) may further include a binder. The binder included in the cathode coating layer (220) may be, for example, a water-based binder. The water-based binder may include at least one of styrene butadiene rubber (SBR), (meth)acrylated styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, (meth)acrylic rubber, butyl rubber, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, poly(meth)acrylonitrile, ethylenepropylenediene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, (meth)acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

[0068] The cathode coating layer (220) may further include a cellulose-based binder capable of imparting viscosity together with a water-based binder. The cellulose-based binder may include at least one of carboxymethyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose, alkali metal salts thereof, or combinations thereof.

[0069] By including a binder in the cathode coating layer (220), the cathode coating layer (220) can be stably formed on the cathode current collector (210). That is, the bonding strength between the cathode coating layer (220) and the cathode current collector (210) can be increased. In addition, cracking of the cathode coating layer (220) is suppressed despite volume changes and / or relative position changes of the cathode coating layer (220) during the charging and discharging process. If the cathode coating layer (220) does not include a binder, the cathode coating layer (220) can be easily separated from the cathode current collector (210). As the cathode coating layer (220) detaches from the cathode current collector (210), the cathode current collector (210) may come into contact with the solid electrolyte layer (300) at the exposed portion of the cathode current collector (210), and accordingly, the possibility of a short circuit occurring increases.

[0070] The cathode coating layer (220) is manufactured, for example, by providing a mixture in which the material constituting the cathode coating layer (220) is dispersed onto a cathode current collector (210). Since the material constituting the cathode coating layer (220) includes a binder, stable dispersion of the coated carbon (AM) in the mixture is possible. For example, when the mixture is applied onto the cathode current collector (210) by a screen printing method, it is possible to suppress clogging of the screen (for example, clogging by aggregates of the coated carbon (AM)) by the binder.

[0071] The cathode coating layer (220) may further include other additives in addition to the coated carbon (AM) and binder. The cathode coating layer (220) may further include, for example, fillers, coating agents, dispersants, ion-conducting aids, etc.

[0072] The negative electrode coating layer (220) may have a smaller thickness compared to the positive electrode active material layer (120). The thickness of the negative electrode coating layer (220) may be, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less of the thickness of the positive electrode active material layer (120). The thickness of the negative electrode coating layer (220) may be, for example, 1 µm to 20 µm, 2 µm to 15 µm, 3 µm to 15 µm, or 3 µm to 7 µm. If the thickness of the negative electrode coating layer (220) is excessively thin, 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) increases excessively, the energy density of the all-solid-state battery (10) decreases, and the internal resistance of the all-solid-state battery (10) due to the negative electrode coating layer (220) increases, which may degrade the cycle characteristics of the all-solid-state battery (10).

[0073] If the thickness of the cathode coating layer (220) is reduced, for example, the charging capacity of the cathode coating layer (220) may also be reduced. The charging capacity of the cathode coating layer (220) is, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5% or less, or 2% or less compared to the charging capacity of the positive active material layer (120). The charging capacity of the cathode coating layer (220) is, for example, 0.1% to 50%, 0.1% to 40%, 0.1% to 30%, 0.1% to 20%, 0.1% to 10%, 0.1% to 5%, or 0.1% to 2% compared to the charging capacity of the positive active material layer (120). If the charging capacity of the cathode coating layer (220) is excessively small, the thickness of the cathode coating layer (220) becomes very thin, and the same defect as the aforementioned defect that occurs when the thickness of the cathode coating layer (220) becomes excessively thin may occur. If the charging capacity of the cathode coating layer (220) increases excessively, the same defect as the aforementioned defect that occurs when the thickness of the cathode coating layer (220) increases excessively may occur.

[0074] Meanwhile, although not illustrated, a carbon layer may be further included to improve adhesion between the cathode coating layer (220) and the solid electrolyte layer (300).

[0075] A solid electrolyte layer (300) may be provided between the anode layer (100) and the cathode layer (200). The solid electrolyte layer (300) may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. The solid electrolyte in the solid electrolyte layer (300) may be the same as or different from the solid electrolyte included in the aforementioned anode active material layer (120).

[0076] In one embodiment, the solid electrolyte included in the solid electrolyte layer (300) may be amorphous, crystalline, or a mixture thereof. Additionally, the solid electrolyte may include, for example, sulfur (S), phosphorus (P), and lithium (Li) as at least constituent elements among sulfide-based solid electrolyte materials. For example, the solid electrolyte may be a material containing Li2S-P2S5. When using a sulfide-based solid electrolyte material containing Li2S-P2S5 to form the solid electrolyte, the molar ratio of Li2S and P2S5 is, for example, in the range of Li2S : P2S5 = 50 : 50 to 90 : 10.

[0077] Sulfide-based solid electrolytes are, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound comprising one or more selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0078] Alternatively, sulfide-based solid electrolytes are Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing (0≤a≤2, 0≤c≤2). Here, X may be F, Br, Cl, or a combination thereof. M may be candium (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.

[0079] The density of the azyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. Since the azyrodite-type solid electrolyte has a density of 1.5 g / cc or higher, the internal resistance of the all-solid-state battery is reduced, and defects such as penetration and short circuit of the solid electrolyte film due to lithium dendrite formation can be prevented. The elastic modulus of the solid electrolyte is, for example, 15 GPa to 35 GPa.

[0080] The solid electrolyte layer (300) may further include a binder. The binder included in the solid electrolyte layer (300) is, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited thereto. For example, the binder may include at least one selected from the group consisting of styrene butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polyvinyl alcohol, vinylidene fluoride / hexafluoropropylene copolymer, polyvinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, and polymethyl methacrylate. 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 negative electrode coating layer (220).

[0081]

[0082] FIG. 2 is a cross-sectional view of an all-solid-state battery (10) according to another embodiment of the present invention.

[0083] Referring to FIG. 2, 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 anode layer (100), and the second solid electrolyte layer (320) may be adjacent to the cathode layer (200).

[0084] 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 2 to 100 times the second thickness (TK2).

[0085]

[0086] FIG. 3 is a plan view of an all-solid-state battery (10) according to another embodiment of the present invention. FIG. 4 is a cross-sectional view along the line A-A' of FIG. 3. In this embodiment, detailed descriptions of technical features that overlap with those previously described with reference to FIG. 1 and FIG. 2 are omitted, and differences are described in detail.

[0087] Referring to FIGS. 3 and 4, the area of ​​the anode layer (100) and the area of ​​the cathode layer (200) may differ from each other. Specifically, the area of ​​the cathode layer (200) may be larger than the area of ​​the anode layer (100). The anode layer (100) may be completely superimposed within the cathode layer (200).

[0088] In one embodiment of the present invention, the first solid electrolyte layer (310) may have substantially the same area as the anode layer (100). The second solid electrolyte layer (320) may have substantially the same area as the cathode layer (200).

[0089] Specifically, 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). 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).

[0090] The all-solid-state battery (10) according to the present embodiment can be manufactured by forming a first laminate of a positive electrode layer (100) and a first solid electrolyte layer (310), forming a second laminate of a negative electrode layer (200) and a second solid electrolyte layer (320), and then laminating the first laminate and the second laminate.

[0091]

[0092] FIG. 5 is a cross-sectional view along line A-A' of FIG. 3, intended to illustrate an all-solid-state battery according to another embodiment of the present invention.

[0093] Referring to FIG. 5, 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 negative electrode coating layer (220). The thickness of the lithium metal layer (400) may increase further during charging of the all-solid-state battery (10). The negative electrode coating layer (220) acts as a protective layer for the lithium metal layer (400) and, at the same time, can suppress the growth of lithium dendrites from the lithium metal layer (400).

[0094] The lithium metal layer (400) may be a thin metal film containing lithium or a lithium alloy. The lithium alloy is not limited to, for example, Li-Al alloy, Li-Sn alloy, Li-In alloy, Li-Ag alloy, Li-Au alloy, Li-Zn alloy, Li-Ge alloy, Li-Si alloy, etc., and any alloy used as a lithium alloy is possible. The lithium metal layer (400) may contain one of these alloys or lithium. Alternatively, the lithium metal layer (400) may contain various types of alloys.

[0095] 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 smaller than the second width (WI2). For example, the fifth width (WI5) may be greater than the first width (WI1) and smaller than the second width (WI2).

[0096]

[0097] FIG. 6 is a cross-sectional view illustrating an all-solid-state battery according to another embodiment of the present invention.

[0098] Referring to FIG. 6, the all-solid-state battery (10) may include a gasket structure (400). The gasket structure (400) can fill the step difference on the side of the all-solid-state battery (10) caused by the difference in area between the first laminate and the second laminate. The gasket structure (400) can surround the sides of the first laminate of the all-solid-state battery (10) along the first and second directions (D1, D2). For example, the thickness of the gasket structure (400) may be substantially the same as the thickness of the first laminate. This prevents damage to the step difference on the side of the all-solid-state battery even when the first laminate and the second laminate, which have different areas, are laminated and pressed. "Substantially the same thickness" may be defined as a thickness sufficient to prevent damage to the step difference on the side of the all-solid-state battery even when the first laminate and the second laminate, which have different areas, are laminated and pressed.

[0099]

[0100] The present invention will be explained in more detail below through examples. However, these examples are intended to illustrate the invention and the scope of the invention is not limited to these examples.

[0101]

[0102] Example 1: Preparation of a cathode

[0103] A SUS foil with a thickness of 10 μm was prepared as a cathode current collector. Carbon black with a primary particle size of about 30 nm was prepared as the carbon material, and zinc phthalocyanine was prepared as the metal phthalocyanine.

[0104] A first solution was prepared by dissolving carbon black in water containing 1 wt% of CMC binder. Zinc phthalocyanine was added such that the weight ratio of zinc phthalocyanine to carbon material was 10:90, and the cathode slurry was prepared such that the weight ratio of zinc phthalocyanine + carbon material, CMC binder, and SBR binder was 100:3:6.

[0105] A manufactured cathode slurry was applied to a SUS sheet using a bar coater, dried in air at 80°C for 10 minutes, and then vacuum dried at 40°C for 10 hours to prepare a cathode laminate. The cathode was manufactured by applying pressure to the laminate.

[0106] The thickness of the cathode coating layer on the manufactured cathode was 10 μm.

[0107]

[0108] Example 2

[0109] A cathode was prepared in the same manner as in Example 1, except that copper phthalocyanine was used instead of zinc phthalocyanine as the metal phthalocyanine. The thickness of the cathode coating layer on the prepared cathode was 10 μm.

[0110]

[0111] Example 3

[0112] A cathode was prepared in the same manner as in Example 1, except that zinc phthalocyanine was added such that the weight ratio of zinc phthalocyanine to carbon material was 3:97. The thickness of the cathode coating layer on the prepared cathode was 10 μm.

[0113]

[0114] Example 4

[0115] A cathode was prepared in the same manner as in Example 3, except that copper phthalocyanine was used instead of zinc phthalocyanine as the metal phthalocyanine. The thickness of the cathode coating layer on the prepared cathode was 10 μm.

[0116]

[0117] Comparative Example 1

[0118] A SUS foil with a thickness of 10 μm was prepared as the cathode current collector. Carbon black with a primary particle size of about 30 nm was prepared as the carbon material, and metal phthalocyanine was not used.

[0119] A first solution was prepared by dissolving carbon black in water containing 1 wt% of CMC binder. The cathode slurry was prepared such that the weight ratio of carbon material, CMC binder, and SBR binder was 100:3:6.

[0120] A manufactured cathode slurry was applied to a SUS sheet using a bar coater, dried in air at 80°C for 10 minutes, and then vacuum dried at 40°C for 10 hours to prepare a cathode laminate. A cathode was manufactured by pressurizing the laminate. The thickness of the cathode coating layer on the manufactured cathode was 10 μm.

[0121]

[0122] Preparation Example: Preparation of an all-solid-state battery

[0123] (Cathode active material)

[0124] Cathode active material LiNi0.8Co0. 15 Mn0. 05 O2 (NCM) powder was prepared.

[0125] (Bipolar layer)

[0126] As the positive active material, the previously explained LiNi0.8Co0. 15 Mn0. 05 O2 (NCM) powder was prepared. A crystalline azirodite-based solid electrolyte (Li6PS5Cl) was prepared as the solid electrolyte. A polytetrafluoroethylene (PTFE) binder (DuPont's Teflon binder) was prepared as the binder. Carbon nanofibers (CNF) were prepared as the conductive material. These materials were mixed in a weight ratio of positive active material:solid electrolyte:conductive material:binder = 84.2:11.5:2.9:1.4, and the mixture was formed into a large sheet to produce a positive electrode sheet. The prepared positive electrode sheet was pressed onto a positive electrode current collector made of carbon-coated aluminum foil with a thickness of 18 μm to produce a positive electrode layer. The thickness of the positive active material layer contained in the positive electrode layer was approximately 100 μm.

[0127] (Cathode layer)

[0128] The cathode prepared according to Examples 1 to 4 and Comparative Example 1 was used as the cathode layer.

[0129] (Solid electrolyte layer)

[0130] A solid electrolyte solution was prepared by adding an azyrodite-type solid electrolyte Li6PS5Cl to an isobutylyl isobutylate binder solution containing an acrylate-based polymer (solid content: 50 wt%, mixing ratio of solid electrolyte to binder: 98.7:1.3 wt%).

[0131] The above solid electrolyte solution was applied to a release polytetrafluoroethylene film and dried at 60°C for 2 hours to produce a solid electrolyte layer with a thickness of 100 μm.

[0132] (Manufacturing of all-solid-state batteries)

[0133] The cathode prepared in Examples 1 to 4 and Comparative Example 1, the solid electrolyte layer prepared above, and the anode layer were stacked in sequence. The stack was sealed in a pouch form and subjected to a warm isostatic press (WIP) at 80°C for 30 minutes at 500 MPa to produce an all-solid-state battery.

[0134]

[0135] Evaluation Example 1: Measurement of initial charge / discharge efficiency

[0136] Using the complete cell prepared in the preparation example, the initial charge-discharge efficiency of the all-solid-state battery was measured as follows. The complete cell was charged to an upper limit voltage of 4.25V with a constant current of 0.1C at 45℃, and then discharged to a discharge cutoff voltage of 2.5V with a constant current of 0.1C. The initial charge capacity and initial discharge capacity were measured, and the results are shown in Table 1. In Table 1, the initial charge-discharge efficiency [%] is expressed by the following Equation 1.

[0137] <Mathematical Formula 1>

[0138] Initial charge / discharge efficiency [%] = (Initial discharge capacity / Initial charge capacity) × 100

[0139] Classification Carbon Material Metal Phthalocyanine Carbon : Metal Phthalocyanine Content Non-initial Charge / Discharge Efficiency [%] Example 1 Carbon Black Zn Phthalocyanine 10 : 9083.8 Example 2 Carbon Black Cu Phthalocyanine 10 : 9083.9 Example 3 Carbon Black Zn Phthalocyanine 3 : 9782.1 Example 4 Carbon Black Cu Phthalocyanine 3 : 9782.0 Comparative Example 1 Carbon Black --81.0

[0140] Referring to Table 1, it can be seen that the all-solid-state battery according to the examples has superior initial efficiency compared to the all-solid-state battery according to the comparative example.

[0141] Evaluation Example 2: Evaluation of All-Solid State Battery Life Characteristics

[0142] The lifespan characteristics of the all-solid-state battery were evaluated by the following charge-discharge test. The charge-discharge test was performed by placing the all-solid-state battery in a 45°C constant temperature bath.

[0143] The first cycle involved charging at a constant current of 0.33C for about 3 hours until the battery voltage reached 4.25V, and then charging at a constant voltage until the current reached 0.1C from 4.25V, followed by a 10-minute rest period. Afterward, the battery was discharged at a constant current of 0.33C for about 3 hours until the battery voltage reached 2.5V, followed by a 10-minute rest period.

[0144] After the second cycle, charging and discharging were performed for up to 100 cycles under the same conditions as the first cycle. Life characteristics are shown in Table 2 below. In Table 2, the capacity retention rate is expressed by the following Equation 2.

[0145] <Mathematical Formula 2>

[0146] Capacity retention rate [%] = [Discharge capacity at the 100th cycle / Discharge capacity at the 1st cycle] × 100

[0147] Classification Carbon Material Metal Phthalocyanine Carbon : Metal Phthalocyanine Content Specific Weight Retention Rate [%] Example 1 Carbon Black Zn Phthalocyanine 10 : 9088 Example 2 Carbon Black Cu Phthalocyanine 10 : 9089 Example 3 Carbon Black Zn Phthalocyanine 3 : 9780 Example 4 Carbon Black Cu Phthalocyanine 3 : 9782 Comparative Example 1 Carbon Black --69

[0148] Referring to Table 2, it can be seen that the all-solid-state battery according to the examples has a superior lifespan compared to the all-solid-state battery according to the comparison. It can be seen that the all-solid-state battery according to Examples 1 and 2 has significantly improved lifespan characteristics compared to the all-solid-state battery according to the comparison example.

[0149] Evaluation Example 3: FE-SEM and SEM-EDAX Analysis

[0150] The cross-section of the cathode before charging and discharging in Example 1 was measured using a field emission scanning electron microscope (FE-SEM), and SEM-EDAX analysis was performed. The results are shown in Table 3.

[0151] Element Atomic %C7 8.5N 3.2O 17.9Metal (Zn, Cu) 0.4

[0152] Although embodiments of the present invention have been described above with reference to the attached drawings, the present invention may be implemented in other specific forms without altering its technical concept or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A negative current collector and a negative coating layer on the negative current collector, wherein The above cathode coating layer comprises a carbon material coated with metal phthalocyanine, and The above carbon material is carbon black, a negative electrode for an all-solid-state battery.

2. In Paragraph 1, The above metal phthalocyanine comprises at least one selected from the group consisting of lithium (Li), copper (Cu), zinc (Zn), silver (Ag), gold (Au), magnesium (Mg), cobalt (Co), iron (Fe), and tin (Sn), for a negative electrode for an all-solid-state battery.

3. In Paragraph 1, A negative electrode for an all-solid-state battery in which the weight ratio of the metal phthalocyanine to the carbon material is 5:95 to 50:

50.

4. In Paragraph 1, The above-described coated carbon material is a negative electrode for an all-solid-state battery having an average size of 10 nm to 500 nm.

5. In Paragraph 1, A cathode for an all-solid-state battery, wherein the thickness of the cathode coating layer is 3 μm to 20 μm.

6. In Paragraph 1, The above-mentioned cathode coating layer is a cathode for an all-solid-state battery that further comprises a binder.

7. In Paragraph 6, The above binder comprises at least one of styrene butadiene rubber (SBR), (meth)acrylated styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, (meth)acrylic rubber, butyl rubber, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, poly(meth)acrylonitrile, ethylene propylenediene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, (meth)acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, or a combination thereof, for a negative electrode for an all-solid-state battery.

8. In Paragraph 1, The above-described cathode is a cathode for an all-solid-state battery that further comprises a lithium metal layer between the cathode current collector and the cathode coating layer.

9. A negative current collector and a negative coating layer on the negative current collector, wherein The above-described cathode coating layer comprises a carbon material coated with zinc (Zn) phthalocyanine, for a cathode of an all-solid-state battery.

10. In Paragraph 9, The above carbon material comprises at least one selected from the group consisting of carbon black, graphene, carbon nanotubes (CNT), carbon nanofibers (CNF), activated carbon, acetylene black, and ketjen black, for a negative electrode for an all-solid-state battery.

11. In Paragraph 9, A negative electrode for an all-solid-state battery in which the weight ratio of the zinc phthalocyanine and the carbon material is 5:95 to 50:

50.

12. In Paragraph 9, A cathode for an all-solid-state battery, wherein the thickness of the cathode coating layer is 3 μm to 20 μm.

13. In Paragraph 9, The above-mentioned cathode coating layer is a cathode for an all-solid-state battery that further comprises a binder.

14. In Paragraph 9, The above-described cathode is a cathode for an all-solid-state battery that further comprises a lithium metal layer between the cathode current collector and the cathode coating layer.

15. A negative current collector and a negative coating layer on the negative current collector, wherein The above cathode coating layer comprises a carbon material coated with metal phthalocyanine, and A negative electrode for an all-solid-state battery in which the weight ratio of the metal phthalocyanine to the carbon material is 5:95 to 50:

50.

16. In Paragraph 15, The above metal phthalocyanine comprises at least one selected from the group consisting of lithium (Li), copper (Cu), zinc (Zn), silver (Ag), gold (Au), magnesium (Mg), cobalt (Co), iron (Fe), and tin (Sn), for a negative electrode for an all-solid-state battery.

17. In Paragraph 15, The above carbon material comprises at least one selected from the group consisting of carbon black, graphene, carbon nanotubes (CNT), carbon nanofibers (CNF), activated carbon, acetylene black, and ketjen black, for a negative electrode for an all-solid-state battery.

18. In Paragraph 15, A cathode for an all-solid-state battery, wherein the thickness of the cathode coating layer is 3 μm to 20 μm.

19. In Paragraph 15, The above cathode coating layer further comprises a binder, The above binder comprises at least one of styrene butadiene rubber (SBR), (meth)acrylated styrene-butadiene rubber, (meth)acrylonitrile-butadiene rubber, (meth)acrylic rubber, butyl rubber, fluororubber, polyethylene oxide, polyvinylpyrrolidone, polyepichlorohydrin, polyphosphazene, poly(meth)acrylonitrile, ethylene propylenediene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, (meth)acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, or a combination thereof, for a negative electrode for an all-solid-state battery.

20. In Paragraph 15, The above-described cathode is a cathode for an all-solid-state battery that further comprises a lithium metal layer between the cathode current collector and the cathode coating layer.

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