Negative electrode for lithium metal battery and lithium metal battery comprising same

Abstract

The present invention relates to a negative electrode for a lithium metal battery and a lithium metal battery including same. More specifically, the negative electrode for a lithium metal battery according to the concept of the present invention includes: a negative electrode current collector; and a negative electrode host layer on the negative electrode current collector, wherein the negative electrode host layer includes a carbon material and a coating layer on the surface of the carbon material. The coating layer includes a lithiophilic material. The negative electrode host layer has a structure including a plurality of pores.

Description

Anode for a lithium metal battery, and a lithium metal battery comprising the same

[0001] The present invention relates to an anode for a lithium metal battery and a lithium metal battery including the same, and more particularly, to an anode for a lithium metal battery including an anode host layer to which a lithium-affinity material is applied, and a lithium metal battery including the same.

[0002]

[0003] Lithium secondary batteries are high-performance secondary batteries with the highest energy density among the currently commercialized secondary batteries and can be used in various fields such as electric vehicles.

[0004] Lithium metal thin films can be used as anodes in lithium secondary batteries. These films are typically manufactured by rolling lithium into a plate shape. However, in lithium secondary batteries using these films as anodes, dendrites form and grow on the film, resulting in unsatisfactory energy density and long-life characteristics. This leaves significant room for improvement.

[0005]

[0006] The problem to be solved by the present invention is to provide a negative electrode for a lithium metal battery capable of suppressing lithium dendrites.

[0007] Another problem to be solved by the present invention is to provide a lithium metal battery having high energy density and excellent lifespan.

[0008]

[0009] According to the concept of the present invention, a negative electrode for a lithium metal battery comprises: a negative electrode current collector; and a negative electrode host layer on the negative electrode current collector, wherein the negative electrode host layer may include a carbon material and a coating layer on a surface of the carbon material.

[0010] The above coating layer may include a lithium-friendly material.

[0011] The above cathode host layer may have a structure including a plurality of pores.

[0012] The above negative host layer may be configured such that lithium is deposited within the plurality of pores.

[0013] According to another concept of the present invention, a negative electrode for a lithium metal battery comprises: a negative electrode current collector; and

[0014] The negative electrode host layer may include a negative electrode current collector, wherein the negative electrode host layer may include a carbon material and a lithium-affinity material doped in the carbon material.

[0015] The above cathode host layer may have a structure including a plurality of pores.

[0016] The above negative host layer may include a covalent bond between atoms of the lithium-affinity material and carbon atoms of the carbon material.

[0017] The above negative host layer may be configured such that lithium is deposited within the plurality of pores.

[0018] According to another concept of the present invention, a lithium metal battery may include a positive electrode including a positive electrode active material; a negative electrode manufactured according to the above-described manufacturing method; and an electrolyte disposed between the positive electrode and the negative electrode.

[0019]

[0020] The present invention utilizes a negative electrode for a lithium metal battery having a novel structure, thereby suppressing dendrite formation and enabling uniform deposition of lithium within the negative electrode. A lithium metal battery comprising the negative electrode according to the present invention can exhibit improved cycle characteristics and lifespan characteristics.

[0021]

[0022] FIG. 1 is a schematic diagram illustrating a lithium metal battery according to embodiments of the present invention.

[0023] FIG. 2 is a schematic diagram illustrating a lithium metal battery after an initial cycle according to embodiments of the present invention.

[0024] Figure 3 is a cross-sectional view illustrating a cathode according to embodiments of the present invention.

[0025] FIG. 4a is an enlarged cross-sectional view of part M of FIG. 3 in a state before charging of the negative electrode according to one embodiment.

[0026] FIG. 4b is an enlarged cross-sectional view of part M of FIG. 3 in a state after charging of the negative electrode according to one embodiment.

[0027] Figure 5 is a flowchart illustrating a method for manufacturing a cathode according to one embodiment of the present invention.

[0028] FIG. 6a is an enlarged cross-sectional view of part M of FIG. 3 in a state before charging of the negative electrode according to another embodiment.

[0029] FIG. 6b is a schematic diagram illustrating the bonding state of carbon atoms and lithium-affinity materials in a negative electrode host layer according to another embodiment.

[0030] FIG. 6c is an enlarged cross-sectional view of part M of FIG. 3 in a state before charging of the negative electrode according to another embodiment.

[0031] Figure 7 is a flowchart illustrating a method for manufacturing a cathode according to another embodiment of the present invention.

[0032] Figures 8 to 10 are schematic diagrams illustrating a lithium battery according to one embodiment.

[0033] Figure 11 is a schematic diagram illustrating a lithium metal battery according to embodiments of the present invention.

[0034]

[0035] To fully understand the structure and effects of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and subject to various modifications. However, the description of these embodiments is provided solely to ensure a complete disclosure of the present invention and to fully inform those skilled in the art of the invention of the scope of the invention.

[0036] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. Furthermore, in the drawings, the thicknesses of the components are exaggerated for the sake of clarity. Parts designated by the same reference numerals throughout the specification represent the same components.

[0037] Unless otherwise specified herein, the singular may also include the plural. Furthermore, unless otherwise specified, "A or B" may mean "including A, including B, or including A and B." As used herein, "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[0038] As used herein, “combination thereof” may mean mixtures, laminates, composites, copolymers, alloys, blends, and reaction products of the components.

[0039] In this specification, “metal” may include both metals and metalloids such as silicon and germanium, in either the elemental or ionic state.

[0040] In this specification, “alloy” may mean a mixture of two or more metals.

[0041] In this specification, “positive electrode active material” may mean a positive electrode material capable of undergoing lithiation and delithiation.

[0042] In this specification, “negative electrode active material” may mean a negative electrode material capable of undergoing lithiation and delithiation.

[0043] In this specification, “lithiation” and “lithiating” may refer to a process of adding lithium to a positive electrode active material or a negative electrode active material.

[0044] In this specification, “delithiation” and “delithiate” may refer to a process of removing lithium from a positive electrode active material or a negative electrode active material.

[0045] In this specification, “charging” and “charging” may refer to a process of providing electrochemical energy to a battery.

[0046] In this specification, “discharging” and “discharging” may refer to the process of removing electrochemical energy from a battery.

[0047] In this specification, “positive electrode” may mean an electrode where electrochemical reduction and lithiation occur during a discharge process.

[0048] In this specification, “negative electrode” may mean an electrode where electrochemical oxidation and delithiation occur during a discharge process.

[0049] In this specification, “lithium-friendly material” means a material that forms and induces lithium metal in a uniform form by minimizing nucleation resistance during the process of reducing lithium ions to lithium metal.

[0050]

[0051] Unless otherwise defined herein, the particle size may be the average particle size. In addition, the particle size refers to the average particle size (D50), which means the diameter of particles with a cumulative volume of 50% by volume in a particle size distribution. The average particle size (D50) can be measured by a method well 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) photograph or a scanning electron microscope (SEM) photograph. Alternatively, the average particle size (D50) value can be obtained by measuring with a measuring device that utilizes dynamic light-scattering, performing data analysis to count the number of particles for each particle size range, and calculating from the counted number. Alternatively, the average particle size (D50) value can be obtained by measuring with a laser diffraction method. When measuring by laser diffraction, more specifically, after the particles to be measured are dispersed 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 ultrasonic waves of approximately 28 kHz at an output of 60 W, and the average particle size (D50) based on 50% of the particle size distribution in the measuring device can be calculated.

[0052]

[0053] FIG. 1 is a schematic conceptual diagram illustrating a lithium metal battery according to embodiments of the present invention. Referring to FIG. 1, the lithium metal battery may include a positive electrode (PEL), a negative electrode (NEL), a separator (SEP), and an electrolyte layer (GPE).

[0054] Lithium metal batteries can use lithium metal as the anode active material. During the charge / discharge process, a lithium-containing metal layer can precipitate and dissolve between the anode current collector (COL1) and the electrolyte layer (GPE). As the lithium metal battery is repeatedly charged and discharged, the lithium-containing metal layer can contain residual impurities within the electrode, electrolyte decomposition products, and other substances.

[0055] The lithium-containing metal layer may contain these impurities, resulting in a rough and hard surface. Lithium dendrites may precipitate on the lithium-containing metal layer with this rough surface. Lithium dendrites continuously grow during charge and discharge, potentially causing short circuits between the positive electrode (PEL) and negative electrode (NEL). Furthermore, uneven lithium dendrite growth on the negative electrode (NEL) during charging can easily cause damage within the cell, significantly expanding the cell volume and hindering long-term operation.

[0056] The positive electrode (PEL) and the negative electrode (NEL) can be separated from each other with a separator (SEP) therebetween. The separator (SEP) can be disposed between the positive electrode (PEL) and the negative electrode (NEL). The positive electrode (PEL), the negative electrode (NEL), and the separator (SEP) can be in contact with the electrolyte layer (GPE). The separator (SEP) can be impregnated into the electrolyte layer (GPE). In one embodiment, not only the separator (SEP), but also the positive electrode (PEL) and the negative electrode (NEL) can be impregnated into the electrolyte layer (GPE).

[0057] The electrolyte layer (GPE) may be a medium for transporting lithium ions between the positive electrode (PEL) and the negative electrode (NEL). Within the electrolyte layer (GPE), the lithium ions may pass through the separator (SEP) and move toward the positive electrode (PEL) or the negative electrode (NEL).

[0058]

[0059] Positive electrode (PEL)

[0060] A positive electrode (PEL) for a lithium metal battery may include a positive electrode current collector (COL2) and a positive electrode active material layer (PAL) formed on the positive electrode current collector (COL2). The positive electrode active material layer (PAL) includes a positive electrode active material and may further include a binder and / or a conductive material. For example, the positive electrode active material layer (PAL) may further include an additive that can function as a sacrificial positive electrode.

[0061] The content of the positive active material in the positive active material layer (PAL) may be 90 wt% to 99.5 wt% with respect to 100 wt% of the positive active material layer (PAL). The content of each of the binder and the conductive agent may be 0.5 wt% to 5 wt% with respect to 100 wt% of the positive active material layer (PAL).

[0062] The above binder can serve to adhere positive electrode active material particles well to each other and also to adhere positive electrode active material well to positive electrode current collector (COL2). Representative examples of the binder include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, polymers containing ethylene oxide, polyvinyl pyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, (meth)acrylated styrene-butadiene rubber, epoxy resin, (meth)acrylic resin, polyester resin, nylon, etc.

[0063] The conductive material may be used to impart conductivity to the electrode. Any conductive material that does not cause a chemical change in the electrode and is electronically conductive may be used. Examples of conductive materials include carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanofibers, and carbon nanotubes; metallic materials containing copper, nickel, aluminum, silver, and the like in the form of metal powder or metal fibers; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0064] Al can be used as the positive electrode collector (COL2), but is not limited thereto.

[0065]

[0066] positive electrode active material

[0067] As the positive active material within the positive active material layer (PAL), a compound capable of reversible intercalation and deintercalation of lithium (lithiated intercalation compound) can be used. Specifically, one or more of a composite oxide of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof can be used.

[0068] The above composite oxide may be a lithium transition metal composite oxide, and specific examples thereof include lithium nickel-based oxide, lithium cobalt-based oxide, lithium manganese-based oxide, lithium iron phosphate-based compound, cobalt-free nickel-manganese-based oxide, or a combination thereof.

[0069] As an example, a compound represented by any one of the following chemical formulas may be used: Li a A 1-b X b O 2-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Mn 2-b X b O 4-c D c(0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b X c About 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni 1-b-c Mn b X c About 2-α D α (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.5, 0<α<2); Li a Ni b Co c L 1 d G e O2(0.90≤a≤1.8, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0≤e≤0.1); Li a NiG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a CoG b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-b G b O2(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn2G b O4(0.90≤a≤1.8, 0.001≤b≤0.1); Li a Mn 1-g G g PO4(0.90≤a≤1.8, 0≤g≤0.5); Li (3-f) Fe2(PO4)3(0≤f≤2); Li a FePO4(0.90≤a≤1.8).

[0070] In the above chemical formula, A is Ni, Co, Mn, or a combination thereof; X is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; L 1 is Mn, Al or a combination thereof.

[0071] A coating layer may be additionally added to the surface of the above-described compound. The coating layer may include, for example, an oxide, a hydroxide, an oxyhydroxide, an oxycarbonate, or a hydroxycarbonate of the coating element of the coating element. The coating layer may be amorphous or crystalline. The coating element in the coating layer may be selected from the group consisting of Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, and Zr. The method for forming the coating layer may be selected within a range that does not adversely affect the physical properties of the positive electrode active material. The coating method may include, for example, spray coating or dipping.

[0072] For example, the cathode active material may be a high-nickel cathode active material in which the nickel content is 80 mol% or more, 85 mol% or more, 90 mol% or more, 91 mol% or more, or 94 mol% or more and 99 mol% or less, based on 100 mol% of metals excluding lithium in the lithium transition metal composite oxide. The high-nickel cathode active material can realize high capacity and thus can be applied to high-capacity, high-density lithium metal batteries.

[0073] In one embodiment, the positive electrode active material may include a layered lithium composite oxide containing nickel. More specifically, the lithium composite oxide may be, but is not limited to, lithium nickel cobalt aluminum oxide (NCA).

[0074]

[0075] Separator (SEP)

[0076] Depending on the type of lithium metal battery, a separator (SEP) may be provided between the positive electrode (PEL) and the negative electrode (NEL). The separator (SEP) may be a multilayer film made of polyethylene, polypropylene, polyvinylidene fluoride, or two or more layers thereof. Of course, a mixed multilayer film such as a polyethylene / polypropylene two-layer separator, a polyethylene / polypropylene / polyethylene three-layer separator, or a polypropylene / polyethylene / polypropylene three-layer separator may also be used.

[0077] The separator (SEP) may include a porous substrate and a coating layer comprising an organic material, an inorganic material, or a combination thereof, positioned on one or both sides of the porous substrate.

[0078] The above porous substrate may be a polymer film formed of any one polymer selected from polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyacetal, polyamide, polyimide, polycarbonate, polyether ketone, polyarylether ketone, polyetherimide, polyamideimide, polybenzimidazole, polyethersulfone, polyphenylene oxide, cyclic olefin copolymer, polyphenylene sulfide, polyethylene naphthalate, glass fiber, Teflon, and polytetrafluoroethylene, or a copolymer or mixture of two or more thereof.

[0079] The organic material may include a polyvinylidene fluoride polymer or a (meth)acrylic polymer.

[0080] The above inorganic materials are Al2O3, SiO2, TiO2, SnO2, CeO2, MgO, NiO, CaO, GaO, ZnO, ZrO2, Y2O3, It may include inorganic particles selected from, but not limited to, SrTiO3, BaTiO3, Mg(OH)2, boehmite, and combinations thereof.

[0081] The organic and inorganic substances may be mixed and present in one coating layer, or a coating layer including an organic substance and a coating layer including an inorganic substance may be present in a laminated form.

[0082]

[0083] Electrolyte layer (GPE)

[0084] The electrolyte layer (GPE) according to embodiments of the present invention may include a liquid electrolyte, a solid electrolyte, a gel electrolyte, or a combination thereof.

[0085] In one embodiment, the liquid electrolyte is an organic electrolyte. The organic electrolyte may include an organic solvent and a lithium salt. The organic solvent may be selected without limitation as long as it is used as an organic solvent in the art. For example, the organic solvent is propylene carbonate, ethylene carbonate, fluoroethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl isopropyl carbonate, dipropyl carbonate, dibutyl carbonate, benzonitrile, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, γ-butyrolactone, dioxolane, 4-methyldioxolane, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dioxane, 1,2-dimethoxyethane, sulfolane, dichloroethane, chlorobenzene, nitrobenzene, diethylene glycol, dimethyl ether or a mixture thereof.

[0086] Lithium salts can be selected without limitation as long as they are used as lithium salts in the relevant technical field. For example, lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, Li(FSO2)2N, LiC4F9SO3, LiAlO2, LiAlCl4, LiN(Cx F 2x+1 SO2)(C y F 2y+1 SO2)(1≤x≤20, 1≤y≤20), LiCl, LiI or a mixture thereof. For example, the concentration of the lithium salt may be 0.1 M to 5.0 M.

[0087] In one embodiment, the solid polymer electrolyte may include a mixture of a lithium salt and a polymer, or a polymer having an ion-conducting functional group. The solid polymer electrolyte may be solid at 25°C and 1 atm. The solid polymer electrolyte may not include a liquid.Polymers in the solid polymer electrolyte include, for example, polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide (PEO), poly(styrene-b-ethylene oxide) block copolymer (PS-PEO), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-b-divinylbenzene) block copolymer, poly(styrene-ethylene oxide-styrene) block copolymer, polystyrene sulfonate (PSS), polyvinyl fluoride (PVF), polymethyl methacrylate (PMMA), poly(methylmethacrylate), polyethylene glycol (PEG), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyethylenedioxythiophene (PEDOT), polypyrrole (PPY), polyacrylonitrile (PAN), Polyaniline, polyacetylene, Nafion, Aquivion, Flemion, Gore, Aciplex, Morgane ADP, sulfonated poly(ether ether ketone) (SPEEK), sulfonated poly(arylene ether ketone ketone sulfone) (SPAEKKS), sulfonated poly(aryl ether ketone) (SPAEK), poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI), poly(styrene sulfonate) (PSS), lithium It may be lithium 9,10-diphenylanthracene-2-sulfonate (DPASLi+) or a combination thereof.The polymer in the solid polymer electrolyte is not limited thereto and may be selected without limitation as long as it is used in polymer electrolytes in the relevant technical field.

[0088] The lithium salt in the solid polymer electrolyte can be selected from among the lithium salts used in the liquid electrolyte described above.

[0089] The polymer in the solid polymer electrolyte may contain 10 or more, 20 or more, 50 or more, or 100 or more repeating units. For example, the weight average molecular weight of the polymer in the solid polymer electrolyte may be 1000 Dalton or more, 10,000 Dalton or more, 100,000 Dalton or more, or 1,000,000 Dalton or more.

[0090] In one embodiment, the gel electrolyte may be a gel-polymer electrolyte. The gel-polymer electrolyte may have a gel state or a semi-solid state. The gel-polymer electrolyte may include a liquid electrolyte and a polymer, or may include an organic solvent and a polymer having an ion-conducting functional group. The gel-polymer electrolyte may be in a gel state or a semi-solid state at 25°C and 1 atm.

[0091] For example, a gel-polymer electrolyte may have a gel state without containing a liquid. The liquid electrolyte used in the gel-polymer electrolyte may be a mixture of a lithium salt and an organic solvent; a mixture of an ionic liquid and an organic solvent; or a mixture of an ionic liquid, a lithium salt, and an organic solvent.

[0092] The polymer in the gel polymer electrolyte may be selected from among the polymers used in the above-described solid polymer electrolyte. The organic solvent in the gel polymer electrolyte may be selected from among the organic solvents used in the above-described liquid electrolyte. The lithium salt in the gel polymer electrolyte may be selected from among the lithium salts used in the above-described liquid electrolyte.

[0093] The ionic liquid in the gel-polymer electrolyte may mean a salt or a molten salt in a liquid state at room temperature, which has a melting point below room temperature and is composed only of ions. The ionic liquid comprises: a) at least one cation selected from the group consisting of ammonium-based, pyrrolidinium-based, pyridinium-based, pyrimidinium-based, imidazolium-based, piperidinium-based, pyrazolium-based, oxazolium-based, pyridazinium-based, phosphonium-based, sulfonium-based, and triazolium-based cations; and b) BF4. - , PF6 - , AsF6 - , SbF6 - , AlCl4 - , HSO4 - , ClO4 - , CH3SO3 - , CF3CO2 - , Cl - , Br - , I - , BF4 - , SO4 - , CF3SO3 - , (FSO2)2N - , (C2F5SO2)2N - , (C2F5SO2)(CF3SO2)N - , and (CF3SO2)2N - It may include at least one anion selected from the group consisting of .

[0094] In one embodiment, a gel-polymer electrolyte can be formed by impregnating a solid polymer electrolyte into a liquid electrolyte.

[0095] In one embodiment, the gel polymer electrolyte may further comprise inorganic particles. The polymer within the gel polymer electrolyte may comprise at least 10, at least 20, at least 50, or at least 100 repeating units. For example, the weight average molecular weight of the polymer within the gel polymer electrolyte may be at least 500 Daltons, at least 1000 Daltons, at least 10,000 Daltons, at least 100,000 Daltons, or at least 1,000,000 Daltons.

[0096] In one embodiment of the present invention, the gel polymer electrolyte may include a polymer formed by polymerization of a multifunctional polymerizable monomer, i.e., a cross-linking agent. The cross-linking agent may be a material that is electrochemically stable in an operating environment (e.g., a voltage of about 4.3 V or higher) of a positive electrode using a positive electrode active material having a nickel content of 90 mol% or higher. For example, the crosslinking agent is pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, propoxylated (3) trimethylolpropane triacrylate (PO(3)TMPTA), propoxylated (6) trimethylolpropane triacrylate (PO(6)TMPTA), ethoxylated trimethylolpropane triacrylate, di(trimethylolpropane) tetraacrylate (Di(trimethylolpropane) tetraacrylate), pentaerythritol triacrylate (PETA), propoxylated glyceryl triacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate (THEICTA), and dipentaerythritol pentaacrylate (DPEPA), dipentaerythritol It may include at least one selected from the group consisting of hexaacrylate (DPHA).

[0097] The content of the crosslinked polymer in the gel-polymer electrolyte may be 1 to 10 parts by weight, 2 to 8 parts by weight, or 3 to 7 parts by weight based on 100 parts by weight of the total weight of the gel-polymer electrolyte. The content of the liquid electrolyte may be 90 to 99 parts by weight, 92 to 98 parts by weight, or 93 to 97 parts by weight based on 100 parts by weight of the total weight of the gel-polymer electrolyte.

[0098] According to one embodiment of the present invention, the electrolyte layer (GPE) may include the gel-polymer electrolyte described above. The separator (SEP) may be impregnated within the gel-polymer electrolyte. The pores within the separator (SEP) may be filled with the gel-polymer electrolyte.

[0099]

[0100] cathode (NEL)

[0101] Referring back to FIG. 1, the negative electrode (NEL) for a lithium metal battery may include a negative electrode current collector (COL1), and a negative electrode host layer (NHL) on the negative electrode current collector (COL1).

[0102] The negative electrode collector (COL1) may have a plate or foil shape.

[0103] In one embodiment, the negative electrode current collector (COL1) may include a base film and a metal layer on one or both sides of the base film.

[0104] The base film of the negative electrode current collector (COL1) may include at least one polymer selected from the group consisting of polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polybutylene terephthalate (PBT), and polyimide (PI). The base film may include an insulating and thermoplastic polymer. The base film of the negative electrode current collector (COL1) may soften or liquefy when a short circuit occurs, thereby blocking battery operation and suppressing a rapid increase in current. The negative electrode current collector (COL1) may additionally include a metal piece and / or a lead tab.

[0105] The negative host layer (NHL) can be provided directly on the surface of the negative current collector (COL1).

[0106] The negative host layer (NHL) may include carbon material and a lithium-affinity material.

[0107] In one embodiment, the carbon material may comprise amorphous hard carbon having a “host” structure, as described below.

[0108] In the present invention, “hard carbon” may refer to an amorphous, non-graphitizing carbon material that does not become graphitized even by high-temperature heat treatment. Such hard carbon may be manufactured by carbonizing resin, wood, fruit shells, coal that does not go through a melting step, or thermosetting polymers. These materials maintain their macromolecular structure even when subjected to high-temperature heat treatment, and crosslinking may be promoted as small molecules are detached (removed). The sites where these small molecules are detached may change into micropores. In the present invention, the particle size of the hard carbon may have an average particle diameter (D50) of 0.1 μm to 500 μm.

[0109]

[0110] The lithium-friendly material may include at least one of an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and an organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI).

[0111] Referring to FIG. 2, FIG. 2 is a schematic diagram illustrating a lithium metal battery after an initial cycle according to embodiments of the present invention. After charging, lithium is deposited between the negative electrode host layer (NHL) and the negative electrode current collector (COL1).

[0112] The lithium metal battery of FIG. 2 may form a lithium electrodeposited layer (NAL) after the initial cycle of operation. The negative electrode (NEL) of the lithium metal battery after the initial cycle may further include a lithium electrodeposited layer (NAL). The lithium electrodeposited layer (NAL) may be interposed between the negative electrode host layer (NHL) and the negative electrode current collector (COL1).

[0113] A lithium electrodeposited layer (NAL) may be formed by depositing lithium metal between a negative electrode host layer (NHL) and a negative electrode current collector (COL1) during charging of a lithium metal battery. The lithium electrodeposited layer (NAL) may include lithium metal or a lithium alloy. The lithium alloy may be an alloy of lithium and another metal capable of being alloyed with lithium. For example, the lithium alloy may include a lithium-silver alloy, a lithium-zinc alloy, a lithium-magnesium alloy, or a lithium-tin alloy.

[0114] The thickness of the lithium electrodeposited layer (NAL) can be, for example, 50 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 1 μm to 50 μm, 1 μm to 40 μm, 5 μm to 40 μm, 1 μm to 35 μm, or 10 μm to 35 μm. The energy density of the lithium metal battery can be improved by the lithium electrodeposited layer (NAL) having a thickness in the above-described range.

[0115] In one embodiment of the present invention, lithium may also be deposited within the negative electrode host layer (NHL). The lithium electrodeposited layer (NAL) may be formed after lithium is deposited within the negative electrode host layer (NHL).

[0116] In one embodiment, the thickness of the lithium electrodeposited layer (NAL) at maximum charge may be 35 μm or less, 30 μm or less, 28 μm or less, 10 μm to 35 μm, 10 μm to 30 μm, or 10 μm to 28 μm.

[0117]

[0118] Figure 3 is a cross-sectional view illustrating a cathode according to embodiments of the present invention.

[0119] Referring to FIG. 3, in one embodiment of the present invention, a negative electrode host layer (NHL) may be positioned on a negative electrode current collector (COL1). The negative electrode host layer (NHL) may include a 3D host layer, which will be described later. The negative electrode host layer (NHL) induces uniform lithium deposition and de-deposition during lithium deposition and de-deposition, thereby enhancing reversibility and improving the life characteristics of the battery. When the battery is discharged, lithium can be de-deposited along the negative electrode host layer (NHL).

[0120] The term “host” used in the present invention refers to a function that can prevent problems such as internal short circuit, discharge, volume expansion of the lithium negative electrode, electrolyte shortage, and acceleration of side reactions by suppressing the growth of lithium dendrites occurring in the lithium negative electrode.

[0121] According to one embodiment, the cathode host layer (NHL) may have a structure of a 3D host layer.

[0122] The host layer can have sufficient strength to maintain its shape without being damaged by the growth of lithium dendrites.

[0123] According to one embodiment, the negative electrode host layer (NHL) can have an appropriate thickness and porosity to prevent volume expansion of the lithium negative electrode due to lithium dendrite growth and to prevent a decrease in energy density of the battery.

[0124] The present invention is to uniformly coat a material that forms and induces lithium metal on a negative electrode host layer (NHL) having a porosity and a pore size and position it on a negative electrode current collector.

[0125] Therefore, it is possible to more effectively grow lithium metal into the pores of the negative electrode host layer (NHL), thereby preventing volume expansion of the lithium electrode, thereby providing a lifespan superior to the conventional technology of coating a negative electrode active material including a carbon material on a negative electrode current collector.

[0126] The negative host layer (NHL) may include the carbon material described above formed in a 3D structure on the negative current collector (COL1). The negative host layer (NHL) may be formed in a 3D host-to-host orthogonal shape, may have holes formed in the middle, may be formed in a mesh-like structure, but is not necessarily limited thereto.

[0127] In one embodiment, the thickness of the negative host layer (NHL) may be thicker than the thickness of the lithium electrodeposition layer (NAL) described above. The thickness of the negative host layer (NHL) may be, for example, 60 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, 1 μm to 60 μm, 1 μm to 50 μm, 5 μm to 50 μm, 1 μm to 45 μm, 1 μm to 30 μm, 1 μm to 20 μm, or 10 μm to 45 μm. When the negative host layer (NHL) has a thickness in the above-described range, the energy density of the lithium metal battery may be improved.

[0128]

[0129] FIG. 4a is an enlarged cross-sectional view of part M of FIG. 3 in a state before charging of the negative electrode according to one embodiment.

[0130] In one embodiment, the cathode host layer may include a carbon material and a coating layer (CTL) on the surface of the carbon material.

[0131] The carbon material may be substantially the same as that described above for the cathode (NEL).

[0132] The coating layer (CTL) may include a lithium-affinity material.

[0133] The lithium-friendly material may include at least one of an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and an organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI).

[0134] For example, the lithium-affinity material may use at least one of titania (TiO2), phosphorus (P), and nitrogen (N).

[0135] The lithium-affinity material may be included in an amount of 0.5 wt% to 5 wt% or 2.5 wt% to 4.5 wt% of the total weight of the carbon material. If the content of the lithium-affinity material is less than 0.5 wt%, the lithium-affinity material may be added in a small amount, making it difficult to induce lithium electrodeposition. Conversely, if the content of the lithium-affinity material exceeds 5 wt%, the amount coated on the outside of the carbon material may increase, which may cause a problem of increased side reactions with the electrolyte.

[0136] Referring to FIGS. 3 and 4A, the cathode host layer (NHL) may be composed of a plurality of first frames (3DH1), a plurality of second frames (3DH2), and a plurality of pores (HL). In one embodiment, the first and second frames (3DH1, 3DH2) may include the carbon material described above.

[0137] The first and second frames (3DH1, 3DH2) may include a coating layer (CTL) on the surface.

[0138] According to one embodiment, the first and second frames (3DH1, 3DH2) may have a coating layer (CTL) formed of the above-described lithium-friendly material component applied to their surfaces.

[0139] In one embodiment, the plurality of frames may have lithium affinity and mechanical stability. Furthermore, the plurality of frames may minimize energy loss and maximize the specific surface area of ​​the battery.

[0140] The first frame (3DH1) may be parallel to the Y-axis and may be composed of a plurality of first frames (3DH1). The height of the first frame (3DH1) may be equal to or smaller than the height of the negative host layer (NHL). The height of the first frame (3DH1) refers to the length of the portion parallel to the Y-axis. The height of the first frame (3DH1) may be greater than the thickness of the lithium electrodeposition layer (NAL) described above. The height of the first frame (3DH1) may be, for example, 60 ㎛ or less, 50 ㎛ or less, 45 ㎛ or less, 40 ㎛ or less, 1 ㎛ to 60 ㎛, 1 ㎛ to 50 ㎛, 5 ㎛ to 50 ㎛, 1 ㎛ to 45 ㎛, or 10 ㎛ to 45 ㎛.

[0141] The thickness of the first frame (3DH1) refers to the length of the portion parallel to the X-axis. The thickness of the first frame (3DH1) may be, for example, 1 nm to 50 nm, 5 nm to 30 nm, 10 nm to 30 nm, or 20 nm to 30 nm.

[0142] The structure of the first frame (3DH1) may be formed such that a carbon layer including the above-described carbon material is formed in a orthogonal shape, and a coating layer (CTL) including the above-described lithium-affinity material may be formed on the surface of the carbon layer.

[0143] The structure of the first frame (3DH1) may be a shape with holes in the middle and may be formed in a structure that is entangled like a net, but is not necessarily limited thereto.

[0144] The second frame (3DH2) may be parallel to the X-axis and may be composed of multiple frames. The horizontal length of the second frame (3DH2) may be equal to or smaller than the horizontal length of the cathode host layer (NHL). The height of the second frame (3DH2) may be equal to the thickness of the first frame (3DH1). The height of the second frame (3DH2) refers to the length of the portion parallel to the Y-axis. The height of the second frame (3DH2) may be, for example, 1 nm to 50 nm, 5 nm to 30 nm, 10 nm to 30 nm, or 20 nm to 30 nm.

[0145] The structure of the second frame (3DH2) may be formed in a orthogonal shape with a carbon layer including the above-described carbon material, and a coating layer (CTL) including the above-described lithium-affinity material may be formed on the surface of the carbon layer.

[0146] The structure of the second frame (3DH2) may be a shape with holes in the middle and may be formed in a structure that is entangled like a net, but is not necessarily limited thereto.

[0147] The thickness of the coating layer (CTL) formed on the surface of the first frame (3DH1) and the second frame (3DH2) may be 0.01 nm to 10 nm, 0.05 nm to 8 nm, 0.1 nm to 5 nm, or 1 nm to 3 nm.

[0148] The void (HL) refers to the space other than the space occupied by the first frame (3DH1) and the second frame (3DH2). The void (HL) is an empty space before the initial cycle, but can be filled with lithium metal (LM) after the initial cycle.

[0149] According to one embodiment, the size of the pore (HL) may be, but is not necessarily limited to, 10 nm to 10 μm or 20 nm to 90 nm. In this case, the size of the pore (HL) means the length of the longest axis of the pore (HL).

[0150] According to one embodiment, the porosity of the negative electrode host layer (NHL) may be 40% to 80%, 50% to 70%, or 40% to 70%. The porosity refers to the ratio of the volume of the pores to the total volume, and in the case of the embodiment of the present invention, it refers to the ratio of the volume of the pores (HL) to the volume value obtained by multiplying the area of ​​the negative electrode current collector (COL1) by the height of the negative electrode host layer (NHL).

[0151]

[0152] FIG. 4b is an enlarged cross-sectional view of part M of FIG. 3 in a state after charging of the negative electrode according to one embodiment.

[0153] Referring to Fig. 4b, after the initial cycle, lithium metal (LM) can be located within multiple pores (HL). Referring to Figs. 3 and 4b, lithium can be deposited between negative host layers (NHL). The negative host layer (NHL) has a 3D structure of a carbon layer, so that lithium metal (LM) can be deposited within the 3D host. The negative host layer (NHL) can suppress volume changes due to lithium dendrites and lithium deposition / desorption during charge / discharge.

[0154] According to one embodiment, even if deposition and desorption of lithium metal (LM) occur during charge and discharge, no structural change occurs in the negative electrode host layer (NHL).

[0155] In one embodiment, during charging and discharging, lithium metal (LM) can be randomly located in multiple pores (HL).

[0156] According to one embodiment, during charging and discharging, lithium metal (LM) can be evenly deposited in a plurality of pores (HL) on the surface of the carbon material by a coating layer (CTL) including a lithium-affinity material.

[0157]

[0158] Figure 5 is a flowchart illustrating a method for manufacturing a cathode according to one embodiment of the present invention.

[0159] Referring to FIG. 5, a method for manufacturing a negative electrode according to one embodiment may include forming a coating layer on a carbon material by coating a lithium-affinity material on the surface of the carbon material (S100); forming a slurry by mixing the carbon material, a binder, and an organic solvent (S200); forming a negative electrode host layer by applying the slurry on a negative electrode current collector (S300); and drying the negative electrode host layer (S400).

[0160] Forming a coating layer (S100) can form a lithium-affinity material on the surface of a carbon material by applying a method such as mixing or deposition.

[0161] The carbon material may be the same as that described above for the cathode. For example, the carbon material may include amorphous hard carbon. The carbon material may be composed of a plurality of first frames, a plurality of second frames, and a plurality of pores.

[0162] The lithium-friendly material can be the same lithium-friendly material as described above for the negative electrode (NEL).

[0163] The lithium-friendly material may include at least one of an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and an organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI).

[0164] For example, the lithium-affinity material may use at least one of titania (TiO2), phosphorus (P), and nitrogen (N).

[0165] Mixing may be accomplished using at least one of a ball mill, a vibration mill, a jet mill, a bead mill, an attrition mill, and a combination thereof.

[0166] Mixing can be performed under mild conditions. For example, mixing can be performed using a high-energy ball milling machine, a thinky mixer, a V-mixer, a twist mixer, or by simple hand mixing.

[0167] In one embodiment, the mixing may be performed using mixing equipment at a rotation speed of 300 rpm to 1,000 rpm for 20 to 30 hours.

[0168] The above mixing can be performed with the carbon material and the lithium-compatible material at a mixing ratio of 1:0.1 to 1:0.3. If the mixing ratio is less than 1:0.1, the coating amount of the lithium-compatible material is very small, making it difficult to achieve the lithium dendrite suppression effect and long-life effect. If the mixing ratio exceeds 1:0.3, the lithium-compatible material is added in excessive amounts, which may increase the resistance caused by the lithium-compatible material.

[0169] Among the lithium-friendly materials input, 20% to 40% may be coated on the surface of the carbon material, and the remaining lithium-friendly materials may remain in the mixing equipment.

[0170] Therefore, when the mixing ratio satisfies the above range, the lithium-affinity material can be coated on the surface of the carbon material in an amount of 0.5 wt% to 5 wt% as described above.

[0171] After the mixing process, an additional heat treatment process may be performed on the mixed material at a temperature of 400°C to 1,000°C. Through this heat treatment process, impurities other than lithium-affinity materials can be removed from the carbon surface.

[0172] Deposition can form a lithium-affinity material on the surface of a carbon material by applying either a physical vapor deposition (PVD) method or a chemical vapor deposition (CVD) method.

[0173] The thickness of the coating layer formed on the surface of the carbon material may be 0.01 nm to 10 nm, 0.05 nm to 8 nm, 0.1 nm to 5 nm, or 1 nm to 3 nm.

[0174] The carbon material having a coating layer formed thereon may contain a lithium-affinity material in an amount of 0.5 wt% to 5 wt% or 2.5 wt% to 4.5 wt% of the total weight of the carbon material.

[0175] Forming a slurry (S200) may include mixing a carbon material on which a coating layer is formed, a binder, and an organic solvent.

[0176] As an example, a slurry may be prepared by adding NMP (N-methyl pyrrolidone) to a carbon material and a binder on which a coating layer is formed and then mixing them.

[0177] Forming a negative electrode host layer (S300) may include a process of applying the slurry onto a negative electrode current collector. The negative electrode current collector refers to the negative electrode portion described above.

[0178] In one embodiment, the slurry can be used to form a cathode host layer on an aluminum current collector.

[0179] Drying the negative electrode host layer (S400) may include a process of heat treating the negative electrode host layer formed on the negative electrode current collector.

[0180] The above heat treatment can be performed at a temperature of 80°C to 180°C. In addition, the drying time can be performed for 2 to 24 hours, but is not limited thereto.

[0181] In one embodiment, a negative electrode having a negative electrode host layer formed by drying a slurry-coated negative electrode collector in a vacuum oven can be manufactured.

[0182] The thickness of the cathode host layer can be, for example, 60 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 1 μm to 60 μm, 1 μm to 50 μm, 5 μm to 50 μm, 1 μm to 45 μm, or 10 μm to 45 μm.

[0183] Finally, a negative electrode can be manufactured including a negative electrode current collector and a negative electrode host layer formed on the negative electrode current collector. The negative electrode host layer can include a carbon material coated with a lithium-affinity material.

[0184]

[0185] FIG. 6a is an enlarged cross-sectional view of part M of FIG. 3 in a state before charging of the negative electrode according to another embodiment.

[0186] In another embodiment, the negative host layer may include a carbon material and a carbon material doped with a lithium-affinity material.

[0187] The carbon material may be substantially the same as that described above for the cathode (NEL).

[0188] The lithium-friendly material may be at least one of an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and an organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI).

[0189] In another embodiment, the lithium-affinity material may use an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), and phosphorus (P) as a doping material.

[0190] The lithium-affinity material may be doped at 0.5 wt% to 5 wt% or 2.5 wt% to 4.5 wt% of the total weight of the carbon material. If the doping content of the lithium-affinity material is less than 0.5 wt%, the lithium-affinity material may be doped in a small amount, making it difficult to induce lithium electrodeposition. Conversely, if the doping content of the lithium-affinity material exceeds 5 wt%, the amount of doping inside and outside the carbon material may increase, which may cause a problem of increased side reactions with the electrolyte.

[0191] Referring to FIG. 3 and FIG. 6a, the cathode host layer (NHL) may be composed of a plurality of first frames (3DH1), a plurality of second frames (3DH2), and a plurality of pores (HL).

[0192] In another embodiment, the first and second frames (3DH1, 3DH2) may include the carbon material described above. The first and second frames (3DH1, 3DH2) may include a lithium-friendly material (LPM) on the inside and outside.

[0193] According to another embodiment, the first and second frames (3DH1, 3DH2) may be doped with the lithium affinity material (LPM) described above on the inside and outside thereof.

[0194] In another embodiment, the plurality of frames may have lithium affinity and mechanical stability. Furthermore, the plurality of frames may minimize energy loss and maximize the specific surface area of ​​the battery.

[0195] The first frame (3DH1) may be parallel to the Y-axis and may be composed of a plurality of first frames (3DH1). The height of the first frame (3DH1) may be equal to or smaller than the height of the negative host layer (NHL). The height of the first frame (3DH1) refers to the length of the portion parallel to the Y-axis. The height of the first frame (3DH1) may be greater than the thickness of the lithium electrodeposition layer (NAL) described above. The height of the first frame (3DH1) may be, for example, 60 ㎛ or less, 50 ㎛ or less, 45 ㎛ or less, 40 ㎛ or less, 1 ㎛ to 60 ㎛, 1 ㎛ to 50 ㎛, 5 ㎛ to 50 ㎛, 1 ㎛ to 45 ㎛, or 10 ㎛ to 45 ㎛.

[0196] The thickness of the first frame (3DH1) refers to the length of the portion parallel to the X-axis. The thickness of the first frame (3DH1) may be, for example, 1 nm to 50 nm, 5 nm to 30 nm, 10 nm to 30 nm, or 20 nm to 30 nm.

[0197] The structure of the first frame (3DH1) may be formed in a orthogonal shape with carbon layers including the above-described carbon material, and the above-described lithium-affinity material (LPM) may be doped into the carbon layers.

[0198] The structure of the first frame (3DH1) may be a shape with holes in the middle and may be formed in a structure that is entangled like a net, but is not necessarily limited thereto.

[0199] The second frame (3DH2) may be parallel to the X-axis and may be composed of multiple frames. The horizontal length of the second frame (3DH2) may be equal to or smaller than the horizontal length of the cathode host layer (NHL). The height of the second frame (3DH2) may be equal to the thickness of the first frame (3DH1). The height of the second frame (3DH2) refers to the length of the portion parallel to the Y-axis. The height of the second frame (3DH2) may be, for example, 1 nm to 50 nm, 5 nm to 30 nm, 10 nm to 30 nm, or 20 nm to 30 nm.

[0200] The structure of the second frame (3DH2) may be formed in a orthogonal shape with carbon layers including the above-described carbon material, and the above-described lithium-affinity material (LPM) may be doped into the carbon layers.

[0201] The structure of the second frame (3DH2) may be a shape with holes in the middle and may be formed in a structure that is entangled like a net, but is not necessarily limited thereto.

[0202] The average particle diameter (D50) of the lithium-affinity material doped inside and outside the first frame (3DH1) and the second frame (3DH2) may be 0.01 nm to 10 nm, 0.05 nm to 8 nm, 0.1 nm to 5 nm, or 1 nm to 3 nm.

[0203] The void (HL) refers to the space other than the space occupied by the first frame (3DH1) and the second frame (3DH2). The void (HL) is an empty space before the initial cycle, but can be filled with lithium metal (LM) after the initial cycle.

[0204] In another embodiment, the size of the pore (HL) may be, but is not necessarily limited to, 10 nm to 10 μm or 20 nm to 90 nm. In this case, the size of the pore (HL) means the length of the longest axis of the pore (HL).

[0205] In another embodiment, the porosity of the negative electrode host layer (NHL) may be 40% to 80%, 50% to 70%, or 40% to 70%. The porosity refers to the ratio of the volume of the pores to the total volume, and in the case of the embodiment of the present invention, it refers to the ratio of the volume of the pores (HL) to the volume value obtained by multiplying the area of ​​the negative electrode current collector (COL1) by the height of the negative electrode host layer (NHL).

[0206]

[0207] FIG. 6b is a schematic diagram illustrating the bonding state of carbon atoms and lithium-affinity materials of a negative electrode host layer according to another embodiment.

[0208] Referring to FIG. 6b, the carbon material present in the negative host layer (NHL) may include atoms of a lithium-affinity material (LPM) and carbon atoms (C).

[0209] In another embodiment, the carbon material included in the negative electrode host layer (NHL) may include a structure in which atoms of a lithium affinity material (LPM) and carbon (C) atoms are directly bonded to each other through covalent bonds.

[0210] According to another embodiment of the present invention, the negative host layer (NHL) may include single bonds or double bonds between atoms of the lithium affinity material (LPM) and carbon (C) atoms.

[0211] The single bond or double bond between the carbon (C) atom and the lithium-affinity material (LPM) atom is a lithium-affinity functional group, which is more advantageous for lithium electrodeposition and can reduce the amount of side reactions with the electrolyte.

[0212]

[0213] FIG. 6c is an enlarged cross-sectional view of part M of FIG. 3 in a state before charging of the negative electrode according to another embodiment.

[0214] Referring to Fig. 6c, after the initial cycle, lithium metal (LM) can be located within multiple pores (HL). Referring to Figs. 3 and 6c, it can be confirmed that lithium is deposited between negative host layers (NHL). The negative host layer (NHL) has a 3D structure of a carbon layer, so that lithium metal (LM) can be deposited within the 3D host. The negative host layer (NHL) can suppress volume changes due to lithium dendrites and lithium deposition / desorption during charge / discharge.

[0215] According to another embodiment, even if deposition and desorption of lithium metal (LM) occur during charge and discharge, no structural change occurs in the negative electrode host layer (NHL).

[0216] In another embodiment, during charging and discharging, lithium metal (LM) can be randomly located in multiple pores (HL).

[0217] According to another embodiment, during charge and discharge, lithium metal (LM) can be uniformly deposited in multiple pores (HL) by a lithium affinity material (LPM) doped in the carbon material.

[0218]

[0219] Figure 7 is a flowchart illustrating a method for manufacturing a cathode according to another embodiment of the present invention.

[0220] Referring to FIG. 7, a method for manufacturing a negative electrode according to one embodiment may include doping a lithium-affinity material into a carbon material (S110); mixing the doped carbon material, a binder, and an organic solvent to form a slurry (S210); applying the slurry onto a negative electrode current collector to form a negative electrode host layer (S310); and drying the negative electrode host layer (S410).

[0221]

[0222] Doping a carbon material with a lithium-affinity material (S110) may include a process of mixing a carbon material and a lithium-affinity material precursor and then performing a heat treatment.

[0223] The carbon material may be the same as that described above for the cathode. For example, the carbon material may include amorphous hard carbon.

[0224] The carbon material may be composed of a plurality of first frames, a plurality of second frames, and a plurality of voids.

[0225] The lithium-compatible material can be the same lithium-compatible material as described above for the negative electrode.

[0226] The lithium-friendly material may include at least one of an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and an organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI).

[0227] For example, a lithium-affinity material can use an inorganic material selected from the group consisting of nitrogen (N), sulfur (S), and phosphorus (P) as a doping material.

[0228] The doped carbon material may contain a lithium-affinity material in an amount of 0.5 wt% to 5 wt% or 2.5 wt% to 4.5 wt% of the total weight of the carbon material.

[0229] Doping can form lithium-affinity materials inside and outside of carbon materials by applying mixing and heat treatment methods.

[0230] Mixing may be performed using at least one of a ball mill, a vibration mill, a jet mill, a bead mill, an attrition mill, and a combination thereof. In one embodiment, the mixing may be performed using mixing equipment at a rotation speed of 300 rpm to 1,000 rpm for 20 to 30 hours.

[0231] The above mixing can be performed with the carbon material and the lithium-compatible material at a mixing ratio of 1:0.1 to 1:0.3. If the mixing ratio is less than 1:0.1, the coating amount of the lithium-compatible material is very small, making it difficult to achieve the lithium dendrite suppression effect and long-life effect. If the mixing ratio exceeds 1:0.3, the lithium-compatible material is added in excessive amounts, which may increase the resistance caused by the lithium-compatible material.

[0232] Among the lithium-compatible materials, 10% to 20% may be combined with carbon atoms. The remaining lithium-compatible materials may remain in the mixing equipment, be carbonized through heat treatment as described below, or be discharged through an exhaust device connected to the heat treatment equipment.

[0233] Therefore, when the mixing ratio satisfies the above range, the lithium-affinity material can be doped into the carbon material in an amount of 0.5 wt% to 5 wt% as described above.

[0234] Heat treatment can be performed to chemically bond carbon atoms and lithium-affinity material atoms.

[0235] The above heat treatment can be performed in a gas atmosphere selected from nitrogen, argon, and combinations thereof. The heat treatment can minimize oxygen involvement by performing it in a nitrogen or argon atmosphere.

[0236] In one embodiment, the heat treatment equipment may be a furnace of various types. For example, it may be a box-type furnace or, considering productivity, a rotary kiln capable of continuous processing.

[0237] The above heat treatment can be performed at a temperature of 400°C to 1,000°C. The heat treatment can be performed for a period of time sufficient to allow sufficient bonding between carbon atoms and lithium-compatible material atoms, and can be performed for 30 minutes to 5 hours. If the heat treatment is performed for less than 30 minutes, the carbon atoms and lithium-compatible material atoms may not bond smoothly.

[0238] Forming a slurry (S210) may include mixing a carbon material doped with a lithium-affinity material, a binder, and an organic solvent.

[0239] As an example, a slurry may be prepared by adding NMP (N-methyl pyrrolidone) to a carbon material and a binder doped with a lithium-affinity material and then mixing them.

[0240] Forming a negative electrode host layer (S310) may include a process of applying the slurry onto a negative electrode current collector. The negative electrode current collector refers to the negative electrode portion described above. In one embodiment, the slurry may be used to form a negative electrode host layer on an aluminum current collector.

[0241] Drying the negative host layer (S410) may include a process of heat treating the negative host layer formed on the negative electrode current collector.

[0242] The above heat treatment can be performed at a temperature of 80°C to 180°C. In addition, the drying time can be performed for 2 to 24 hours, but is not limited thereto.

[0243] In one embodiment, a negative electrode having a negative electrode host layer formed by drying a slurry-coated negative electrode collector in a vacuum oven can be manufactured.

[0244] The thickness of the cathode host layer can be, for example, 60 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 1 μm to 60 μm, 1 μm to 50 μm, 5 μm to 50 μm, 1 μm to 45 μm, or 10 μm to 45 μm.

[0245] Finally, a negative electrode including a negative electrode current collector and a negative electrode host layer formed on the negative electrode current collector can be manufactured.

[0246] The above negative host layer may include a carbon material doped with a lithium-affinity material.

[0247] The above doped carbon material may include atoms of a lithium-affinity material, carbon atoms, etc. In one embodiment, the above doped carbon material may have a structure in which atoms of a lithium-affinity material and carbon atoms are bonded by single bonds or double bonds.

[0248]

[0249] lithium metal battery

[0250] Referring to FIG. 8, a lithium battery (LBT) according to an embodiment of the present invention may include the aforementioned positive electrode (PEL), the aforementioned negative electrode (NEL), and the separator (SEP). The positive electrode (PEL), the negative electrode (NEL), and the separator (SEP) may be wound or folded to form a battery structure (BTS). The battery structure (BTS) may be accommodated in a battery case (CAS). An electrolyte layer may be formed by injecting an electrolyte into the battery case (CAS). The lithium battery (LBT) may be manufactured by sealing the battery case (CAS) with a cap assembly (CAB). The battery case (CAS) may be cylindrical, but is not necessarily limited to this shape, and may be, for example, square, thin-film, etc.

[0251] Referring to FIG. 9, a lithium battery (LBT) according to one embodiment of the present invention may include the above-described positive electrode (PEL), the above-described negative electrode (NEL), and the separator (SEP). The separator (SEP) is disposed between the positive electrode (PEL) and the negative electrode (NEL), and the positive electrode (PEL), the negative electrode (NEL), and the separator (SEP) may be wound or folded to form a battery structure (BTS).

[0252] The formed battery structure (BTS) can be accommodated in a battery case (CAS). An electrode tab (ELT) that serves as an electrical path for conducting the current formed in the battery structure (BTS) to the outside can be included. An electrolyte layer can be formed by injecting an electrolyte into the battery case (CAS). The battery case (CAS) can be sealed to manufacture a lithium battery (LBT). The battery case (CAS) is not necessarily limited to a square shape, but may be, for example, cylindrical, thin-film, etc.

[0253] Referring to FIG. 10, a lithium battery (LBT) according to one embodiment of the present invention may include the aforementioned positive electrode (PEL), the aforementioned negative electrode (NEL), and the separator (SEP). The separator (SEP) may be disposed between the positive electrode (PEL) and the negative electrode (NEL) to form a battery structure (BTS).

[0254] A battery structure (BTS) can be stacked in a bi-cell structure and then accommodated in a battery case (CAS). An electrode tab (ELT) that serves as an electrical path for conducting current formed in the battery structure (BTS) to the outside can be included. An electrolyte layer can be formed by injecting an electrolyte into the battery case (CAS). The battery case (CAS) can be sealed to manufacture a lithium battery (LBT). The battery case (CAS) is not necessarily limited to a square shape, and may be, for example, cylindrical, thin-film, etc.

[0255] A pouch-type lithium battery may correspond to a lithium battery (LBT) of each of FIGS. 6 to 8 that uses a pouch as a battery case (CAS). The pouch-type lithium battery may include at least one battery structure (BTS). The battery structure (BTS) may be laminated in a bi-cell structure, then impregnated with an electrolyte layer, and accommodated and sealed in a pouch to manufacture a pouch-type lithium battery.

[0256] For example, the above-described positive electrode, negative electrode, and separator may be simply laminated and housed in a pouch in the form of an electrode assembly. The electrode assembly may be wound or folded into a jelly roll shape and then housed in the pouch. An electrolyte layer may be formed by injecting an electrolyte solution into the pouch.

[0257] Lithium batteries have excellent cycle life and high-rate characteristics, making them suitable for use in electric vehicles (EVs). For example, they can be used in plug-in hybrid electric vehicles (PHEVs). They can also be used in applications requiring large amounts of power storage, such as electric bicycles and power tools.

[0258] Multiple lithium batteries can be stacked to form a battery module. Multiple battery modules can form a battery pack. Such a battery pack can be used in any device requiring high capacity and output. Examples include laptops, smartphones, and electric vehicles. For example, a battery module may include multiple batteries and a frame supporting them.

[0259] A battery pack may include, for example, a plurality of battery modules and a bus bar connecting them. The battery modules and / or the battery pack may further include a cooling device. The plurality of battery packs may be controlled by a battery management system. The battery management system may include a battery pack and a battery control device connected to the battery pack.

[0260]

[0261] A lithium battery including a solid electrolyte is described in more detail below. A lithium metal battery according to one embodiment of the present invention may be, for example, an all-solid-state lithium battery including a solid electrolyte. By including the aforementioned negative electrode, the all-solid-state lithium battery can have improved capacity and superior lifespan characteristics.

[0262] FIG. 11 is a schematic conceptual diagram illustrating a lithium metal battery according to embodiments of the present invention. Referring to FIG. 11, the all-solid-state lithium battery may include a positive electrode (PEL), the aforementioned negative electrode (NEL), and a solid electrolyte layer (SEL) interposed between the positive electrode (PEL) and the negative electrode (NEL). The positive electrode (PEL) may include a positive electrode current collector (COL2) and a positive electrode active material layer (PAL). The positive electrode active material layer (PAL) may include a positive electrode active material, a solid electrolyte, a conductive material, and a binder. The positive electrode active material, the conductive material, and the binder may be substantially the same as or similar to those described in the positive electrode active material layer (PAL) with reference to FIG. 1 above.

[0263] The solid electrolyte may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. Examples of the sulfide-based solid electrolyte include Li2S-P2S5, Li2S-P2S5-LiX (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 (m, n are positive numbers, capital letter “Z” represents Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, capital letter “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).

[0264] Sulfide-based solid electrolytes include, 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 (0≤x≤2) may be an argyrodite-type compound including at least one selected from. In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I. The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. Since the argyrodite-type solid electrolyte has a density of 1.5 g / cc or more, the internal resistance of the all-solid-state battery is reduced, and the defect of the solid electrolyte membrane being penetrated and short-circuited due to the formation of lithium dendrites can be prevented. The elastic modulus of the solid electrolyte may be, for example, 15 GPa to 35 GPa.

[0265] The solid electrolyte in the positive active material layer (PEL) may have a smaller average particle diameter (D50) than the solid electrolyte in the solid electrolyte layer (SEL), which will be described later. For example, the average particle diameter (D50) of the solid electrolyte in the positive active material layer (PEL) 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 diameter (D50) of the solid electrolyte in the solid electrolyte layer (SEL).

[0266] When the total amount of the positive electrode active material, the solid electrolyte, the conductive material, and the binder is 100 parts by weight, the positive electrode active material layer (PEL) may include 85 parts by weight to 92 parts by weight of the positive electrode active material. The positive electrode active material layer (PEL) may include 0.5 parts by weight to 1.5 parts by weight of the binder.

[0267] Within the positive active material layer (PEL), the conductive material may be present in an amount of 1 to 50 parts by weight relative to 100 parts by weight of the solid electrolyte. If the conductive material is present in an amount less than 1 part by weight relative to 100 parts by weight of the solid electrolyte, the electrical conductivity of the positive active material layer (PEL) may be reduced. If the conductive material is present in an amount greater than 50 parts by weight relative to 100 parts by weight of the solid electrolyte, the conductive material ratio may be excessively high, and a covering layer covering the surface of the solid electrolyte may not be properly formed.

[0268] According to embodiments, the positive electrode active material layer (PEL) may further include at least one additive selected from the group consisting of a filler, a coating agent, a dispersant, and an ion conductive additive, in addition to the positive electrode active material, solid electrolyte, conductive agent, and binder described above.

[0269] The solid electrolyte layer (SEL) is disposed between the positive electrode (PEL) and the negative electrode (NEL) and may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. The solid electrolyte in the solid electrolyte layer (SEL) may be the same as or similar to the solid electrolyte in the positive electrode active material layer (PEL) described above.

[0270] The solid electrolyte layer (SEL) may further include a binder. The binder in the solid electrolyte layer (SEL) may be, but is not limited to, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, or the like. The binder in the solid electrolyte layer (SEL) may be the same as or similar to the binder in the positive active material layer (PAL).

[0271] The negative electrode (NEL) of the all-solid-state lithium battery may be substantially the same as or similar to the negative electrode (NEL) described above with reference to FIGS. 1 to 7.

[0272]

[0273] Hereinafter, the present invention will be described in more detail through examples. However, these examples are intended to exemplify the present invention and the scope of the present invention is not limited to these examples.

[0274]

[0275] Example 1

[0276] 9 g of amorphous hard carbon having a host structure and 1 g of titania (TiO2) were placed in a Thinky-mixer and a mixing process was performed at 500 rpm for 24 hours to produce a carbon material coated with a lithium-affinity material. The carbon material produced in Example 1 was coated with titania (TiO2) at approximately 3 wt% of the total weight of the carbon material.

[0277] The above carbon material and binder were added to NMP at a mixing ratio of 9.5:0.5, and then mixed to prepare a cathode slurry.

[0278] The above negative electrode slurry was applied to a negative electrode current collector to form a negative electrode coating layer, and then dried at 80°C for 10 hours to manufacture a negative electrode having a negative electrode host layer with a thickness of approximately 30 μm formed on the negative electrode current collector. Here, the porosity of the manufactured negative electrode host layer is approximately 50%.

[0279]

[0280] Example 2

[0281] A negative electrode was manufactured in the same manner as in Example 1, except that 9 g of amorphous hard carbon having a host structure and 1 g of a phosphorus precursor were used. The carbon material manufactured in Example 2 was coated with phosphorus (P) at approximately 3 wt% of the total weight of the carbon material.

[0282]

[0283] Example 3

[0284] 8 g of amorphous hard carbon having a host structure, 2 g of nitrogen precursor, and 2 g of zirconia balls were placed in a ball mill container and a mixing process was performed. The mixing process was performed using a planetary ball mill at 500 rpm for 24 hours.

[0285] The mixed powder was calcined at 800°C for 2 hours in a nitrogen (N2) atmosphere to produce a carbon material doped with a lithium affinity material. The carbon material produced in Example 3 was doped with nitrogen (N) at approximately 3 wt% of the total weight of the carbon material.

[0286] The above carbon material and binder were added to NMP at a mixing ratio of 9.5:0.5, and then mixed to prepare a cathode slurry.

[0287] The above negative electrode slurry was applied to a negative electrode current collector to form a negative electrode coating layer, and then dried at 80°C for 10 hours to manufacture a negative electrode having a negative electrode host layer with a thickness of approximately 30 μm formed on the negative electrode current collector. Here, the porosity of the manufactured negative electrode host layer is approximately 50%.

[0288]

[0289] Example 4

[0290] A negative electrode was manufactured according to the same method as in Example 1, except that 5 g of amorphous hard carbon having a host structure and 5 g of titania (TiO2) were used. The carbon material manufactured in Comparative Example 3 was coated with titania (TiO2) at approximately 15 wt% of the total weight of the carbon material.

[0291]

[0292] Example 5

[0293] A negative electrode was manufactured according to the same method as in Example 1, except that 9.9 g of amorphous hard carbon having a host structure and 0.1 g of titania (TiO2) were used. The carbon material manufactured in Comparative Example 4 was coated with titania (TiO2) at approximately 0.3 wt% of the total weight of the carbon material.

[0294]

[0295] Comparative Example 1

[0296] A negative electrode was manufactured using the same method as Example 1, except that only black carbon was used without the process of mixing a lithium-friendly material.

[0297] Specifically, black carbon and binder were added to NMP at a mixing ratio of 9.5:0.5, and then mixed to prepare a cathode slurry.

[0298] The above negative electrode slurry was applied to a negative electrode current collector to form a negative electrode coating layer, and then drying was performed at 80°C for 10 hours to manufacture a negative electrode having a carbon layer of about 30 μm thickness formed on the negative electrode current collector.

[0299]

[0300] Comparative Example 2

[0301] A negative electrode was manufactured using the same method as Example 1, except that only amorphous hard carbon having a host structure was used without a process of mixing a lithium-friendly material.

[0302] Specifically, hard carbon and binder were added to NMP at a mixing ratio of 9.5:0.5, and then mixed to prepare a cathode slurry.

[0303] The above negative electrode slurry was applied to a negative electrode current collector to form a negative electrode coating layer, and then drying was performed at 80°C for 10 hours to manufacture a negative electrode in which a negative electrode host layer with a thickness of about 30 μm was formed on the negative electrode current collector.

[0304]

[0305] Production Example 1: Manufacturing of a Lithium Metal Battery

[0306] (Polar electrode manufacturing)

[0307] Li 1.04 Ni 0.8 Co 0.15 Al 0.5O2A positive electrode active material slurry was prepared by uniformly mixing the powder and carbon conductive material (Super-P; Timcal Ltd.) at a weight ratio of 90:5, and then adding a PVDF (polyvinylidene fluoride) binder solution to obtain a weight ratio of active material:carbon conductive material:binder = 90:5:5.

[0308] The prepared slurry was coated on a 15 ㎛ thick aluminum substrate using a doctor blade. The coating layer was dried under reduced pressure at 120°C and then rolled using a roll press to produce a positive electrode in the form of a sheet.

[0309]

[0310] (Manufacturing of coin cells)

[0311] A polypropylene separator (Celgard 3510) was placed between the previously manufactured positive and negative electrodes (Examples and Comparative Examples), and a composition for forming a gel-polymer electrolyte was injected. Thermal cross-linking was performed in an oven at 70°C for 2 hours to manufacture a lithium metal battery containing the gel-polymer electrolyte. The lithium metal battery had a structure of positive electrode / gel-type polymer electrolyte (separator) / negative electrode current collector. The pores of the separator were filled with the gel-type polymer electrolyte.

[0312] A composition for forming a gel-polymer electrolyte can be prepared by mixing a crosslinking agent, dipentaerythritol hexaacrylate (DPHA), a liquid electrolyte, and a radical thermal initiator (t-Butylperoxy pivalate: t-BPP).

[0313] As a liquid electrolyte, a 42:58 weight ratio mixed solvent of diethyl carbonate (DEC) and fluoroethylene carbonate (FEC) was used, to which 0.6 M LiBF4 and 0.6 M LiDFOB (lithium difluoro(oxalate)borate) were added.

[0314]

[0315] Evaluation Example 1: Life Characteristics

[0316] A lithium metal battery was manufactured using the negative electrodes of the examples and comparative examples according to Manufacturing Example 1. The charge / discharge characteristics of the lithium metal battery were evaluated under the following conditions.

[0317] The battery was charged at a constant current of 0.1 C rate at 25°C until the voltage reached 4.2 V (vs. Li), and then cut-off was achieved at a current of 0.05 C rate while maintaining 4.2 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.1 C rate until the voltage reached 3.0 V (vs. Li) to perform a formation cycle.

[0318] The lithium metal battery, which had undergone a Mars cycle, was charged at a constant current of 0.2 C rate at 25°C until the voltage reached 4.2 V (vs. Li), and then cut-off at a current of 0.05 C rate while maintaining 4.2 V in constant voltage mode. Subsequently, the battery was discharged at a constant current of 0.2 C rate until the voltage reached 3.0 V (vs. Li) (1 st cycle). These cycles are 150 th The cycle was repeated under the same conditions.

[0319] In every charge / discharge cycle, a 10-minute pause was provided after each charge / discharge cycle.

[0320] The life evaluation is defined by Equation 1 below. The results of the room temperature charge-discharge experiment are shown in Table 1 below.

[0321] <Formula 1>

[0322] Life [cycle] = [discharge capacity / initial discharge capacity] × 100 is the number of cycles when the value reaches 80%.

[0323] Lifespan (SOH80%)Example 1121 cycles @80%Example 2109 cycles @80%Example 3102 cycles @80%Example 495 cycles @80%Example 590 cycles @80%Comparative Example 131 cycles @80%Comparative Example 265 cycles @80%

[0324] Referring to Table 1 above, it can be seen that the lithium metal battery manufactured in the example can have significantly improved life characteristics compared to the lithium metal battery manufactured in the comparative example.

[0325] The negative electrode of a lithium metal battery according to embodiments of the present invention can effectively suppress dendrites by depositing lithium into the pores beneath and within the carbon layer of a host structure to which a lithium-affinity material is applied. As a result, the lithium metal battery according to embodiments of the present invention can have improved life efficiency.

[0326]

[0327] Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the patent claims, the detailed description of the invention, and the attached drawings, and it is obvious that this also falls within the scope of the present invention.

Claims

1. Negative current collector; and Including a negative electrode host layer on the above negative electrode collector, The above negative host layer includes a carbon material and a coating layer on the surface of the carbon material, and the coating layer includes a lithium-affinity material. The above cathode host layer has a structure including a plurality of pores, Cathode for lithium metal batteries.

2. In paragraph 1, Further comprising a lithium electrodeposition layer between the negative electrode current collector and the negative electrode host layer, Cathode for lithium metal batteries.

3. In paragraph 1, The above negative host layer is configured such that lithium is deposited within the plurality of pores. Cathode for lithium metal batteries.

4. In paragraph 1, The above lithium-friendly material is: An inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and Comprising at least one organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI). Cathode for lithium metal batteries.

5. In paragraph 1, The above carbon material includes amorphous hard carbon, Cathode for lithium metal batteries.

6. In paragraph 1, The content of the lithium-friendly material is 0.5 wt% to 5 wt% of the total weight of the carbon material, Cathode for lithium metal batteries.

7. In paragraph 1, The thickness of the above cathode host layer is 1 ㎛ to 60 ㎛. Cathode for lithium metal batteries.

8. In paragraph 1, The above cathode host layer is, A structure further comprising a plurality of first frames in a first direction and a plurality of second frames in a second direction intersecting the first direction, The thickness of the above first frames is 1 nm to 50 nm, The height of the second frames is 1 nm to 50 nm, Cathode for lithium metal batteries.

9. In paragraph 1, The size of the above pores is 10 nm to 10 μm, Cathode for lithium metal batteries.

10. In paragraph 1, The porosity of the above cathode host layer is 40% to 80%, Cathode for lithium metal batteries.

11. Negative current collector; and Including a negative electrode host layer on the above negative electrode collector, The above negative host layer includes a carbon material and a lithium-affinity material doped into the carbon material, The above cathode host layer has a structure including a plurality of pores, Cathode for lithium metal batteries.

12. In paragraph 11, The above negative host layer comprises a covalent bond between atoms of the lithium-affinity material and carbon atoms of the carbon material. Cathode for lithium metal batteries.

13. In paragraph 11, Further comprising a lithium electrodeposition layer between the negative electrode current collector and the negative electrode host layer, Cathode for lithium metal batteries.

14. In paragraph 11, The above cathode host layer is, configured such that lithium is deposited within the plurality of pores; Cathode for lithium metal batteries.

15. In paragraph 11, The above lithium-friendly material is: An inorganic material selected from the group consisting of nitrogen (N), sulfur (S), phosphorus (P), silver (Ag), zinc (Zn), silicon (Si), tin (Sn), titania (TiO2), alumina (Al2O3), zirconia (ZrO2), and silicon carbide (SiC); and Comprising at least one organic material selected from the group consisting of polyvinylidene fluoride (PVdF) and polyimide (PI). Cathode for lithium metal batteries.

16. In paragraph 11, The content of the lithium-friendly material is 0.5 wt% to 5 wt% of the total weight of the carbon material, Cathode for lithium metal batteries.

17. In paragraph 11, The thickness of the above cathode host layer is 1 ㎛ to 60 ㎛, The above cathode host layer is, A structure further comprising a plurality of first frames in a first direction and a plurality of second frames in a second direction intersecting the first direction, The thickness of the above first frames is 1 nm to 50 nm, The height of the second frames is 1 nm to 50 nm, Cathode for lithium metal batteries.

18. In paragraph 11, The size of the above pores is 10 nm to 10 μm, The porosity of the above cathode host layer is 40% to 80%, Cathode for lithium metal batteries.

19. A cathode containing a cathode active material; A cathode according to any one of claims 1 to 10; and Comprising an electrolyte disposed between the positive and negative electrodes, Lithium metal battery.

20. In paragraph 19, The above positive electrode active material comprises a lithium composite oxide having a layered structure containing nickel. Lithium metal battery.

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