Centrifugal pressurizer for battery, and all-solid-state battery manufacturing method using same

Abstract

The present invention relates to a centrifugal pressurizing container, a centrifugal pressurizer comprising same, and an all-solid-state battery manufacturing method using same. More specifically, the centrifugal pressuring container comprises: a container body having an accommodation part formed on the inner surface of a sidewall thereof, the accommodation part having an electrode stack loaded thereon; and a fixing member for fixing the electrode stack, wherein the container body is formed such that pressure is applied to the accommodation part by rotation.

Description

Battery centrifugal pressurizer and method for manufacturing an all-solid-state battery using the same

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

[0002] Recent industrial demands have led to the active development of batteries with high energy density and safety. For example, lithium-ion batteries are being used not only in information and communication devices, but also in the automotive sector. Safety is particularly important in the automotive sector, as it is directly related to life.

[0003] All-solid-state batteries are being proposed, replacing the electrolyte with a solid electrolyte. By eliminating the use of flammable organic dispersion media, all-solid-state batteries can significantly reduce the risk of fire or explosion in the event of a short circuit.

[0004] The problem to be solved by the present invention is to provide a device and method capable of applying a high pressure of several hundred MPa to an electrode laminate for a long period of time.

[0005] Another problem that the present invention seeks to solve is to provide a device and method that can apply a high pressure of several hundred MPa to an electrode laminate for a long period of time without using a pressurizing medium such as water or oil.

[0006] A centrifugal pressurized vessel according to the concept of the present invention comprises a vessel body having a receiving portion formed on the inner side of a side wall, the receiving portion being configured to receive an electrode stack; and a fixing member configured to fix the electrode stack, wherein the vessel body can be configured to apply pressure to the receiving portion by rotation.

[0007] A centrifugal pressurizer according to another concept of the present invention may include: a rotor; a vacuum chamber configured to accommodate the rotor, the vacuum chamber configured to be able to control an internal pressure; a rotation driving unit configured to rotate the rotor; and a centrifugal pressurization vessel accommodated within the rotor. The centrifugal pressurization vessel may include: a vessel body having a receiving portion provided on an inner side wall thereof, the receiving portion configured to accommodate an electrode laminate; and a fixing member configured to fix the electrode laminate.

[0008] A method for manufacturing an all-solid-state battery according to another concept of the present invention includes applying centrifugal force to an electrode laminate to pressurize the electrode laminate, wherein the electrode laminate may include a positive electrode layer, a negative electrode layer facing the positive electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer.

[0009]

[0010] The centrifugal pressurizing vessel and the battery centrifugal pressurizing device including the same according to embodiments of the present invention can apply high pressures of several hundred MPa to the electrode laminate for an extended period of time. Furthermore, by applying uniform pressure to the electrode laminate, an all-solid-state battery with excellent interfacial adhesion can be manufactured.

[0011] The centrifugal pressurizing vessel and the battery centrifugal pressurizing device including the same according to embodiments of the present invention can prevent contamination of the electrode laminate by not using a pressurizing medium such as water or oil.

[0012] The method for manufacturing an all-solid-state battery according to embodiments of the present invention can manufacture an all-solid-state battery having excellent interfacial adhesion by applying centrifugal force to an electrode laminate using the above-described battery centrifugal pressurizer.

[0013] FIG. 1 is a cross-sectional view of an all-solid-state battery according to embodiments of the present invention.

[0014] Figure 2a is a schematic diagram of a battery centrifugal pressurizer according to embodiments of the present invention.

[0015] FIG. 2b is a cross-sectional view of a battery centrifugal pressurizer according to embodiments of the present invention.

[0016] FIG. 3 is a schematic diagram of a centrifugal pressurized vessel according to embodiments of the present invention.

[0017] FIGS. 4 and 5 are enlarged views of a receiving portion formed on the inner side of a side wall of a centrifugal pressurized vessel according to embodiments of the present invention.

[0018] FIG. 6 and FIG. 8 are conceptual diagrams for explaining a fixing member and an electrode laminate fixing method using the same according to embodiments of the present invention.

[0019] FIGS. 9 and 10 are conceptual diagrams for explaining the arrangement of receiving portions formed on the inner side of a side wall of a centrifugal pressurized vessel according to embodiments of the present invention.

[0020] Figures 11 to 13 are conceptual diagrams for explaining a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] As used herein, “combination thereof” may mean mixtures, laminates, composites, copolymers, alloys, blends, and reaction products of the components.

[0025] 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.

[0026]

[0027] All-solid-state batteries

[0028] FIG. 1 is a cross-sectional view illustrating an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 1, an all-solid-state battery (10) according to one embodiment of the present invention is illustrated. The all-solid-state battery (10) may include 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 present invention is not limited thereto, and 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).

[0029] The positive electrode layer (100) may include a positive electrode current collector (110) and a positive electrode active material layer (120) disposed on the positive electrode current collector (110). The positive electrode active material layer (120) may include a positive electrode active material, a solid electrolyte, a conductive material, and a binder.

[0030] The positive electrode current collector (110) can provide a reference surface on which the positive electrode active material layer (120) is arranged. The positive electrode current collector (110) can have a plate or foil shape. For example, the positive electrode current collector (110) can include 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.

[0031] Unlike that illustrated in FIG. 1, in one embodiment of the present invention, the positive electrode current collector (110) may be omitted. Although not illustrated, a carbon layer having a thickness of 0.1 μm to 4 μm may be additionally disposed between the positive electrode current collector (110) and the positive electrode active material layer (120) to increase the bonding strength between the positive electrode current collector (110) and the positive electrode active material layer (120).

[0032] The cathode active material may be a material that can reversibly absorb and desorb lithium ions. For example, the cathode active material may include, but is not limited to, 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, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide. The cathode active materials may be used alone or as a mixture of two or more thereof.

[0033] Lithium transition metal oxides include, 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 may be a compound represented by any one of Fe2(PO4)3(0≤f≤2), LiFePO4. In these compounds, the capital letter “A” is Ni, Co, Mn, or a combination thereof, the capital letter “B” is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof, the capital letter “D” is O, F, S, P, or a combination thereof, the capital letter “E” is Co, Mn, or a combination thereof, the capital letter “F” is F, S, P, or a combination thereof, the capital letter “G” is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof, the capital letter “Q” is Ti, Mo, Mn, or a combination thereof, the capital letter “I” is Cr, V, Fe, Sc, Y, or a combination thereof, and the capital letter “J” is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

[0034] 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 atomic layers and metal atomic layers are alternately and regularly arranged in a direction, and thereby each atomic layer forms a two-dimensional plane. The "cubic rock salt structure" refers to the sodium chloride type (NaCl type) structure, which is a type of crystal structure, and specifically refers to a structure in which the face-centered cubic lattice (fcc) formed by each cation and anion is arranged with a displacement of half of the ridge of the unit lattice. Lithium transition metal oxides having this layered rock salt structure include, for example, LiNi x Co y Al z O2(NCA) or LiNi x Co y Mnz O2(NCM) (0 <x<1,0<y<1, 0<z<1, x+y+z=1) 등의 삼원계 리튬전이금속산화물일 수 있다. 양극 활물질이 층상암염형 구조를 갖는 삼원계 리튬전이금속산화물을 포함하는 경우, 전고체 전지(10)의 에너지 밀도가 커지고 열안정성이 향상될 수 있다.

[0035] The above-described compound included in the positive electrode active material may be covered by a coating layer (not shown). The positive electrode active material may also be a mixture of the above-described compound and a compound to which a coating layer is added. Meanwhile, the coating layer added to the surface of the positive electrode active material may include, for example, an oxide, a hydroxide, an oxyhydroxide, an oxycarbonate, or a hydroxycarbonate of the coating elements below. The compound forming the coating layer may be 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 may be selected within a range that does not adversely affect the physical properties of the positive electrode active material. The method for forming the coating layer may include, for example, a spray coating method or an immersion method.

[0036] When the positive electrode active material includes nickel (Ni) as a ternary lithium transition metal oxide such as NCA or NCM, for example, the capacity density of the all-solid-state battery (10) can be increased, thereby reducing metal dissolution of the positive electrode active material in a charged state. As a result, the cycle characteristics of the all-solid-state battery (10) in a charged state can be improved. Meanwhile, the “cycle characteristics” are characteristics indicating the degree to which the all-solid-state battery (10) is deteriorated due to charge / discharge of the all-solid-state battery (10). An all-solid-state battery (10) with high cycle characteristics can have a small degree of deterioration of the all-solid-state battery (10) due to charge / discharge, and an all-solid-state battery (10) with low cycle characteristics can have a large degree of deterioration of the all-solid-state battery (10) due to charge / discharge.

[0037] The shape of the positive electrode active material may include particle shapes such as a sphere or an ellipsoid, for example. The particle size and content of the positive electrode active material are not particularly limited.

[0038] 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).

[0039] 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 It may be an argyrodite-type compound including at least one selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0040] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing (0≤a≤2, (0≤c≤2)), where X may be F, Br, Cl, or a combination thereof. M is 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. Can be.

[0041] 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.

[0042] The solid electrolyte included in the positive electrode active material layer (120) may have a smaller median particle size (D50) than the solid electrolyte included in the solid electrolyte layer (300). For example, the median 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 median particle size (D50) of the solid electrolyte included in the solid electrolyte layer (300). Meanwhile, the median particle size (D50) may be a median diameter measured using a laser particle size distribution meter.

[0043] The positive electrode active material layer (120) may include a conductive material. The conductive material may have conductivity without causing a chemical change in the all-solid-state battery (10), thereby increasing the conductivity of the positive electrode active material and the solid electrolyte. The conductive material may include a carbon-based material. The conductive material may include, for example, one or more selected from graphite, carbon black, acetylene black, carbon nanofibers, and carbon nanotubes.

[0044] The positive electrode active material layer (120) may further include a binder. The binder may include a material for binding the positive electrode active material, solid electrolyte, and conductive material included in the positive electrode active material layer (120) and improving bonding strength with the positive electrode current collector (110). For example, the binder may include polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, or polymethyl methacrylate.

[0045] 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 (120) may include 85 parts by weight to 92 parts by weight of the positive electrode active material. The positive electrode active material layer (120) may include 0.5 parts by weight to 1.5 parts by weight of the binder.

[0046] Within the positive electrode active material layer (120), 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 electrode active material layer (120) 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 thus a covering layer covering the surface of the solid electrolyte may not be properly formed.

[0047] According to embodiments, the positive electrode active material layer (120) may further include at least one additive selected from the group consisting of a filler, a coating agent, a dispersant, and an ion conductive auxiliary agent in addition to the above-described positive electrode active material, solid electrolyte, conductive agent, and binder.

[0048] The solid electrolyte layer (300) is disposed between the positive electrode layer (100) and the negative electrode layer (200) and may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. The solid electrolyte included in the solid electrolyte layer (300) may be the same as or different from any one of the materials that may be included in the solid electrolyte included in the positive electrode active material layer (120) described above.

[0049] The solid electrolyte layer (300) of one embodiment may include a sulfide-based solid electrolyte. The sulfide-based solid electrolyte may be manufactured by treating starting materials such as Li2S and P2S5 by a melting rapid cooling method or a mechanical milling method. In addition, a heat treatment may be performed after the treatment. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. In addition, the solid electrolyte may include, for example, at least sulfur (S), phosphorus (P), and lithium (Li) as constituent elements among the above-described sulfide-based solid electrolyte materials. For example, the solid electrolyte may be a material including Li2S-P2S5. When using a sulfide-based solid electrolyte material including Li2S-P2S5 to form the solid electrolyte, the mixing molar ratio of Li2S and P2S5 is, for example, in the range of Li2S:P2S5=50:50 to 90:10.

[0050] 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 It may be an argyrodite-type compound including at least one selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0051] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing (0≤a≤2, (0≤c≤2)), where X may be F, Br, Cl, or a combination thereof. M is 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. Can be.

[0052] The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. When 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 is, for example, 15 GPa to 35 GPa.

[0053] The solid electrolyte layer (300) may further include a binder. The binder in the solid electrolyte layer (300) may be, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited thereto. The binder of the solid electrolyte layer (300) may be the same as or different from the binder included in the positive electrode active material layer (120) or the binder included in the negative electrode coating layer (220).

[0054] The negative electrode layer (200) may include a negative electrode current collector (210) and a negative electrode coating layer (220) on the negative electrode current collector (210). The negative electrode current collector (210) may provide a reference surface on which the negative electrode coating layer (220) is disposed. The negative electrode current collector (210) may include, for example, a material that does not react with lithium, i.e., does not form an alloy or a compound with lithium. For example, the negative electrode current collector (210) may include at least one metal selected from the group consisting of copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni). The thickness of the negative electrode current collector (210) may be 1 μm to 20 μm, more specifically 5 μm to 15 μm, and more specifically 7 μm to 10 μm.

[0055] The negative electrode current collector (210) may be composed of one of the above-described metals, or may include an alloy or coating material of two or more metals. The negative electrode current collector (210) may have, for example, a plate shape or a foil shape. Meanwhile, in one embodiment, the negative electrode current collector (210) may be omitted.

[0056] The negative electrode coating layer (220) can allow lithium metal to grow between it and the negative electrode current collector (210) when the all-solid-state battery (10) is charged. The negative electrode coating layer (220) can act as a protective layer for the lithium metal and simultaneously suppress the precipitation and growth of lithium dendrites.

[0057] The cathode coating layer (220) may include a metal and carbon. For example, the cathode coating layer (220) may include at least one metal selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn). The cathode coating layer (220) may include at least one carbon selected from the group consisting of carbon black, acetylene black, furnace black, ketjen black, and graphene. In one embodiment, the cathode coating layer (220) may include a mixture of carbon black and silver (Ag).

[0058] The cathode coating layer (220) may further include additives other than metal and carbon. The cathode coating layer (220) may further include, for example, at least one additive selected from the group consisting of a binder, a filler, a coating agent, a dispersant, and an ion conductive additive.

[0059] The negative electrode coating layer (220) may have a smaller thickness than 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 um to 20 um, 2 um to 10 um, or 3 um to 7 um. If the thickness of the negative electrode coating layer (220) is too 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 deteriorating the cycle characteristics of the all-solid-state battery (10). If the thickness of the cathode coating layer (220) increases excessively, the energy density of the all-solid-state battery (10) may decrease and the internal resistance of the all-solid-state battery (10) due to the cathode coating layer (220) may increase, thereby deteriorating the cycle characteristics of the all-solid-state battery (10).

[0060] Meanwhile, although not shown, a carbon layer may be further included to improve adhesion between the cathode coating layer (220) and the solid electrolyte layer (300).

[0061] In one embodiment, the width (or widths) of the anode layer (100) may be smaller than the width (or widths) of the cathode layer (200). For example, the anode layer (100) may have a first width (W1) in a first direction (D1), and the cathode layer (200) may have a second width (W2) in the first direction (D1). The first width (W1) may be smaller than the second width (W2). Since the first width (W1) is smaller than the second width (W2), a gasket may be further provided around the perimeter of the anode layer (100) to compensate for this.

[0062] In another embodiment, although not shown, the width (or widths) of the anode layer (100) may be substantially the same as the width (or widths) of the cathode layer (200). For example, the first width (W1) of the anode layer (100) and the second width (W2) of the cathode layer (200) may be substantially the same.

[0063] According to embodiments of the present invention, the solid electrolyte layer (300) may include a positive electrode electrolyte layer (300a) and a negative electrode electrolyte layer (300b). The positive electrode electrolyte layer (300a) and the negative electrode electrolyte layer (300b) may be laminated to form a single solid electrolyte layer (300). The positive electrode electrolyte layer (300a) may be in contact with the positive electrode active material layer (120), and the negative electrode electrolyte layer (300b) may be in contact with the negative electrode coating layer (220).

[0064] For example, the positive electrode electrolyte layer (300a) and the negative electrode electrolyte layer (300b) may include solid electrolytes having the same composition. As another example, the positive electrode electrolyte layer (300a) and the negative electrode electrolyte layer (300b) may include solid electrolytes having different compositions.

[0065] The positive electrolyte layer (300a) may have a first width (W1), and the negative electrolyte layer (300b) may have a second width (W2).

[0066] In one embodiment, the width (or widths) of the positive electrolyte layer (300a) may be smaller than the width (or widths) of the negative electrolyte layer (300b). The first width (W1) of the positive electrolyte layer (300a) may be smaller than the second width (W2) of the negative electrolyte layer (300b).

[0067] Referring back to FIG. 1, the all-solid-state battery (10) may have a shape in which a second electrode (ETL2) is laminated on a first electrode (ETL1).

[0068] In one embodiment, the first electrode (ETL1) may include a cathode layer (200) and a cathode electrolyte layer (300b) on the cathode layer (200). The second electrode (ETL2) may include a cathode layer (100) and a cathode electrolyte layer (300a) on the cathode layer (100). The second electrode (ETL2) may be laminated on the first electrode (ETL1) such that the cathode electrolyte layer (300b) of the first electrode (ETL1) and the anode electrolyte layer of the second electrode (ETL2) face each other.

[0069] In one embodiment, a first electrode (ETL1) may be formed by stacking a cathode electrolyte layer (300b) on a cathode layer (200). A second electrode (ETL2) may be formed by stacking a cathode electrolyte layer (300a) on a cathode layer (100). In addition, by pressing the first electrode (ETL1), the interface between the cathode layer (200) and the cathode electrolyte layer (300b) may be activated, and by pressing the second electrode (ETL2), the interface between the cathode layer (100) and the cathode electrolyte layer (300a) may be activated. The pressing may be performed using a centrifugal pressurizer described below.

[0070]

[0071] Hereinafter, the centrifugal pressurizer of the present invention will be described in more detail with reference to FIGS. 5 to 10.

[0072] battery centrifugal pressurizer

[0073] FIG. 2A is a schematic diagram illustrating a centrifugal pressurizer according to embodiments of the present invention. FIG. 2B is a cross-sectional diagram illustrating a centrifugal pressurizer according to embodiments of the present invention. Referring to FIGS. 2A and 2B, a centrifugal pressurizer (CCP) may include a vacuum chamber (VAC); a rotor (ROT); a rotation drive unit (RDU) configured to rotate the rotor (ROT); and a centrifugal pressurization vessel (CPC).

[0074] A vacuum chamber (VAC) may be configured to accommodate a rotor (ROT). An opening may be formed on one side of the vacuum chamber (VAC), and the rotor (ROT) may be accommodated through the opening. The vacuum chamber (VAC) may include a chamber cover covering the opening.

[0075] Additionally, the vacuum chamber (VAC) may be configured to form and maintain an internal vacuum state. In one embodiment, the vacuum chamber (VAC) may include a gas exhaust port. Through the gas exhaust port, gas within the vacuum chamber (VAC) may be exhausted outside the vacuum chamber (VAC).

[0076] In one embodiment, the centrifugal pressurizer (CCP) may further include a vacuum pump. The vacuum pump may suck gas inside the vacuum chamber (VAC) through a gas outlet of the vacuum chamber (VAC). The gas outlet of the vacuum chamber (VAC) may be connected to the vacuum pump. By maintaining a vacuum state inside the vacuum chamber (VAC), high-speed rotation of the rotor (ROT), described below, can be achieved.

[0077] The rotor (ROT) may be configured to accommodate a centrifugal pressurization vessel (CPC). In one embodiment, an opening may be formed on one side of the rotor (ROT), and the centrifugal pressurization vessel (CPC) may be accommodated through the opening.

[0078] In addition, the rotor (ROT) may be configured to rotate by power transmitted from a rotational drive unit (RDU) described later. In one embodiment, the rotor (ROT) may include a rotational drive shaft (RDS). The rotational drive shaft (RDS) may transmit rotational power from the rotational drive unit (RDU) described later to the rotor (ROT). Through this, the rotor (ROT) receiving the rotational power and the centrifugal pressurization vessel (CPC) accommodated therein may rotate together. As the centrifugal pressurization vessel (CPC) rotates, a centrifugal force may be applied to the electrode stack (ETS) accommodated therein.

[0079] A rotary drive unit (RDU) can be configured to rotate a rotor (ROT).

[0080] In one embodiment, the rotary drive unit (RDU) may include a stationary part that is fixed to a vacuum chamber (VAC) and a rotary part that rotates a rotor.

[0081] The rotary drive unit (RDU) can generate rotational power and transmit it to the rotational drive shaft of the rotor (ROT).

[0082] In one embodiment, the rotary drive unit (RDU) may include a servo motor. The servo motor can be used to precisely control the rotational speed of the rotor, thereby applying a constant centrifugal force to the electrode stack (ETS) housed within the centrifugal pressurization vessel (CPC).

[0083] A centrifugal pressurized vessel (CPC) can be configured to accommodate an electrode stack (ETS).

[0084] In one embodiment, the electrode stack (ETS) may include 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), as described above with reference to FIG. 1.

[0085] In another embodiment, the electrode stack (ETS) may be the first electrode (ETL1) or the second electrode (ETL2) described above with reference to FIG. 1.

[0086] In one embodiment, although not shown, the cell centrifugal pressurizer (CCP) may further include a heating unit. The heating unit may be configured to heat the interior of the cell centrifugal pressurizer (CCP). This may further activate the electrode stack (ETS) interface.

[0087] As the above-described rotor (ROT) rotates, a constant centrifugal force may be applied to the electrode stack (ETS) accommodated in the centrifugal pressurization vessel (CPC). Through this, the interfaces of the electrode stack (ETS) may be brought into close contact. Specifically, the interface of the negative electrode (200) and the negative electrode electrolyte layer (300b) may be brought into close contact, thereby increasing the interaction between the negative electrode layer (200) and the negative electrode electrolyte layer (300b). Similarly, the interface of the positive electrode layer (100) and the positive electrode electrolyte layer (300a) may be brought into close contact, thereby increasing the interaction between the positive electrode layer (100) and the positive electrode electrolyte layer (300a). In addition, the interfaces of the negative electrode electrolyte layer (300b) and the positive electrode electrolyte layer (300a) may be brought into close contact, thereby increasing the interaction between them.

[0088]

[0089] The centrifugal pressurized vessel is described in more detail with reference to FIGS. 3 to 8 below.

[0090] centrifugal pressurized vessel

[0091] FIG. 3 is a schematic diagram illustrating a centrifugal pressurization vessel according to embodiments of the present invention. Referring to FIG. 3, the centrifugal pressurization vessel (CPC) may include a container body (CAB). The container body (CAB) may have an opening formed on one side. In one embodiment, the centrifugal pressurization vessel (CPC) may further include a container cover (CAC) that covers the opening of the container body (CAB).

[0092] An electrode stack can be accommodated through an opening of a container body (CAB). A receiving portion (REP) for accommodating the electrode stack can be formed on the inner side of a side wall (SIW) of the container body (CAB).

[0093] Figures 4 and 5 are enlarged views illustrating a receiving portion (REP) formed on a side wall (SIW) of a container body (CAB). Referring to Figure 4, the receiving portion (REP) can be configured to allow an electrode stack (ETS) to be mounted thereon.

[0094] In one embodiment, the electrode stack (ETS) may include 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), as described above with reference to FIG. 1.

[0095] In another embodiment, the electrode stack (ETS) may be the first electrode (ETL1) or the second electrode (ETL2) described above with reference to FIG. 1. 333

[0096] In one embodiment, the area of ​​the receptacle (REP) may be substantially equal to or greater than the area of ​​the electrode stack (ETS) being accommodated.

[0097] In one embodiment, a plurality of receiving portions (REP) may be formed on the inner surface of the side wall (SIW) of the container body (CAB).

[0098] In one embodiment, the receiving portion (REP) may include a flat portion to allow the electrode stack (ETS) to be stably seated.

[0099] In one embodiment, referring to FIG. 5, the receiving portion (REP) may be recessed to receive at least a portion of the electrode stack (ETS). For example, the thickness of the electrode stack (ETS) received in the receiving portion (REP) may be less than the total thickness of the electrode stack (ETS). Alternatively, the depth of the recessed receiving portion (REP) may be greater than the thickness of the electrode stack (ETS), so that the electrode stack (ETS) may be completely received in the recessed receiving portion (REP).

[0100] The electrode stack (ETS) can be more stably positioned in the recessed receiving portion (REP).

[0101] The fixing member (FAS) may be configured to fix the electrode stack (ETS) mounted on the receiving portion (REP). FIGS. 6 to 8 are drawings for explaining the fixing member according to embodiments of the present invention. Referring to FIG. 6, the fixing member (FAS) may be a pouch. Referring to FIG. 7, the fixing member (FAS) may be a band. Referring to FIG. 8, the fixing member (FAS) may be a pair of tongs. One end of the fixing member (FAS) may be fixed to a side wall (SIW) of the container body (CAB). The fixing means for the side wall (SIW) of the fixing member (FAS) may include, but is not limited to, Velcro attachment, adhesive attachment, etc.

[0102] FIG. 9 and FIG. 10 are drawings for explaining the arrangement of the receiving portion (REP) according to embodiments of the present invention.

[0103] Referring to FIG. 9, the receiving portion (REP) may be provided parallel to the rotation axis (ax1) of the container body (CAB). In one embodiment, the container body (CAB) may have a prism shape. For example, the shape of the container body (CAB) may be a square prism, a pentagonal prism, a hexagonal prism, a heptagonal prism, an octagonal prism, etc.

[0104] Referring to FIG. 10, the receiving portion (REP) may be provided at an angle relative to the rotation axis (ax1) of the container body (CAB), so that the electrodes may be installed at an angle relative to the rotation axis (ax1) of the container body (CAB). For example, the distance between the receiving portion (REP) and the rotation axis (ax1) may increase from the top to the bottom of the container body (CAB). In one embodiment, the electrode stack (ETS) may be placed at the bottom of the container body (CAB) at a distance from the rotation axis (ax1). Through this, the magnitude of the maximum centrifugal force applied to the electrode stack (ETS) can be increased, and as a result, miniaturization of the centrifuge can be realized.

[0105] The container body (CAB) may be configured to apply pressure to the receiving portion (REP) by rotation.

[0106] The rotation axis (ax1) of the container body (CAB) can be aligned with the rotation axis of the rotor (ROT).

[0107] As an example, referring to FIG. 10, the container body (CAB) may have a truncated pyramid shape. For example, the shape of the container body (CAB) may be a square truncated pyramid, a pentagonal truncated pyramid, a hexagonal truncated pyramid, a heptagonal truncated pyramid, an octagonal truncated pyramid, etc.

[0108]

[0109] Hereinafter, a method for manufacturing an all-solid-state battery using the above-described battery centrifugal pressurizer will be described with reference to FIGS. 11 to 13.

[0110] All-solid-state battery manufacturing method

[0111] Figures 11 to 13 are drawings for explaining a method of centrifugally pressurizing an electrode stack (ETS).

[0112] A method for manufacturing an all-solid-state battery according to embodiments of the present invention may include applying a centrifugal force to an electrode stack (ETS).

[0113] As an example, referring to FIG. 11, the electrode stack (ETS) may include a positive electrode layer (100) described with reference to FIG. 1, 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).

[0114] In another embodiment, although not shown, the electrode stack (ETS) may be the first electrode (ETL1) or the second electrode (ETL2) described with reference to FIG. 1.

[0115] Applying centrifugal force to the electrode stack (ETS) may specifically include placing the electrode stack (ETS) in a battery centrifugal pressurizer (CCP) described with reference to FIGS. 2 to 10 and rotating it.

[0116] Referring to Fig. 11, the electrode stack (ETS) can be mounted in a receiving portion (REP) of a centrifugal pressurizing vessel (CPC) constituting a centrifugal pressurizer. The mounted electrode stack (ETS) can be fixed by a fixing member (FAS).

[0117] Referring to Fig. 12, a centrifugal pressurized vessel (CPC) containing an electrode stack (ETS) can apply centrifugal force to the electrode stack (ETS) by rotating. Specifically, the centrifugal pressurized vessel (CPC) can be placed in a rotor (ROT) and the rotor (ROT) can be rotated. The rotation axis (ax1) of the container body (CBD) of the centrifugal pressurized vessel (CPC) can be aligned with the rotation axis of the rotor (ROT). The rotor (ROT) can rotate by receiving rotational power from a rotation drive unit (RDU) within a vacuum chamber (VAC). The vacuum chamber (VAC) can control internal pressure by discharging internal gas to the outside. In addition, the vacuum chamber (VAC) can maintain a vacuum state. By rotating the rotor (ROT) in a vacuum state, high-speed rotation can be achieved, and thereby, a desired centrifugal force can be applied to the electrode stack (ETS).

[0118] The rotation speed (rpm) of the rotor (ROT) can be appropriately selected depending on the diameter of the rotor (ROT), the material, mass, thickness, etc. of the electrode stack (ETS). In one embodiment, the rotation speed (rpm) of the rotor (ROT) can be appropriately selected so as to apply a pressure of 100 MPa to 1000 MPa to the electrode stack (ETS).

[0119] In one embodiment, the rotational speed (rpm) of the rotor (ROT) can be appropriately selected so that a relative centrifugal force of 100,000 G to 1,000,000 G is applied to the electrode stack (ETS). In one embodiment, referring again to FIG. 12, the electrode stack (ETS) can be arranged parallel to the rotational axis (ax1) of the container body (CBD) and then rotated. Through this, uniform pressure can be applied to the entire area of ​​the electrode stack (ETS).

[0120] In another embodiment, referring to FIG. 13, the electrode stack (ETS) may be arranged at an angle relative to the rotational axis (ax1) of the container body (CBD) and then rotated. For example, the electrode stack (ETS) may be arranged at the bottom of the container body (CBD) so that it is configured to move away from the rotational axis (ax1) from the top to the bottom. Through this, the maximum centrifugal force applied to the electrode stack (ETS) can be increased even with a relatively small-sized device.

[0121]

[0122] In one embodiment, centrifugal pressurization can be performed in conjunction with heating. For example, heating can be performed simultaneously with centrifugal pressurization via a heating unit of a centrifugal pressurizer (CCP).

Claims

1. A container body having a receiving portion formed on the inner side wall, the receiving portion being configured to allow an electrode stack to be placed thereon; and Including a fixing member configured to fix the electrode laminate, A centrifugal pressurized container, wherein the container body is configured to apply pressure to the receiving portion by rotation.

2. In paragraph 1, A centrifugal pressurized vessel, wherein the receiving portion includes a flat portion for stably seating the electrode stack.

3. In paragraph 1, A centrifugal pressurized vessel, wherein the receiving portion is recessed to receive at least a portion of the electrode stack.

4. In paragraph 1, A centrifugal pressurized container, wherein the receiving portion is provided parallel to the rotation axis of the container body.

5. In paragraph 1, A centrifugal pressurized vessel, wherein the receiving portion is provided at an angle with respect to the rotation axis of the vessel body.

6. In paragraph 1, The above-mentioned container body is a centrifugal pressurized container having a prism or pyramidal shape.

7. In paragraph 1, The above-mentioned fixing member is a pouch, band or forceps, a centrifugal pressurized vessel.

8. In paragraph 1, The above electrode laminate is a centrifugal pressurized vessel, which is an electrode including a solid electrolyte layer or an all-solid-state battery including a solid electrolyte layer.

9. Rotor; A vacuum chamber configured to accommodate the rotor, the vacuum chamber being configured to control internal pressure; A rotation drive unit configured to rotate the rotor; and Including a centrifugal pressurized vessel accommodated within the rotor, The above centrifugal pressurized vessel: A container body having a receiving portion provided on the inner side of the side wall, the receiving portion being configured to allow an electrode stack to be seated thereon; and A battery centrifugal pressurizer comprising a fixing member configured to fix the electrode laminate.

10. In paragraph 9, A centrifugal pressurizer, wherein the vacuum chamber comprises a gas outlet.

11. In paragraph 9, A centrifugal pressurizer in which the above-mentioned receiving portion is provided in parallel with the rotation axis of the above-mentioned container body.

12. In paragraph 9, A centrifugal pressurizer in which the above-mentioned receiving portion is provided at an angle with respect to the rotation axis of the above-mentioned container body.

13. In paragraph 9, The above-mentioned container body is a centrifugal pressurizer having a prism or pyramidal shape.

14. In paragraph 9, A battery centrifugal pressurizer, wherein the electrode laminate is an electrode including a solid electrolyte layer or an all-solid-state battery including a solid electrolyte layer.

15. In paragraph 9, A centrifugal pressurizer further comprising a heating unit.

16. Including applying centrifugal force to the electrode stack to pressurize it, A method for manufacturing an all-solid-state battery, wherein the electrode laminate comprises a positive electrode layer, a negative electrode layer facing the positive electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer.

17. In paragraph 16, A method for manufacturing an all-solid-state battery, wherein the relative centrifugal force applied to the electrode laminate is 100,000 G to 1,000,000 G.

18. In paragraph 16, Applying centrifugal force to the above electrode stack: Fixing the electrode stack in a centrifugal pressurized vessel; and A method for manufacturing an all-solid-state battery, comprising rotating the centrifugal pressurized vessel.

19. In paragraph 18, A method for manufacturing an all-solid-state battery, wherein the electrode stack is provided parallel to the rotation axis of the centrifugal pressurized vessel.

20. In paragraph 18, A method for manufacturing an all-solid-state battery, wherein the electrode laminate is provided at an angle with respect to the rotation axis of the centrifugal pressurizing vessel.

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