Pressing device for electrode body

Abstract

The present invention relates to a pressing device for an electrode body. More specifically, the pressing device comprises: a vessel vertically extending, the vessel including an inner space for accommodating an object to be pressed; a heating jacket surrounding the vessel; an upper closure provided on an upper portion of the vessel to seal an upper portion of the inner space; a lower closure provided on a lower portion of the vessel to seal a lower portion of the inner space; a lower flange provided below the vessel; and a heating unit provided on a lower surface of the lower flange. The heating unit is configured to heat the lower portion of the inner space.

Description

Electrode body pressurizing device

[0001] The present invention relates to a pressurizing device for an electrode body, and more particularly, to a pressurizing device for an all-solid-state battery.

[0002]

[0003] Recent industrial demands have led to the active development of batteries with high energy density and safety. Recently, all-solid-state batteries, which replace the electrolyte with a solid electrolyte, have been proposed. All-solid-state batteries are made by laminating a cathode, a solid electrolyte, and an anode, then pressurizing and densifying them. These batteries utilize a solid electrolyte instead of the electrolyte found in conventional secondary batteries. By eliminating the use of flammable organic dispersion media, all-solid-state batteries significantly reduce the risk of fire or explosion in the event of a short circuit. Consequently, these all-solid-state batteries can exhibit high stability. These all-solid-state batteries can be manufactured using either wet isostatic pressing or dry pressing methods.

[0004]

[0005] The problem to be solved by the present invention is to provide a pressurizing device for an electrode body with improved process efficiency.

[0006]

[0007] According to the concept of the present invention, a pressurizing device may include a vessel extending vertically, the vessel including an internal space for accommodating a pressurized object; a heating jacket surrounding the vessel; an upper closure provided at an upper portion of the vessel to seal an upper portion of the internal space; a lower closure provided at a lower portion of the vessel to seal a lower portion of the internal space; a lower flange provided below the vessel; and a heating unit provided on a lower surface of the lower flange, wherein the heating unit may be configured to heat the lower portion of the internal space.

[0008] According to another concept of the present invention, a pressurizing device comprises a vessel extending vertically, the vessel including an internal space for accommodating a pressurized object; a heating jacket surrounding the vessel; an upper closure provided at an upper portion of the vessel to seal an upper portion of the internal space; a lower closure provided at a lower portion of the vessel to seal a lower portion of the internal space; and a heating unit provided below the vessel, wherein the heating unit may include: an outer wall; an inner wall disposed on an inner side of the outer wall; a bottom portion connected to the outer wall and the inner wall; a heating wire interposed between the outer wall and the inner wall; an air inlet penetrating the outer wall; and an air outlet provided at the bottom portion.

[0009]

[0010] The pressurizing device of the electrode body according to the present invention can substantially wet-compress the electrode body isotropically using a pressurizing medium. Here, a heating unit may be provided at the lower portion of the pressurizing device. The heating unit heats the lower portion of the pressurizing device, thereby improving the temperature difference between the upper pressurizing region and the lower pressurizing region. As the temperature is improved, the capacity of the pressurizing vessel can be increased. This allows for processing a large number of unit cells.

[0011]

[0012] FIG. 1 is a plan view of an all-solid-state battery according to embodiments of the present invention.

[0013] Figure 2 is a cross-sectional view taken along line A-A' of Figure 1.

[0014] FIG. 3 is a cross-sectional view taken along line A-A' of FIG. 1 to explain an all-solid-state battery according to another embodiment of the present invention.

[0015] Figures 4 and 5 are cross-sectional views showing a pressurizing device according to one embodiment of the present invention.

[0016] FIG. 6 is a perspective view illustrating a heating unit according to embodiments of the present invention.

[0017] FIG. 7 is a perspective view illustrating a heating unit according to embodiments of the present invention.

[0018] Figures 8 and 9 are drawings for explaining a pressurized object according to the present embodiment.

[0019]

[0020] 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.

[0021] 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.

[0022] Embodiments described herein will be described with reference to cross-sectional and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents. Accordingly, the regions illustrated in the drawings have a schematic nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific shapes of regions of the device and are not intended to limit the scope of the invention. Although terms such as first, second, and third are used to describe various components in various embodiments of the present specification, these components should not be limited by such terms. These terms are used only to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments thereof.

[0023] The terminology used herein is for the purpose of describing embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise. As used herein, the words "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[0024] 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.

[0025]

[0026] Fig. 1 is a plan view of an all-solid-state battery according to embodiments of the present invention. Fig. 2 is a cross-sectional view taken along line A-A' of Fig. 1.

[0027] Referring to FIGS. 1 and 2, the all-solid-state battery (10) according to the present invention 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).

[0028] A positive electrode layer (100) according to one embodiment of the present invention 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.

[0029] 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 include a plate or foil including, for example, 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.

[0030] Meanwhile, 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).

[0031] The positive electrode active material of the positive electrode active material layer (120) may include a material that can reversibly absorb and desorb lithium ions. The positive electrode active material may include a plurality of particles. The positive electrode active material may include, for example, lithium transition metal oxides such as lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganate, lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, but is not necessarily limited thereto. The positive electrode active materials may be each alone or may be a mixture of two or more types.

[0032] 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-cMn 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-fA 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.

[0033] 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 Mn zO2(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.

[0034] 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 is amorphous or crystalline. The coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. The coating layer may include, for example, Li2O-ZrO2 (LZO). The method for forming the coating layer is selected within a range that does not adversely affect the physical properties of the positive electrode active material. The method for forming the coating layer includes, for example, spray coating, dipping, etc.

[0035] 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 are improved. Meanwhile, the "cycle characteristics" are characteristics indicating the degree to which the all-solid-state battery (10) is deteriorated by charge / discharge of the all-solid-state battery (10). An all-solid-state battery (10) with high cycle characteristics may 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 may have a large degree of deterioration of the all-solid-state battery (10) due to charge / discharge.

[0036] The positive electrode active material may have a particle shape such as a sphere or an ellipsoid, for example. The particle size and content of the positive electrode active material are not particularly limited.

[0037] The solid electrolyte of the positive electrode active material layer (120) may have a particle shape. The solid electrolyte may be dispersed between the positive electrode active materials. 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).

[0038] 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-xPS 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.

[0039] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X c It 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.

[0040] 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.

[0041] The solid electrolyte in the positive electrode active material layer (120) may have a smaller average particle diameter than the first and second solid electrolytes in the solid electrolyte layer (300) described later. For example, the average particle diameter of the solid electrolyte in the positive electrode active material layer (120) may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the average particle diameter of the solid electrolyte in the solid electrolyte layer (300). Meanwhile, the average particle diameter may be a median diameter measured using a laser particle size distribution meter.

[0042] 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.

[0043] The positive electrode active material layer (120) may further include a binder. The binder may bind the positive electrode active material, the solid electrolyte, and the conductive material within the positive electrode active material layer (120) to each other. The binder may include a material for improving the bonding strength between the positive electrode active material layer (120) and the positive electrode current collector (110). The binder may include, for example, polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, and polymethyl methacrylate.

[0044] Based on 100 parts by weight of the total of the positive electrode active material, the solid electrolyte, the conductive material, and the binder, the positive electrode active material layer (120) may include 85 parts by weight or more and 92 parts by weight or less of the positive electrode active material. Based on 100 parts by weight of the total of the positive electrode active material, the solid electrolyte, the conductive material, and the binder, the positive electrode active material layer (120) may include 0.5 parts by weight or more and 1.5 parts by weight or less of the binder.

[0045] Based on 100 parts by weight of the solid electrolyte, the positive electrode active material layer (120) may include 1 part by weight or more and 50 parts by weight or less of a conductive material. If the conductive material is included in the positive electrode active material layer (120) in an amount of less than 1 part by weight based on 100 parts by weight of the solid electrolyte, the proportion of the conductive material may decrease, thereby lowering the electrical conductivity of the positive electrode active material layer (120). If the conductive material is included in the positive electrode active material layer (120) in an amount of more than 50 parts by weight based on 100 parts by weight of the solid electrolyte, the proportion of the conductive material may be excessively high, so that a covering layer covering the surface of the solid electrolyte may not be properly formed.

[0046] The positive electrode active material layer (120) may further include additives such as fillers, coating agents, dispersants, and ion conductive aids in addition to the above-described positive electrode active material, solid electrolyte, conductive agent, and binder.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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).

[0051] 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.

[0052] 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 cell.

[0053] 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).

[0054] A solid electrolyte layer (300) may be provided between the positive electrode layer (100) and the negative electrode layer (200). The solid electrolyte layer (300) may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. The solid electrolyte in the solid electrolyte layer (300) may be the same as or different from any one of the materials included in the solid electrolyte in the positive electrode active material layer (120) described above.

[0055] The solid electrolyte layer (300) may include a first solid electrolyte layer (310) and a second solid electrolyte layer (320). The first solid electrolyte layer (310) may be adjacent to the positive electrode layer (100), and the second solid electrolyte layer (320) may be adjacent to the negative electrode layer (200).

[0056] Referring to FIG. 2, the first solid electrolyte layer (310) may include a first solid electrolyte. The first solid electrolyte may have a particle shape such as a sphere or an ellipsoid. The first solid electrolyte may include a sulfide-based solid electrolyte. The first 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.

[0057] In one embodiment, the first solid electrolyte is Li 7-x PS 6-x Clx (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x The first solid electrolyte may include an argyrodite-type compound including at least one selected from (0≤x≤2). The first solid electrolyte may include an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0058] In another embodiment, the first solid electrolyte is Li 7-a M a PS 6-c X c Argyrodite-type compounds may include, wherein X may be Cl, Br, or a combination thereof. M may be Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, or a combination thereof. Each of a and c may be a real number between 0 and 2.

[0059] 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 first solid electrolyte is, for example, 15 GPa to 35 GPa.

[0060] The first solid electrolyte layer (310) may further include a binder. The binder included 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 first solid electrolyte layer (310) 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).

[0061] The second solid electrolyte layer (320) may include a second solid electrolyte. The second solid electrolyte may have a particle shape such as a sphere or ellipsoid.

[0062] The second solid electrolyte may include a sulfide-based solid electrolyte. The description of the second solid electrolyte may be the same as or similar to that described above for the first solid electrolyte. In one embodiment, the second solid electrolyte may have substantially the same composition as the first solid electrolyte. In another embodiment, the second solid electrolyte may have a similar composition to the first solid electrolyte.

[0063] The second solid electrolyte can be in direct contact with the negative electrode coating layer (220). As a result, the second solid electrolyte can suppress lithium dendrites formed between the negative electrode coating layer (220) and the negative electrode current collector (210). The second solid electrolyte can effectively suppress negative electrode side reactions. As a result, the cell performance of the all-solid-state battery (10) according to the present invention can be improved.

[0064] The first solid electrolyte layer (310) may have a first thickness (TK1), and the second solid electrolyte layer (320) may have a second thickness (TK2). The first thickness (TK1) and the second thickness (TK2) may be the same or different. In one embodiment, the first thickness (TK1) may be greater than the second thickness (TK2). For example, the first thickness (TK1) may be 1.1 to 5 times the second thickness (TK2).

[0065] Referring back to FIGS. 1 and 2, the positive electrode layer (100) and the first solid electrolyte layer (310) may form a positive electrode composite layer (CSH). The negative electrode layer (200) and the second solid electrolyte layer (320) may form a negative electrode composite layer (ASH). The positive electrode composite layer (CSH) may be laminated on the negative electrode composite layer (ASH).

[0066] The area of ​​the cathode composite layer (ASH) and the area of ​​the cathode composite layer (CSH) may be different. Specifically, the area of ​​the cathode composite layer (ASH) may be larger than that of the cathode composite layer (CSH). The cathode composite layer (CSH) may be completely overlapped within the cathode composite layer (ASH).

[0067] In one embodiment of the present invention, the first solid electrolyte layer (310) may have substantially the same area as the positive electrode layer (100). The second solid electrolyte layer (320) may have substantially the same area as the negative electrode layer (200).

[0068] Specifically, the positive electrode composite layer (CSH) may have a first width (WI1) in a first direction (D1). The negative electrode composite layer (ASH) may have a second width (WI2) in the first direction (D1). The first width (WI1) may be smaller than the second width (WI2). The positive electrode composite layer (CSH) may have a third width (WI3) in the second direction (D2). The negative electrode composite layer (ASH) may have a fourth width (WI4) in the second direction (D2). The third width (WI3) may be smaller than the fourth width (WI4).

[0069] The all-solid-state battery (10) according to the present embodiment can be manufactured by forming a negative electrode composite layer (ASH) on a first carrier film, forming a positive electrode composite layer (CSH) on a second carrier film, and then laminating the negative electrode composite layer (ASH) and the positive electrode composite layer (CSH).

[0070] FIG. 3 is a cross-sectional view taken along line A-A' of FIG. 1, illustrating an all-solid-state battery according to another embodiment of the present invention. In the embodiments described below, detailed descriptions of technical features overlapping with those previously described with reference to FIGS. 1 and 2 will be omitted, and differences will be described in detail.

[0071] Referring to FIG. 3, the all-solid-state battery (10) according to the present invention may further include a gasket (GSK). The gasket (GSK) may be provided to surround the cathode composite layer (CSH). The gasket (GSK) may fill the step on the side of the all-solid-state battery (10) caused by the difference in area between the anode composite layer (ASH) and the cathode composite layer (CSH). The gasket (GSK) may surround the four side surfaces of the cathode composite layer (CSH). For example, the thickness of the gasket (GSK) may be substantially the same as the thickness of the cathode composite layer (CSH).

[0072] The upper surface of the second solid electrolyte layer (320) may include a first region in contact with the first solid electrolyte layer (310) and a second region in contact with the gasket (GSK). The second region may be a peripheral region of the upper surface of the second solid electrolyte layer (320). The second region may surround the first region.

[0073]

[0074] Figures 4 and 5 are cross-sectional views showing a pressurizing device according to one embodiment of the present invention.

[0075] Referring to FIGS. 4 and 5, a pressurizing device (A) may be provided. The pressurizing device (A) may include a vessel (VSS), a heating jacket (HJ), an upper closure (CLS1), a lower closure (CLS2), a lower flange (UP), a lower wedge block (UWB), and a heating unit (HU).

[0076] The vessel (VSS) may have a cylindrical exterior. That is, the vessel (VSS) may extend vertically. The vessel (VSS) may include an interior space (IS) for accommodating a pressurized object. Here, a detailed description of the pressurized object accommodated in the interior space (IS) will be described later. The interior space (IS) may be filled with a pressurized medium (not shown) surrounding the pressurized object. For example, the pressurized medium may be water. The interior space (IS) may include a cylindrical empty space (ETS). The central axis of the empty space (ETS) may be parallel to the first direction (D1).

[0077] A heating jacket (HJ) can surround the vessel (VSS). For example, the heating jacket (HJ) can be bonded to the outer surface of the vessel (VSS). The heating jacket (HJ) can heat the vessel (VSS). That is, the heating jacket (HJ) can heat the vessel (VSS) and maintain a constant temperature.

[0078] An upper closure (CLS1) may be provided at the upper portion of the vessel (VSS). The upper closure (CLS1) may function as a cover that seals the upper portion of the vessel (VSS). For example, the upper closure (CLS1) may seal the upper portion of the internal space (IS).

[0079] A lower closure (CLS2) may be provided at the lower portion of the vessel (VSS). The lower closure (CLS2) may function as a cover that seals the lower portion of the vessel (VSS). For example, the lower closure (CLS2) may seal the lower portion of the internal space (IS). At least one of the upper closure (CLS1) and the lower closure (CLS2) may be configured to be openable.

[0080] A lower flange (UP) may be provided below the vessel (VSS). The lower flange (UP) may support the vessel (VSS). A portion of the upper surface of the lower flange (UP) may be joined to a portion of the lower surface of the vessel (VSS).

[0081] The lower wedge block (UWB) may be placed at the bottom of the heating unit (HU). The lower wedge block (UWB) may support the pressure transmitted to the upper closure (CLS1) and the lower closure (CLS2) together with a yoke (not shown) according to the increase in pressurized medium. The upper closure (CLS1) and the lower closure (CLS2) may perform the function of connecting a pipe supplying the pressurized medium to the internal space (IS).

[0082] A heating unit (HU) may be provided below the vessel (VSS). More specifically, the heating unit (HU) may be provided on the lower surface of the lower flange (UP). The heating unit (HU) may be configured to heat the lower closure (CLS2) and the lower portion of the lower flange (UP) (see FIG. 4) or the lower portion of the lower flange (UP) (see FIG. 5). A detailed description of the heating unit (HU) will be provided below.

[0083]

[0084] FIG. 6 is a perspective view illustrating a heating unit according to embodiments of the present invention.

[0085] Referring to Fig. 6, the heating unit (HU) can prevent heat loss in the internal space (IS) of the vessel (VSS). More specifically, the heating unit (HU) can prevent heat loss that occurs when the lower flange (UP) and the lower closure (CLS2) are exposed to the outside air at room temperature. The heating unit (HU) can include an outer wall (EW), an inner wall (IW), a bottom (FL), an air inlet (AI), a heating wire (HL), and an air outlet (AO).

[0086] The outer wall (EW) can be joined to the lower surface of the lower flange (UP). The upper surface of the outer wall (EW) can be joined to the lower surface of the lower flange (UP). The outer wall (EW) can include a slope. The inner wall (IW) can be arranged on the inner side of the outer wall (EW). The inner wall (IW) can also include a slope. The height of the inner wall (IW) can be lower than the height of the outer wall (EW). That is, the upper surface of the inner wall (IW) may not contact the upper surface of the lower flange (UP). The floor portion (FL) can be connected to the outer wall (EW) and the inner wall (IW). The floor portion (FL) can extend only partially toward the center. That is, the floor portion (FL) can have a space provided in the center. The space of the floor portion (FL) can be filled by a lower wedge block (UWB).

[0087] An air inlet (AI) may be provided in the outer wall (EW). More specifically, at least one air inlet (AI) may be provided on the outer side of the outer wall (EW). Air may be supplied through the air inlet (AI). The air inlet (AI) may be supplied with air by an air pump. A description of the air pump will be provided later. The air inlet (AI) may be configured to inject air into the space between the outer wall (EW) and the inner wall (IW). The air may be heated by contacting the heating wire (HL) and may flow through the inner wall (IW) while contacting the lower surface of the lower flange (UP) and the outer surface of the lower closure (CLS2). This increases the temperature of the lower closure (CLS2), thereby reducing the temperature difference between the lower closure (CLS2) and the pressurized medium.

[0088] A heating wire (HL) may be interposed between the outer wall (EW) and the inner wall (IW). The heating wire (HL) may be configured to heat air injected into the space between the outer wall (EW) and the inner wall (IW) through the air inlet (AI). For this purpose, the heating wire (HL) may be heated by an electrical heat source. A description of the electrical heat source will be provided below.

[0089] An air outlet (AO) may be provided at the bottom (FL). The air outlet (AO) may be configured to circulate heated air within the heating unit (HU). More specifically, the air outlet (AO) may discharge heated air while passing through the heating wire (HL). The air discharged through the air outlet (AO) may be connected and circulated to the air inlet (AI) via an air pump. As a result, the air may be circulated between the outer wall (EW) and the inner wall (IW).

[0090] Although not shown separately, an electric heat source, an air pump, and a control unit for heating and controlling the heating unit (HU) may be provided. The electric heat source may be connected to the heating wire (HL) to heat the heating wire (HL). The air pump may be configured to be connected to at least one of the air inlet (AI) and the air outlet (AO) to supply and circulate air. The control unit may be connected to the heating unit (HU) to set a desired temperature. In addition, the control unit may control the electric heat source through a temperature sensor measurement value to control the temperature and to reach and maintain the set value.

[0091]

[0092] Fig. 7 is a perspective view illustrating a heating unit according to embodiments of the present invention. In the embodiments described below, detailed descriptions of technical features that overlap with those previously described with reference to Fig. 5 will be omitted, and differences will be described in detail.

[0093] Referring to Fig. 7, the heating unit (HU) can heat the lower flange (UP) by directly contacting the lower surface of the lower flange (UP) through heat conduction. The heating unit (HU) can include a heating pad (HP) and a heating wire (HL).

[0094] The heating pad (HP) may be attached to the lower surface of the lower flange (UP). That is, the upper surface of the heating pad (HP) may be in contact with a portion of the lower surface of the lower flange (UP). The heating pad (HP) may have a ring shape with a central axis extending in the first direction. That is, the heating pad (HP) may be provided with an empty space on the inside. The empty space provided on the inside of the heating pad (HP) may be present to avoid interference with the lower closure (CLS2).

[0095] The heating wire (HL) may be embedded within the heating pad (HP). The heating wire (HL) may be configured to be heated within the heating pad (HP) and directly heat the lower flange (UP). For this purpose, the heating wire (HL) may be heated by an electrical heat source.

[0096] Although not shown separately, an electric heat source and a control unit for heating and controlling the heating unit (HU) may be provided. The electric heat source may be connected to the heating wire (HL) to heat the heating wire (HL). The control unit may be connected to the heating unit (HU) to set a desired temperature. In addition, the control unit may control the electric heat source through a temperature sensor measurement value to control the temperature, and may reach and maintain the set value.

[0097]

[0098] Figures 8 and 9 are drawings for explaining a pressurized object according to the present embodiment.

[0099] Hereinafter, the all-solid-state battery described with reference to FIGS. 1 to 3 above is referred to as an electrode body (10). The electrode body (10) may include not only the electrode plates constituting the all-solid-state battery described above, but also a laminated structure (SST) including at least one electrode plate. In other words, the electrode body (10) may collectively refer to electrode plates that require densification through a high-pressure pressurization process.

[0100] Referring to Fig. 8, a pressurized object may be provided. The pressurized object may include a laminated structure (SST) to be described later. The laminated structure (SST) to be described later may include a plurality of pressurized units (PSU). Hereinafter, one of the plurality of pressurized units (PSU) will be described with reference to Fig. 8. The die plate (DP) may provide a plurality of landing portions (LAD). The plurality of landing portions (LAD) may be on the same surface as the die plate (DP) or may be an area engraved in a third direction (D3) from the upper surface of the die plate (DP). The plurality of landing portions (LAD) may be configured so that an electrode body (10) to be described later may be mounted thereon.

[0101] The die plate (DP) can serve as a substrate for supporting the electrode body (10) to be described later. The die plate (DP) can be configured to stably support the electrode body (10) to be described later even under high pressure. The die plate (DP) can include a metal having sufficient rigidity to prevent bending and twisting of the electrode body (10) when a pressurizing process is performed on the electrode body (10). For example, the die plate (DP) can include a hard metal such as SUS (Steel Use Stainless).

[0102] An electrode body (10) may be provided on a plurality of landing portions (LADs) of a die plate (DP). In one embodiment, the electrode body (10) may include the negative electrode composite layer and the positive electrode composite layer described above (see FIG. 2). The negative electrode composite layer and the positive electrode composite layer may be laminated. The lower surface and upper surface of the electrode body (10) may be in direct contact with the upper surface and lower surface of the plurality of landing portions (LADs), respectively.

[0103] A fixing film (OFL) may be provided on the upper and lower surfaces of the electrode body (10). The fixing film (OFL) may directly cover the upper and lower surfaces of the electrode body (10) and the upper and lower surfaces of the die plate (DP). The fixing film (OFL) may fix the electrode body (10) so that it does not come off.

[0104] The fixing film (OFL) may be a film that fixes the electrode body (10) to the upper and lower surfaces of the die plate (DP). The fixing film (OFL) may be fixed to the die plate (DP) by a laminating method or the like. For example, the fixing film (OFL) may include a polymer material such as PE.

[0105] As described above, the die plate (DP), the electrode body (10), and the fixed film (OFL) can be sequentially laminated. The laminated die plate (DP), the electrode body (10), and the fixed film (OFL) can form a pressurizing unit (PSU).

[0106] Referring to FIG. 9, for example, the laminated structure (SST) may include a plurality of pressurized units (PSUs) stacked along a third direction. The plurality of stacked pressurized units (PSUs) may constitute the laminated structure (SST). The above-described laminated structure (SST) may be provided in multiple numbers.

[0107] Although not shown separately, a transfer basket may be provided. A plurality of stacked structures (SST) may be loaded into the transfer basket. In one embodiment, the plurality of stacked structures (SST) may be arranged in any configuration for optimal stacking when viewed in plan. The transfer basket may be configured to load the plurality of stacked structures (SST). The transfer basket may support the plurality of stacked structures (SST). In one embodiment, the transfer basket may be configured to have sufficient strength to support and transport the plurality of stacked structures (SST). For example, the transfer basket may comprise a metal such as stainless steel. The transfer basket into which the plurality of stacked structures (SST) are loaded may be provided in an empty space (ETS) of the vessel (VSS).

[0108] The pressurizing device according to the present embodiment may be provided with a heating unit at the bottom of the pressurizing device. By heating the lower flange of the pressurizing device using forced convection, the temperature difference between the upper pressurizing region and the lower pressurizing region can be improved. Furthermore, by directly contacting the lower flange of the pressurizing device and heating it using heat conduction, the temperature difference between the upper pressurizing region and the lower pressurizing region can be improved. By improving the temperature, the capacity of the pressurizing vessel can be increased. This allows for processing a large number of unit cells.

[0109] While embodiments of the present invention have been described with reference to the attached drawings, the present invention may be implemented in other specific forms without altering the technical spirit or essential features thereof. Therefore, it should be understood that the embodiments described above are exemplary in all respects and are not limiting.

Claims

1. A vertically extending vessel, said vessel including an internal space for accommodating a pressurized object; A heating jacket surrounding the vessel; An upper closure provided at the upper portion of the vessel to seal the upper portion of the internal space; A lower closure provided at the lower portion of the vessel to seal the lower portion of the internal space; a lower flange provided below the above vessel; and Including a heating unit provided on the lower surface of the lower flange, A pressurizing device, wherein the heating unit is configured to heat the lower portion of the internal space.

2. In paragraph 1, The above heating unit: outer wall; An inner wall placed on the inner side of the outer wall; A floor portion connected to the outer wall and the inner wall; A heating wire interposed between the outer wall and the inner wall; At least one air inlet provided on the outside of said outer wall; and A pressurizing device comprising an air outlet provided at the bottom portion.

3. In paragraph 1, The above heating unit: A heating pad attached to the lower surface of the lower flange; and A pressurizing device comprising a heating wire embedded in the above heating pad.

4. In paragraph 1, The above inner space is a pressurized device including a cylindrical empty space.

5. In paragraph 2, The heating unit further comprises a pressurizing device comprising an air pump connected to at least one air inlet.

6. In paragraph 1, A pressurizing device further comprising a lower wedge block disposed below the heating unit.

7. In paragraph 1, The above heating unit is a pressurized device including an electric heat source.

8. In paragraph 1, A pressurizing device in which the upper surface of the above heating unit is in contact with the lower surface of the above lower flange.

9. In paragraph 1, The above pressurized object includes a laminated structure, The above laminated structure is a pressurizing device including a plurality of pressurizing units.

10. In paragraph 9, The above plurality of pressurized units: A die plate providing multiple landing portions; An electrode body stacked above and below the die plate; and A pressurizing device including an outer body stacked above and below the electrode body.

11. In paragraph 10, A pressurizing device provided with a pouch for sealing each of the plurality of pressurizing units.

12. In paragraph 1, The above heating unit is a pressurizing device including a control unit.

13. In paragraph 1, A pressurizing device in which the internal space is filled with a pressurizing medium surrounding the pressurized object.

14. A vertically extending vessel, said vessel including an internal space for accommodating a pressurized object; A heating jacket surrounding the vessel; An upper closure provided at the upper portion of the vessel to seal the upper portion of the internal space; A lower closure provided at the lower portion of the vessel to seal the lower portion of the internal space; and Including a heating unit provided under the above vessel, The above heating unit: outer wall; An inner wall placed on the inner side of the outer wall; A floor portion connected to the outer wall and the inner wall; A heating wire interposed between the outer wall and the inner wall; an air inlet penetrating the outer wall; and A pressurizing device comprising an air outlet provided at the bottom portion.

15. In paragraph 14, The above air inlet is configured to inject air into the space between the outer wall and the inner wall, The above heating wire is configured to heat the injected air, A pressurizing device wherein the air outlet is configured to circulate the heated air within the heating unit.

16. In paragraph 14, A pressurizing device in which the internal space is filled with a pressurizing medium surrounding the pressurized object.

17. In paragraph 14, A pressurizing device further comprising a lower wedge block disposed below the heating unit.

18. In paragraph 14, The above heating unit is a pressurizing device including a control unit.

19. In paragraph 14, The heating unit further comprises a pressurizing device comprising an air pump connected to at least one air inlet.

20. In paragraph 14, The above pressurized object includes a laminated structure, The above laminated structure is a pressurizing device including a plurality of pressurizing units.

Images