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

Abstract

The present invention relates to a film for manufacturing an all-solid-state battery, and more specifically, comprises: a base film; a main film on top of the base film; and a protective film on top of the main film, wherein the base film includes a first adhesive surface to which the main film is adhered, the main film includes a second adhesive surface to which the protective film is adhered, and the second adhesive surface has greater adhesive strength than the first adhesive surface.

Description

Film for manufacturing all-solid-state batteries and method for manufacturing all-solid-state batteries using the same

[0001] The present invention relates to an all-solid-state battery manufacturing device and a method for manufacturing an all-solid-state battery using the same, and more specifically, to a multilayer film for transporting an all-solid-state battery cell.

[0002]

[0003] 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.

[0004] 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.

[0005]

[0006] The problem to be solved by the present invention is to provide a film for manufacturing an all-solid-state battery capable of selecting and removing cells with misalignment.

[0007] Another problem to be solved by the present invention is to provide a method for manufacturing an all-solid-state battery using the film for manufacturing an all-solid-state battery.

[0008]

[0009] A film for manufacturing an all-solid-state battery according to one embodiment of the present invention comprises: a base film; a main film on the base film; and a protective film on the main film, wherein the base film includes a first adhesive surface to which the main film is adhered; the main film includes a second adhesive surface to which the protective film is adhered; and the adhesive strength of the second adhesive surface may be greater than the adhesive strength of the first adhesive surface.

[0010] A method for manufacturing an all-solid-state battery according to another embodiment of the present invention may include: supplying a multilayer film including a base film and a main film on the base film; providing a monocell on the main film; checking for misalignment of the monocell on the main film; and cutting and removing a portion of the main film where the misaligned monocell is located.

[0011]

[0012] The film for manufacturing an all-solid-state battery according to the present invention can selectively remove only misaligned cells during cell transfer. This allows the manufacturing process for an all-solid-state battery to be performed efficiently.

[0013]

[0014] FIG. 1 is a cross-sectional view illustrating an all-solid-state battery according to embodiments of the present invention.

[0015] FIG. 2 is a perspective view showing a film for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0016] FIG. 3 and FIG. 4 are front views of films for manufacturing all-solid-state batteries according to embodiments of the present invention.

[0017] FIG. 5 is a drawing showing a plan view of a film for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0018] FIG. 6 is a plan view illustrating a portion of a main film among films for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0019] FIG. 7 is a front view of a film for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0020] FIG. 8 is a drawing showing a plan view of a film for manufacturing an all-solid-state battery according to one embodiment of the present invention.

[0021] FIGS. 9 to 11 are plan views of a film for manufacturing an all-solid-state battery step by step for removing misaligned cells according to embodiments of the present invention.

[0022] FIGS. 12A and 12B are plan views showing misalignment according to embodiments of the present invention.

[0023] FIG. 13a and FIG. 13b are conceptual diagrams illustrating removal of a main film according to embodiments of the present invention.

[0024] Figure 14 is a conceptual diagram for explaining an all-solid-state battery pressurization method according to embodiments of the present invention.

[0025] Figure 15 is a flowchart showing the sequence of a method for manufacturing an all-solid-state battery according to one embodiment of the present invention.

[0026]

[0027] 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.

[0028] 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.

[0029] 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.

[0030] As used herein, “combination thereof” may mean mixtures, laminates, composites, copolymers, alloys, blends, and reaction products of the components.

[0031]

[0032] FIG. 1 is a cross-sectional view illustrating an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 1, a mono-cell (MNC) of an all-solid-state battery according to one embodiment of the present invention is illustrated. The mono-cell (MNC) 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 mono-cell (MNC) 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). The mono-cell (MNC) may be a cell stack.

[0033] 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.

[0034] 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.

[0035] 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).

[0036] 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.

[0037] 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 Bb 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 Mr 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 Mr 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 b HAVE BEEN c G d O2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1), Li a Ni b Co c Mr 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 bO2(0.90≤a≤1, 0.001≤b≤0.1), Li a Mn2G b O4(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-f It 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.

[0038] The cathode active material may include, for example, a lithium salt of a transition metal oxide having a layered rock salt type structure among the lithium transition metal oxides described above. The "layered rock salt type structure" is, for example, a cubic rock salt type structure. <111> It is a structure in which oxygen 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 z 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, 모노셀(MNC)의 에너지 밀도가 커지고 열안정성이 향상될 수 있다.

[0039] 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.

[0040] When the positive electrode active material is a ternary lithium transition metal oxide such as NCA or NCM and contains nickel (Ni), it may be possible to increase the capacity density of the monocell (MNC) and reduce metal dissolution of the positive electrode active material in a charged state. As a result, the cycle characteristics of the monocell (MNC) in a charged state may be improved. Meanwhile, the “cycle characteristics” are characteristics indicating the degree to which the monocell (MNC) deteriorates due to charge / discharge of the monocell (MNC). A monocell (MNC) with high cycle characteristics may have a small degree of deterioration due to charge / discharge, and a monocell (MNC) with low cycle characteristics may have a large degree of deterioration due to charge / discharge.

[0041] 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.

[0042] 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).

[0043] 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.

[0044] Alternatively, the sulfide-based solid electrolyte is Li 7-a MaPS 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.

[0045] 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.

[0046] 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.

[0047] The positive electrode active material layer (120) may include a conductive material. The conductive material may be conductive without causing chemical changes in the mono-cell (MNC), thereby increasing the conductivity of the positive electrode active material and the solid electrolyte. The conductive material may include a carbon-based material. For example, the conductive material may include one or more selected from graphite, carbon black, acetylene black, carbon nanofibers, and carbon nanotubes.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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).

[0058] 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.

[0059] 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.

[0060] The negative electrode coating layer (220) can allow lithium metal to grow between the negative electrode current collector (210) and the monocell (MNC) when charging. The negative electrode coating layer (220) can act as a protective layer for the lithium metal and suppress the precipitation and growth of lithium dendrites.

[0061] 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).

[0062] 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.

[0063] 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 μm to 20 μm, 2 μm to 10 μm, or 3 μm to 7 μm. 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 monocell (MNC). If the thickness of the cathode coating layer (220) increases excessively, the energy density of the monocell (MNC) may decrease and the internal resistance of the monocell (MNC) due to the cathode coating layer (220) may increase, thereby deteriorating the cycle characteristics of the monocell (MNC).

[0064] 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).

[0065] According to embodiments of the present invention, the width (or width) of the anode layer (100) may be smaller than the width (or width) 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.

[0066] According to embodiments of the present invention, the solid electrolyte layer (300) may include a positive electrode solid electrolyte layer (300a) and a negative electrode solid electrolyte layer (300b). The positive electrode solid electrolyte layer (300a) and the negative electrode solid electrolyte layer (300b) may be laminated to form one solid electrolyte layer (300). The positive electrode solid electrolyte layer (300a) may be in contact with the positive electrode active material layer (120), and the negative electrode solid electrolyte layer (300b) may be in contact with the negative electrode coating layer (220).

[0067] For example, the positive electrode solid electrolyte layer (300a) and the negative electrode solid electrolyte layer (300b) may include solid electrolytes having the same composition. As another example, the positive electrode solid electrolyte layer (300a) and the negative electrode solid electrolyte layer (300b) may include solid electrolytes having different compositions.

[0068] The positive electrode solid electrolyte layer (300a) may have a first width (W1), and the negative electrode solid electrolyte layer (300b) may have a second width (W2). In other words, the width (or width) of the positive electrode solid electrolyte layer (300a) may be smaller than the width (or width) of the negative electrode solid electrolyte layer (300b). The first width (W1) of the positive electrode solid electrolyte layer (300a) may be smaller than the second width (W2) of the negative electrode solid electrolyte layer (300b). Since the first width (W1) of the positive electrode solid electrolyte layer (300a) is smaller than the second width (W2) of the negative electrode solid electrolyte layer (300b), a gasket may be further provided around the periphery of the positive electrode solid electrolyte layer (300a) to compensate for this.

[0069] Referring back to FIG. 1, the cathode layer (100) and the cathode solid electrolyte layer (300b) can constitute a first electrode layer (ETL1). The anode layer (100) and the anode solid electrolyte layer (300a) can constitute a second electrode layer (ETL2).

[0070]

[0071] FIG. 2 is a perspective view of a film for manufacturing an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 2, the film for manufacturing an all-solid-state battery may include a base film (BSF) and a main film (MNF) on the base film (BSF).

[0072] The main film (MNF) may include a plurality of cutting lines (CTLs), as illustrated in FIG. 2. The plurality of cutting lines (CTLs) may extend parallel to each other in a first direction (D1). In addition, the plurality of cutting lines (CTLs) may be arranged to be spaced apart from each other in a second direction (D2). The distance at which the plurality of cutting lines (CTLs) are spaced apart from each other may be greater than the width of the monocell (MNC). In other words, the plurality of cutting lines (CTLs) may be arranged to be spaced apart from each other so that the monocell (MNC) can be included. The width of the monocell (MNC) may refer to a short side of the monocell (MNC). The plurality of cutting lines (CTLs) may each be a cutting line or a pre-cut line. The cutting line or the pre-cut line may be for easily cutting the main film (MNF).

[0073] The width (MNFWD) of the main film may be greater than the width (BSFWD) of the base film. Referring to FIG. 2, the side of the base film (BSF) may protrude from the main film (MNF) in a direction parallel to the first direction (D1). This may be to facilitate the removal of only the main film (MNF).

[0074]

[0075] FIGS. 3 and 4 are front views of films for manufacturing all-solid-state batteries according to embodiments of the present invention. Referring to FIG. 3, the film for manufacturing all-solid-state batteries may include a base film (BSF), a main film (MNF), and a protective film (PTF). The base film (BSF) may include a first adhesive surface (ASD1), and the main film (MNF) may include a second adhesive surface (ASD2). A first adhesive (ADM1) may be applied onto the first adhesive surface (ASD1), and a second adhesive (ADM2) may be applied onto the second adhesive surface (ASD2).

[0076] The base film (BSF) may be a film for moving the monocell (MNC). The base film (BSF) may be a mother film. In addition, the base film (BSF) may be a moving film, but is not necessarily limited thereto. The base film (BSF) may be manufactured by including at least one of polyethylene terephthalate (PET), aluminum (Al), or stainless steel (SUS). The base film (BSF) may be wound by a roller and supplied as a film. At this time, the base film (BSF) may play a role in maintaining the main tension so that the film for manufacturing an all-solid-state battery located between a plurality of rollers does not wrinkle.

[0077] The base film (BSF) may include a first adhesive surface (ASD1). The first adhesive surface (ASD1) may be a surface where the base film (BSF) and the main film (MNF) come into contact, as illustrated in FIG. 3. The first adhesive surface (ASD1) may be an upper surface of the base film (BSF). In addition, the first adhesive surface (ASD1) may be a surface where the normal direction of the base film (BSF) is parallel to the third direction (D3).

[0078] The first adhesive surface (ASD1) may include a first adhesive (ADM1). The first adhesive (ADM1) may be applied to part or all of the first adhesive surface (ASD1). The first adhesive (ADM1) may be applied by spraying or by coating, but is not necessarily limited thereto.

[0079] The first adhesive (ADM1) may be used to fix the main film (MNF) on the base film (BSF). The first adhesive (ADM1) may serve to fix the main film (MNF). The first adhesive (ADM1) may include at least one selected from the group consisting of an acrylic adhesive, a silicone adhesive, and a rubber adhesive. The adhesive strength of the first adhesive (ADM1) may be 20 gf / 25 mm to 900 gf / 25 mm. The first adhesive (ADM1) may have a low-adhesion or release coating formed thereon. The adhesive strength of the first adhesive (ADM1) may be a value measured based on KS T 1028.

[0080] The main film (MNF) may be positioned on the base film (BSF). The main film (MNF) may be positioned on the first adhesive surface (ASD1). Additionally, the main film (MNF) may be positioned on the first adhesive (ADM1). The main film (MNF) may be in direct contact with the monocell (MNC).

[0081] The main film (MNF) may include a second adhesive surface (ASD2). The second adhesive surface (ASD2) may be a surface where the main film (MNF) and the protective film (PTF) come into contact, as illustrated in FIG. 3. The second adhesive surface (ASD2) may be an upper surface of the main film (MNF). In addition, the second adhesive surface (ASD2) may be a surface where the normal direction of the main film (MNF) is parallel to the third direction (D3).

[0082] The second adhesive surface (ASD2) may include a second adhesive (ADM2). The second adhesive (ADM2) may be applied to part or all of the second adhesive surface (ASD2). The second adhesive (ADM2) may be applied by spraying or by coating, but is not necessarily limited thereto.

[0083] The second adhesive (ADM2) may be used to fix the monocell (MNC) on the main film (MNF). The second adhesive (ADM2) may serve to fix the monocell (MNC). The second adhesive (ADM2) may include at least one selected from the group consisting of an acrylic adhesive, a silicone adhesive, and a rubber adhesive. The adhesive strength of the second adhesive (ADM2) may be 20 gf / 25 mm to 900 gf / 25 mm. The second adhesive (ADM2) may have a low-adhesion or release coating formed thereon. The adhesive strength of the second adhesive (ADM2) may be a value measured based on KS T 1028.

[0084] The adhesive strength of the second adhesive (ADM2) may be greater than that of the first adhesive (ADM1). The second adhesive (ADM2) may be for fixing the monocell. The adhesive strength of the first adhesive (ADM1) may only be required to be sufficient to fix the main film (MNF). If the adhesive strength of the second adhesive (ADM2) is less than that of the first adhesive (ADM1), the monocell (MNC) positioned on the main film (MNF) may not be easily fixed. In addition, if the adhesive strength of the second adhesive (ADM2) is less than that of the first adhesive (ADM1), the main film (MNF) may not be easily removed from the base film (BSF). The adhesive strength of the first adhesive (ADM1) may be the same as that of the first adhesive surface (ASD1). Additionally, the adhesive strength of the second adhesive (ADM2) may be the same as the adhesive strength of the second adhesive surface (ASD2).

[0085] The protective film (PTF) may be a film for protecting the main film (MNF). The protective film (PTF) may be positioned on the main film (MNF). The protective film (PTF) may be positioned on the second adhesive surface (ASD2). Additionally, the protective film (PTF) may be positioned on the second adhesive (ADM2). The protective film (PTF) may be a release film.

[0086] The base film (BSF), main film (MNF), and protective film (PTF) can be supplied in a rolled form. Additionally, the base film (BSF), main film (MNF), and protective film (PTF) can be composed of a flexible material.

[0087] FIG. 4 is a front view of a film for manufacturing an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 4, a base film (BSF) may be positioned at the lowermost portion of the film for manufacturing an all-solid-state battery. A first adhesive surface (ASD1) may be positioned on the base film (BSF). The base film (BSF) may include a first adhesive (ADM1). A main film (MNF) may be positioned on the base film (BSF). A second adhesive surface (ASD2) may be positioned on the main film (MNF). The main film (MNF) may include a second adhesive (ADM2). A protective film (PTF) may be positioned on the main film (MNF).

[0088]

[0089] FIG. 5 and FIG. 6 are plan views illustrating a main film (MNF) among films for manufacturing an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 5, the main film (MNF) may include a plurality of cutting lines (CTL), and each of the cutting lines (CTL) may be spaced apart from each other while maintaining a constant interval in the second direction (D2). The interval between the cutting lines (CTL) may be greater than the length of a short side of the monocell. FIG. 6 is a plan view illustrating a case where a portion of the main film (MNF) is removed. The main film (MNF) may be cut along the cutting lines (CTL). A portion of the main film (MNF) may be cut along adjacent cutting lines (CTL) among a plurality of cutting lines (CTL) formed on the main film (MNF). A portion of the main film (MNF) cut along adjacent cutting lines (CTL) may have the same shape as the main film (MNF) illustrated in FIG. 6.

[0090] When a portion of the main film (MNF) is cut along cut lines (CTL) that are spaced apart from each other, the portion of the cut main film (MNF) may be formed by a plurality of main films (MNF) as shown in FIG. 6. The portion of the main film (MNF) that is separated from the base film (BSF) may include a plurality of regions, and the plurality of regions may be simultaneously cut and separated from the base film (BSF). That is, when a plurality of misaligned cells (ERC) are adjacent to each other, some regions of the main film (MNF) where the misaligned cells (ERC) are located may be simultaneously cut.

[0091]

[0092] FIG. 7 is a front view of a film for manufacturing an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 7, the film for manufacturing an all-solid-state battery may have a main film (MNF) positioned on a base film (BSF) and a monocell (MNC) positioned on the main film (MNF). As illustrated in FIG. 7, the width (MNFWD) of the main film may be greater than the width (BSFWD) of the base film. This may be to easily remove the main film (MNF) by gripping a portion of the main film (MNFWD) that protrudes beyond the width (BSFWD) of the base film when removing a portion of the main film (MNF) to which an alignment error cell (ERC) is attached. When the width (MNFWD) of the main film is equal to or less than the width (BSFWD) of the base film, a main film tag portion (TGP) to be described later may be gripped to remove a portion of the main film (MNF).

[0093]

[0094] FIG. 8 is a plan view of a film for manufacturing an all-solid-state battery according to an embodiment of the present invention. Referring to FIG. 8, the main film (MNF) may further include tag portions (TGP) at both ends with respect to the first direction (D1). The tag portions (TGP) may be formed to more easily grip the main film (MNF) and thereby easily remove the main film (MNF) from the base film (BSF). The tag portions (TGP) may be formed at both ends of the main film (MNF) that are positioned opposite to each other in the first direction (D1), or may be formed only on a portion thereof. The shape of the tag portions (TGP) may be a rectangular shape as illustrated in FIG. 8, but is not necessarily limited thereto, and any shape that can grip the edge of the film may be included. The tag portions (TGP) may include the same material as the main film (MNF). Additionally, the tag portion (TGP) may include the same material as the base film (BSF) or the protective film (PTF). The tag portion (TGP) may be included in the main film (MNF) when the width (MNFWD) of the main film is equal to or smaller than the width (BSFWD) of the base film. Additionally, the tag portion (TGP) may be included in the main film (MNF) when the width (MNFWD) of the main film is greater than the width (BSFWD) of the base film.

[0095]

[0096] FIGS. 9 to 11 are plan views illustrating a film for manufacturing an all-solid-state battery in each step of removing an misaligned cell (ERC) according to embodiments of the present invention. An all-solid-state battery mono-cell (MNC) may be positioned on a main film (MNF). A plurality of mono-cells (MNC) positioned on the main film (MNF) may include a misaligned cell (ERC). Referring to FIG. 9, some of the films for manufacturing an all-solid-state battery arranged in a row are illustrated. Although FIG. 9 only illustrates a main film (MNF) including four mono-cells (MNC), a plurality of mono-cells (MNC) may be positioned on the main film (MNF).

[0097] As illustrated in FIG. 9, the monocell (MNC) may be positioned between the cut lines (CTL) of the main film (MNF). The term "between the cut lines (CTL)" may refer to the space between adjacent cut lines (CTL) among a plurality of spaced-apart cut lines (CTL). The monocell (MNC) may be provided and transported between adjacent cut lines (CTL) among the plurality of cut lines (CTL).

[0098] Referring to FIG. 9, one misaligned cell (ERC) among four monocells (MNC) located on the main film (MNF) can be identified. The misaligned cell (ERC) may be the second-to-last monocell (MNC) located based on the second direction (D2). The misaligned cell (ERC) may be located not parallel to a plurality of cut lines (CTL) based on the first direction (D1).

[0099] Fig. 10 is a plan view showing a state in which the main film (MNF) where the misaligned cell (ERC) is located is cut along an adjacent cutting line. The base film (BSF) may be exposed in the area where the main film (MNF) where the misaligned cell (ERC) is located has been removed. The exposed base film (BSF) may include a first adhesive surface (ASD1). In addition, the exposed base film (BSF) may also include a portion of the first adhesive (ADM1).

[0100] Figure 11 is a plan view showing a main film (MNF) with multiple misaligned cells (ERC) located cut along a cutting line.

[0101]

[0102] Figures 12a and 12b are plan views illustrating misalignment according to embodiments of the present invention. Figure 12a illustrates a monocell without misalignment, and Figure 12b illustrates a monocell (MNC) with misalignment.

[0103] Referring to FIG. 12a, a monocell (MNC) positioned on a main film (MNF) may include a virtual first axis (X1). The first axis (X1) may be an axis parallel to a first direction (D1). In addition, the first axis (X1) may be an axis parallel to a plurality of cutting lines (CTL) formed on the main film (MNF). The non-poor alignment of the monocell (MNC) may mean that the first axis (X1) of the monocell (MNC) is parallel to the first direction (D1). In addition, the non-poor alignment of the monocell may mean that the first axis (X1) of the monocell (MNC) is parallel to the plurality of cutting lines (CTL). In addition, the non-poor alignment of the monocell may mean that the first axis (X1) of the monocell (MNC) is perpendicular to the second direction and the third direction (D3) at the same time.

[0104] Referring to FIG. 12b, a monocell (MNC) positioned on a main film (MNF) may be positioned on the main film (MNF) with a first axis (X1) tilted. A misaligned cell (ERC) may include a virtual first axis (X1) and a virtual second axis (X2). The virtual first axis (X1) is the same axis as the first axis (X1) illustrated in FIG. 12a, and may be the same as the first axis (X1) when the alignment is not poor. That is, the second axis (X2) may exist only in the misaligned cell (ERC). The second axis (X2) may not be parallel to the first axis (X1). In addition, the second axis (X2) may not be parallel to the first direction (D1) or the plurality of cutting lines (CTL).

[0105] The degree of misalignment of a monocell can be expressed by the size of the alignment angle (ALA), which is the angle formed by the first axis (X1) and the second axis (X2). The alignment angle (ALA) may be an angle indicating the degree to which the first axis (X1) is tilted clockwise toward the second axis (X2). If the alignment angle (ALA) is 0°, the monocell (MNC) may be non-misaligned. On the other hand, if the alignment angle (ALA) is not 0°, the alignment may be referred to as an misaligned cell (ERC). A misaligned cell (ERC) according to embodiments of the present invention may mean a case where the alignment angle (ALA) is 1° or more. In addition, a misaligned cell (ERC) according to embodiments of the present invention may mean a case where the alignment angle (ALA) is 2° or more.

[0106]

[0107] FIG. 13A and FIG. 13B are conceptual diagrams illustrating the removal of a main film (MNF) according to embodiments of the present invention. The main film (MNF) can be held by a gripper (GRP). Additionally, it can be removed by a device that can hold an end of the main film (MNF) other than the gripper (GRP). When the width (MNFWD) of the main film is larger than the width (BSFWD) of the base film, the gripper (GRP) can hold the portion of the main film (MNF) that protrudes beyond the base film (BSF). On the other hand, when the width (MNFWD) of the main film is equal to or smaller than the width (BSFWD) of the base film, the gripper (GRP) can remove the main film (MNF) by holding the tag portion (TGP) formed on the main film (MNF).

[0108] Referring to Fig. 13b, a portion of the main film (MNF) gripped by the gripper (GRP) can be removed along the cutting line (CTL). When removing the main film (MNF), it can be removed by a single gripper (GRP) or by gripping both ends of the main film (MNF) with a plurality of grippers (GRP), but is not necessarily limited thereto. In addition, the main film (MNF) can be gripped by a plurality of grippers (GRP) to remove a plurality of misaligned cells (ERC).

[0109]

[0110] Figure 14 is a conceptual diagram illustrating a method for pressurizing an all-solid-state battery according to embodiments of the present invention. A monocell (MNC) supplied by a film for manufacturing an all-solid-state battery can be pressed by a pair of pressurizing rollers (RL).

[0111] The film for manufacturing an all-solid-state battery may be a multilayer film. That is, the multilayer film may include a base film (BSF) and a main film (MNF). The monocell positioned on the multilayer film may be pressed by a pair of press rollers (RL). The multilayer film and the monocell (MNC) may be pressed by the press rollers (RL).

[0112] The main film (MNF) on which the misaligned cells (ERC) are located can be removed before being fed to the pressure roller (RL). If the main film (MNF) on which the misaligned cells (ERC) are located is removed, only the base film (BSF) portion can be pressed by the pressure roller (RL). In other words, the base film (BSF) portion from which a portion of the main film (MNF) among the multilayer films is removed may not be pressed. This is because the distance between the pair of pressure rollers (RL) is greater than the thickness of the base film (BSF), so no pressure may be applied to the base film (BSF).

[0113]

[0114] FIG. 15 is a flowchart showing a method for manufacturing an all-solid-state battery according to embodiments of the present invention. Referring to FIG. 15, an all-solid-state battery can be manufactured by a manufacturing method including the steps of forming a cell stack by stacking a second electrode body on a first electrode body (S100), providing a cell stack on a main film (MNF) (S110), checking for misalignment of the cell stack located on the main film (MNF) (S120), cutting and removing a portion of the main film on which the misaligned cell (ERC) stack is located (S130), and pressing the cell stack and the multilayer film (S140). The cell stack may be the same as a monocell (MNC), or may be a bimonocell in the form of stacking not only a monocell (MNC) but also a monocell (MNC) and a monocell (MNC), but is not necessarily limited thereto. The cell stack may also mean a cell for an all-solid-state battery. Additionally, the first electrode body may be identical to the first electrode layer (ETL1), and the second electrode body may be identical to the second electrode layer (ETL2).

[0115]

[0116] The film for manufacturing an all-solid-state battery according to embodiments of the present invention, unlike conventional films for manufacturing all-solid-state batteries, includes multiple cut lines (CTLs) to selectively remove only misaligned cells (ERCs). This method for removing misaligned cells (ERCs) can simplify the all-solid-state battery manufacturing process, thereby increasing process efficiency.

[0117]

[0118] 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, the embodiments described above should be understood to be illustrative in all respects and not restrictive.

Claims

1. A base film; a main film on the base film; and a protective film on the main film, The base film includes a first adhesive surface to which the main film is adhered, The above main film includes a second adhesive surface to which the above protective film is adhered, A film for manufacturing an all-solid-state battery, wherein the adhesive strength of the second adhesive surface is greater than the adhesive strength of the first adhesive surface.

2. In paragraph 1, The above main film includes a plurality of cutting lines extending parallel to each other in the first direction, The above multiple cutting lines are arranged spaced apart from each other in the second direction, A film for manufacturing an all-solid-state battery, wherein each of the above plurality of cutting lines is a cutting line or a pre-cutting line.

3. In paragraph 1, A film for manufacturing an all-solid-state battery, wherein the width of the main film is greater than the width of the base film.

4. In paragraph 2, The width of the above main film is equal to or smaller than the width of the above base film, The above main film comprises two ends positioned opposite to each other in the first direction, The above film for manufacturing an all-solid-state battery further includes tag portions located at both ends.

5. In paragraph 1, The first adhesive surface includes a first adhesive, A film for manufacturing an all-solid-state battery, wherein the first adhesive comprises at least one selected from the group consisting of an acrylic adhesive, a silicone adhesive, and a rubber adhesive.

6. In paragraph 1, The second adhesive surface includes a second adhesive, A film for manufacturing an all-solid-state battery, wherein the second adhesive comprises at least one selected from the group consisting of an acrylic adhesive, a silicone adhesive, and a rubber adhesive.

7. In paragraph 5, A film for manufacturing an all-solid-state battery, wherein the first adhesive has an adhesive strength of 20 gf / 25 mm to 900 gf / 25 mm.

8. In paragraph 6, A film for manufacturing an all-solid-state battery, wherein the second adhesive has an adhesive strength of 20 gf / 25 mm to 900 gf / 25 mm.

9. In paragraph 1, A film for manufacturing an all-solid-state battery, wherein at least one of the base film or the main film comprises at least one of polyethylene terephthalate (PET), Al, or stainless steel (SUS).

10. Supplying a multilayer film including a base film and a main film on the base film; Providing a monocell on the above main film; Checking for misalignment of the monocell on the main film; and A method for manufacturing an all-solid-state battery, comprising cutting and removing a portion of the main film on which the misaligned monocell is located.

11. In paragraph 10, A method for manufacturing an all-solid-state battery, wherein the misalignment is confirmed by a difference of 2° or more in the alignment angle between the first axis located at the center of the monocell and the second axis located on the main film.

12. In paragraph 10, The above main film includes a plurality of cutting lines extending parallel to each other in the first direction, The above multiple cutting lines are arranged spaced apart from each other in the second direction, A method for manufacturing an all-solid-state battery, wherein each of the plurality of cutting lines is a cutting line or a pre-cutting line.

13. In paragraph 10, A method for manufacturing an all-solid-state battery, wherein the width of the main film is greater than the width of the base film.

14. In paragraph 12, A method for manufacturing an all-solid-state battery, wherein the above monocell is provided between adjacent cutting lines among the plurality of cutting lines.

15. In paragraph 12, A method for manufacturing an all-solid-state battery, wherein a portion of the main film on which the misaligned monocell is located is cut along the cutting lines and separated from the base film.

16. In paragraph 15, A portion of the main film separated from the base film includes a plurality of regions, A method for manufacturing an all-solid-state battery, wherein the plurality of regions are simultaneously cut out and separated from the base film.

17. In paragraph 10, A method for manufacturing an all-solid-state battery, wherein the first adhesive surface located on the upper surface of the main film has an adhesive force capable of fixing the monocell.

18. In paragraph 10, The above monocell comprises a first electrode layer and a second electrode layer, The first electrode layer includes a cathode layer and a cathode solid electrolyte layer, The second electrode layer includes an anode layer and an anode solid electrolyte layer, A method for manufacturing an all-solid-state battery, wherein the positive electrode solid electrolyte layer is laminated on the negative electrode solid electrolyte layer to form a solid electrolyte layer.

19. In paragraph 10, A method for manufacturing an all-solid-state battery, further comprising: line pressing the multilayer film; and the monocell on the multilayer film.

20. In paragraph 19, A method for manufacturing an all-solid-state battery, wherein, among the multilayer films, a portion of the base film from which a portion of the main film has been removed is not pressurized.

Images