Adhesive film, all-solid-state battery comprising same, and method for manufacturing all-solid-state battery

Abstract

The present invention relates to an adhesive film, an all-solid-state battery comprising same, and a method for manufacturing the all-solid-state battery. More specifically, included is a network structure of first and second linear polymers, wherein the first linear polymer comprises a first main chain and at least one first side chain, the second linear polymer comprises a second main chain and at least one second side chain, and the first and second side chains are ionically bonded to each other.

Description

Adhesive film, all-solid-state battery including the same, and method for manufacturing an all-solid-state battery

[0001] The present invention relates to an adhesive film, an all-solid-state battery including the same, and a method for manufacturing an all-solid-state battery.

[0002] Recently, driven by industrial demands, the development of batteries with high energy density and safety is actively underway. For example, lithium-ion batteries are being commercialized not only in the fields of information and communication devices but also in the automotive sector. In the automotive sector, safety is considered particularly important because it is directly related to human life.

[0003] Recently, all-solid-state batteries in which liquid electrolytes are replaced with solid electrolytes have been proposed. By not using flammable organic dispersion media, all-solid-state batteries can significantly reduce the likelihood of fire or explosion in the event of a short circuit. Therefore, these all-solid-state batteries can offer significantly higher safety compared to lithium-ion batteries that use liquid electrolytes.

[0004] The problem that the present invention aims to solve is to provide an adhesive film capable of bonding the interfaces of different solid electrolyte layers and reducing voids within the interfaces.

[0005] Another problem that the present invention aims to solve is to provide an all-solid-state battery with improved performance (resistance, etc.) and a method for manufacturing the same.

[0006] An adhesive film according to one embodiment of the present invention comprises a network structure of a first linear polymer and a second linear polymer, wherein the first linear polymer comprises a first main chain and at least one first side chain represented by the following structural formula 1, and the second linear polymer comprises a second main chain and at least one second side chain represented by the following structural formula 2, and the first side chain and the second side chain may be ionically bonded to each other:

[0007] [Structural Formula 1]

[0008]

[0009] R1 and R2 are each independently hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and L1 is a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group.

[0010] [Structural Formula 2]

[0011]

[0012] The above R3 may be hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0013] A solid-state battery according to one embodiment of the present invention comprises a positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein the solid electrolyte layer comprises: a first solid electrolyte layer comprising first electrolyte particles; an adhesive film on the first solid electrolyte layer; and a second solid electrolyte layer on the adhesive film comprising second electrolyte particles, and the adhesive film may be the adhesive film described above.

[0014] A method for manufacturing an all-solid-state battery according to one embodiment of the present invention comprises: forming a negative electrode laminate by stacking and pressing a negative electrode layer and a first solid electrolyte layer; forming a positive electrode laminate by stacking and pressing a positive electrode layer and a second solid electrolyte layer; forming an adhesive film; and forming a composite by providing and pressing the adhesive film between the first solid electrolyte layer and the second solid electrolyte layer, wherein forming the adhesive film comprises: forming a mixture of the first linear polymer, the second linear polymer, and a solvent; forming the mixture into a film; and heat-treating the film-formed mixture, wherein the first linear polymer comprises a first main chain and at least one first side chain represented by the following structural formula 1, and the second linear polymer may comprise a second main chain and at least one second side chain represented by the following structural formula 2:

[0015] [Structural Formula 1]

[0016]

[0017] R1 and R2 are each independently hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and L1 is a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group.

[0018] [Structural Formula 2]

[0019]

[0020] The above R3 is hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0021] An adhesive film according to one embodiment of the present invention can bond the interfaces of different solid electrolyte layers and reduce voids within the interfaces.

[0022] The all-solid-state battery according to one embodiment of the present invention can have its performance (resistance, etc.) improved.

[0023] A method for manufacturing an all-solid-state battery according to one embodiment of the present invention can provide an all-solid-state battery with improved performance (resistance, etc.).

[0024] FIG. 1 is a cross-sectional view of an all-solid-state battery according to embodiments of the present invention.

[0025] FIG. 2 is a cross-sectional view of a solid electrolyte layer according to embodiments of the present invention.

[0026] Figure 3 is an enlarged view of the M region of Figure 2.

[0027] FIG. 4 is a schematic diagram illustrating a first linear polymer according to embodiments of the present invention.

[0028] FIG. 5 is a schematic diagram illustrating a second linear polymer according to embodiments of the present invention.

[0029] FIG. 6 is a flowchart illustrating a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0030] FIG. 7 is a schematic diagram illustrating step S100 of a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0031] FIG. 8 is a schematic diagram illustrating step S300 of a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0032] FIG. 9 is a flowchart illustrating step S500 of a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0033] FIGS. 10, FIGS. 11 and FIGS. 12 are schematic diagrams for explaining step S500 of a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0034] FIG. 13 is a schematic diagram illustrating step S900 of a method for manufacturing an all-solid-state battery according to embodiments of the present invention.

[0035] In order to fully understand the structure and effects of the present invention, preferred embodiments of the present invention are described with reference to the attached drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and various modifications can be made. The description of these embodiments is provided merely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention.

[0036] In this specification, when a component is described as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. Additionally, in the drawings, the thicknesses of the components are exaggerated for the effective description of the technical content. Throughout the specification, parts indicated by the same reference numeral represent the same components.

[0037] The embodiments described herein will be described with reference to cross-sectional and / or plan views, which are exemplary illustrations of the invention. In the drawings, the thicknesses of films and regions are exaggerated for effective description of the technical content. Accordingly, the regions illustrated in the drawings are schematic in nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific forms of regions of the device and are not intended to limit the scope of the invention. Although terms such as first, second, third, etc., have been used to describe various components in the various embodiments of this specification, these components should not be limited by such terms. These terms are used merely to distinguish one component from another. The embodiments described and illustrated herein also include their complementary embodiments.

[0038] The terms used herein are for describing the embodiments and are not intended to limit the invention. In this specification, the singular form includes the plural form unless specifically stated otherwise in the text. As used herein, 'comprises' and / or 'comprising' do not exclude the presence or addition of one or more other components to the mentioned components.

[0039]

[0040] FIG. 1 is a cross-sectional view of an all-solid-state battery (10) according to one embodiment of the present invention.

[0041] Referring to FIG. 1, an all-solid-state battery (10) according to one embodiment includes a positive electrode layer (100), a negative electrode layer (200) facing the positive electrode layer (100), and a solid electrolyte layer (300) disposed between the positive electrode layer (100) and the negative electrode layer (200). However, the all-solid-state battery (10) may further include an additional functional layer, such as an adhesion-enhancing layer, disposed between the positive electrode layer (100) and the solid electrolyte layer (300) or between the negative electrode layer (200) and the solid electrolyte layer (300).

[0042] An anode layer (100) of one embodiment includes an anode current collector (110) and an anode active material layer (120) disposed on the anode current collector (110). The anode active material layer (120) may include an anode active material, a solid electrolyte, a conductive material, and a binder.

[0043] The positive current collector (110) can provide a reference surface on which the positive active material layer (120) is placed. The positive current collector (110) may include, for example, a plate or foil comprising indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

[0044] Meanwhile, unlike as illustrated in FIG. 1, the positive current collector (110) may be omitted in one embodiment of the present invention. Although not illustrated, a carbon layer with a thickness of 0.1 μm to 4 μm may be further disposed between the positive current collector (110) and the positive active material layer (120) to increase the bonding strength between the positive current collector (110) and the positive active material layer (120).

[0045] The cathode active material is a material capable of reversibly absorbing and desorbing lithium ions. The cathode active material may include, for example, lithium transition metal oxides such as lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganate, and lithium iron phosphate, as well as nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide, but is not necessarily limited to these. Each cathode active material may be a single material or a mixture of two or more materials.

[0046] Lithium transition metal oxides are, for example, Li a A 1-b B b D2(0.90≤a≤1, 0≤b≤0.5), Li a E 1-b B b O 2-c D c (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05), LiE 2-b B b O 4-c D c (0≤b≤0.5, 0≤c≤0.05), Li a Ni 1-b-c Co b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Co b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Mn b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2), Li a Ni 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 Ni 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 Ni 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 bO2(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-f It is a compound represented by any one of Fe2(PO4)3 (0≤f≤2) or LiFePO4. In such compounds, the uppercase “A” is Ni, Co, Mn, or a combination thereof; the uppercase “B” is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; the uppercase “D” is O, F, S, P, or a combination thereof; the uppercase “E” is Co, Mn, or a combination thereof; the uppercase “F” is F, S, P, or a combination thereof; the uppercase “G” is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; the uppercase “Q” is Ti, Mo, Mn, or a combination thereof; the uppercase “I” is Cr, V, Fe, Sc, Y, or a combination thereof; and the uppercase “J” is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

[0047] The cathode active material may include, for example, a lithium salt of a transition metal oxide having a layered rock salt type structure among the lithium transition metal oxides described above. The "layered rock salt type structure" is, for example, a cubic rock salt type structure. <111> It is a structure in which oxygen and metal atomic layers are alternately and regularly arranged in a specific direction, thereby forming a two-dimensional plane for each atomic layer. The "cubic rock salt type structure" represents a sodium chloride (NaCl type) structure, which is a type of crystal structure; specifically, it exhibits a structure in which face-centered cubic lattices (fcc) formed by cations and anions, respectively, are offset from each other by half the ridge of the unit lattice. Lithium transition metal oxides having such a layered rock salt type structure are, 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. 양극활물질이 층상암염형 구조를 갖는 삼원계 리튬전이금속산화물을 포함하는 경우, 전고체 전지(10)의 에너지 밀도가 커지고 열안정성이 향상될 수 있다.

[0048] The aforementioned compound contained in the cathode active material may be covered by a coating layer (not shown). The cathode active material may also be a mixture of the aforementioned compound and the compound to which the coating layer is added. Meanwhile, the coating layer added to the surface of the cathode active material may include, for example, oxides, hydroxides, oxyhydroxides, oxycarbonates, or hydroxycarbonates of the following coating elements. The compounds forming this coating layer are amorphous or crystalline. The coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. The coating layer may include, for example, Li2O-ZrO2 (LZO). The method for forming the coating layer is selected within a range that does not adversely affect the physical properties of the cathode active material. The method for forming the coating layer is, for example, spray coating or immersion.

[0049] When the positive electrode active material is a ternary lithium transition metal oxide such as NCA or NCM and contains nickel (Ni), the capacity density of the all-solid-state battery (10) is increased, and the metal leaching of the positive electrode active material in the charged state can be reduced. As a result, the cycle characteristics of the all-solid-state battery (10) in the charged state are improved. Meanwhile, “cycle characteristics” is a characteristic that indicates the degree of deterioration of the all-solid-state battery (10) due to charging and discharging of the all-solid-state battery (10). An all-solid-state battery (10) with high cycle characteristics has a small degree of deterioration due to charging and discharging, while an all-solid-state battery (10) with low cycle characteristics may have a large degree of deterioration due to charging and discharging.

[0050] The shape of the cathode active material may include particle shapes such as spheres or ellipsoids. The particle size and content of the cathode active material are not particularly limited.

[0051] The solid electrolyte may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. Sulfide-based solid electrolytes include, for example, Li2S-P2S5, Li2S-P2S5-LiX (where X is a halogen element), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, and Li2S-P2S5-Z m S n (m, n are positive numbers, uppercase “Z” is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, uppercase “M” is one of P, Si, Ge, B, Al, Ga, In), Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may include at least one selected from (0≤x≤2).

[0052] Sulfide-based solid electrolytes are, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound comprising one or more selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0053] Alternatively, sulfide-based solid electrolytes are Li 7-a M a PS 6-c X c It may be an argyrodite-type compound containing (0≤a≤2, 0≤c≤2). Here, X may be F, Br, Cl, or a combination thereof. M can be scandium (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. there is.

[0054] The density of the azyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. By having a density of 1.5 g / cc or higher for the azyrodite-type solid electrolyte, the internal resistance of the all-solid-state battery is reduced, and defects such as penetration and short circuit of the solid electrolyte film due to lithium dendrite formation can be prevented. The elastic modulus of the solid electrolyte may be, for example, 15 GPa to 35 GPa.

[0055] The solid electrolyte included in the positive electrode active material layer (120) may have a smaller average particle size (D50) of intermediate particle size compared to the solid electrolyte included in the solid electrolyte layer (300). For example, the average particle size (D50) of the solid electrolyte included in the positive electrode active material layer (120) may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the average particle size (D50) of the solid electrolyte included in the solid electrolyte layer (300). Meanwhile, the average particle size (D50) may be a median diameter measured using a laser particle size distribution meter.

[0056] The positive electrode active material layer (120) may include a conductive material. The conductive material may have conductivity without causing chemical changes in the all-solid-state battery (10), thereby increasing the conductivity of the positive 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.

[0057] The positive active material layer (120) may further include a binder. The binder may include a material for bonding the positive active material, solid electrolyte, and conductive material included in the positive active material layer (120), and for improving the bonding strength with the positive current collector (110). The binder may include, for example, polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, and polymethyl methacrylate.

[0058] Based on 100 parts by weight of the total positive active material, solid electrolyte, conductive material, and binder, the positive active material layer (120) may contain 85 parts by weight or more and 92 parts by weight or less of the positive active material. Based on 100 parts by weight of the total positive active material, solid electrolyte, conductive material, and binder, the positive active material layer (120) may contain 0.5 parts by weight or more and 1.5 parts by weight or less of the binder.

[0059] Based on 100 parts by weight of solid electrolyte, the positive active material layer (120) may contain 1 part by weight or more and 50 parts by weight or less of a conductive material. If the conductive material is included in the positive active material layer (120) in an amount less than 1 part by weight based on 100 parts by weight of solid electrolyte, the proportion of the conductive material decreases, and the electrical conductivity of the positive active material layer (120) may decrease. If the conductive material is included in the positive active material layer (120) in an amount exceeding 50 parts by weight based on 100 parts by weight of solid electrolyte, the proportion of the conductive material is excessively high, and a coating layer covering the surface of the solid electrolyte may not be properly formed.

[0060] The positive active material layer (120) may further include additives such as fillers, coating agents, dispersants, and ion conductivity aids in addition to the positive active material, solid electrolyte, conductive material, and binder described above.

[0061] The solid electrolyte layer (300) is disposed between the anode layer (100) and the cathode layer (200) and includes a sulfide-based solid electrolyte with 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 can be included in the solid electrolyte included in the aforementioned anode active material layer (120).

[0062] The solid electrolyte layer (300) of one embodiment may include a sulfide-based solid electrolyte. The sulfide-based solid electrolyte may be manufactured by processing starting materials, such as Li2S or P2S5, by a melt quenching method or a mechanical milling method. Additionally, heat treatment may be performed after such processing. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. Furthermore, the solid electrolyte may include sulfur (S), phosphorus (P), and lithium (Li) as at least constituent elements among the sulfide-based solid electrolyte materials described above, for example. For example, the solid electrolyte may be a material containing Li2S-P2S5. When using a sulfide-based solid electrolyte material containing Li2S-P2S5 to form the solid electrolyte, the molar ratio of Li2S and P2S5 is, for example, in the range of Li2S : P2S5 = 50 : 50 to 90 : 10.

[0063] Sulfide-based solid electrolytes are, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound comprising one or more selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0064] Alternatively, sulfide-based solid electrolytes are Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing (0≤a≤2, 0≤c≤2). Here, X may be F, Br, Cl, or a combination thereof. M can be scandium (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. there is.

[0065] The density of the azyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. Since the azyrodite-type solid electrolyte has a density of 1.5 g / cc or higher, the internal resistance of the all-solid-state battery is reduced, and defects such as penetration and short circuit of the solid electrolyte film due to lithium dendrite formation can be prevented. The elastic modulus of the solid electrolyte is, for example, 15 GPa to 35 GPa.

[0066] The solid electrolyte layer (300) may further include a binder. The binder included in the solid electrolyte layer (300) is, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited to these. 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).

[0067] 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 placed. The negative electrode current collector (210) may include, for example, a material that does not react with lithium, that is, does not form any alloys or compounds with lithium. 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 about 10 μm. 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.

[0068] The negative current collector (210) may be composed of one of the metals described above, or may include an alloy of two or more metals or a coating material. The negative current collector (210) may, for example, have a plate-like or foil-like shape. Meanwhile, in one embodiment, the negative current collector (210) may be omitted.

[0069] The negative electrode layer (200) may further include a second electrode tab extending from one side of the negative electrode current collector (210). The second electrode tab may be welded to an electrode lead and connected to an external terminal. The electrode lead welded to the second electrode tab may be different from the electrode lead welded to the first electrode tab.

[0070] The negative electrode coating layer (220) can cause lithium metal to grow between the all-solid-state battery (10) and the negative electrode current collector (210) during charging. Alternatively, the negative electrode coating layer (220) can cause lithium metal to grow or form an alloy with lithium inside the all-solid-state battery (10) during charging. The negative electrode coating layer (220) can serve as a protective layer for lithium metal and simultaneously suppress the precipitation and growth of lithium dendrites.

[0071] The cathode coating layer (220) may include 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).

[0072] The cathode coating layer (220) may further include other additives in addition to metal and carbon. The cathode coating layer (220) may further include at least one additive selected from the group consisting of, for example, binders, fillers, coating agents, dispersants, and ion-conducting aids.

[0073] For example, the loading amount of the cathode coating layer (220) is 0.1 mg / cm² 2 Up to 5 mg / cm² 2 It could be.

[0074] The negative electrode coating layer (220) may have a smaller thickness compared to the positive electrode active material layer (120). The thickness of the negative electrode coating layer (220) may be, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, or 5% or less of the thickness of the positive electrode active material layer (120). The thickness of the negative electrode coating layer (220) may be, for example, 1 µm to 20 µm, 2 µm to 10 µm, or 3 µm to 7 µm. The thickness of the negative electrode coating layer (220) may be about 10 µm. If the thickness of the negative electrode coating layer (220) is excessively thin, lithium dendrites formed between the negative electrode coating layer (220) and the negative electrode current collector (210) may cause the negative electrode coating layer (220) to collapse, thereby degrading the cycle characteristics of the all-solid-state battery (10). If the thickness of the negative electrode coating layer (220) increases excessively, the energy density of the all-solid-state battery (10) decreases and the internal resistance of the all-solid-state battery (10) due to the negative electrode coating layer (220) increases, which may degrade the cycle characteristics of the all-solid-state battery (10).

[0075] 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).

[0076]

[0077] Referring to FIG. 1, the positive active material layer (120) may have a first width (WI1) in a first direction (D1). The negative coating layer (220) may have a second width (WI2) in a first direction (D1).

[0078] For example, the first width (WI1) of the positive active material layer (120) may be substantially the same as the second width (WI2) of the negative coating layer (220). In this specification, substantially the same width may be defined as the difference between the two widths being within 10%.

[0079] As another example, the first width (WI1) of the positive active material layer (120) may be smaller than the second width (WI2) of the negative coating layer (220).

[0080] Hereinafter, the solid electrolyte layer (300) of the present invention will be described in detail.

[0081]

[0082] solid electrolyte layer (300)

[0083] FIG. 2 is an enlarged view of a solid electrolyte layer (300) according to embodiments of the present invention.

[0084] Referring to FIGS. 1 and 2, the solid electrolyte layer (300) is disposed between the anode layer (100) and the cathode layer (200) and may include a first solid electrolyte layer (SEL1), an adhesive film (ADF), and a second solid electrolyte layer (SEL2).

[0085] The first solid electrolyte layer (SEL1) can be placed on the cathode coating layer (220).

[0086] The first solid electrolyte layer (SEL1) may include a first electrolyte particle (SE1). The first electrolyte particle (SE1) may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. The solid electrolyte included in the first solid electrolyte layer (SEL1) may be the same as or different from any one of the materials that may be included in the solid electrolyte included in the aforementioned positive electrode active material layer (120).

[0087] The first solid electrolyte layer (SEL1) of one embodiment may include a sulfide-based solid electrolyte. The sulfide-based solid electrolyte may be manufactured by processing starting materials, such as Li2S or P2S5, by a melt quenching method or a mechanical milling method. Additionally, heat treatment may be performed after such processing. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. Furthermore, the solid electrolyte may include sulfur (S), phosphorus (P), and lithium (Li) as at least constituent elements among the sulfide-based solid electrolyte materials described above, for example. For example, the solid electrolyte may be a material containing Li2S-P2S5. When using a sulfide-based solid electrolyte material containing Li2S-P2S5 to form the solid electrolyte, the molar ratio of Li2S and P2S5 is, for example, in the range of Li2S : P2S5 = 50 : 50 to 90 : 10.

[0088] Sulfide-based solid electrolytes are, for example, Li 7-x1 PS 6-x1 Cl x1 (0≤x1≤2), Li 7-x1 PS 6-x1 Br x1 (0≤x1≤2), and Li 7-x1 PS 6-x1 I x1 It may be a first argyrodite-type compound comprising one or more selected from (0≤x1≤2). In particular, the sulfide-based solid electrolyte may be a first argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0089] Alternatively, sulfide-based solid electrolytes are Li 7-a1 M1 a1 PS 6-c1 X1 c1It may be a first argyrodite-type compound containing (0≤a1≤2, 0≤c1≤2). Here, X1 may be F, Br, Cl, or a combination thereof. M1 may be scandium (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. there is.

[0090] The density of the first azyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. By having a density of 1.5 g / cc or higher for the first azyrodite-type solid electrolyte, the internal resistance of the lithium metal battery is reduced, and defects such as penetration and short circuit of the solid electrolyte film due to lithium dendrite formation can be prevented. The elastic modulus of the solid electrolyte is, for example, 15 GPa to 35 GPa.

[0091] The first solid electrolyte layer (SEL1) may further include a binder. The binder included in the first solid electrolyte layer (SEL1) is, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited to these. The binder of the first solid electrolyte layer (SEL1) 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).

[0092] The thickness (TK1) of the first solid electrolyte layer (SEL1) may be 15㎛ to 100㎛. For example, the thickness (TK1) of the first solid electrolyte layer (SEL1) may be 15㎛ to 90㎛, 15㎛ to 80㎛, 15㎛ to 70㎛, 15㎛ to 60㎛, 15㎛ to 50㎛, 20㎛ to 50㎛, or 30㎛ to 40㎛.

[0093] The first solid electrolyte layer (SEL1) may have a third width (WL1) in the first direction (D1). For example, the third width (WL1) of the first solid electrolyte layer (SEL1) may be substantially the same as the second width (WI2) of the cathode coating layer (220).

[0094] The second solid electrolyte layer (SEL2) can be placed on the lower surface of the positive active material layer (120).

[0095] The second solid electrolyte layer (SEL2) may include second electrolyte particles (SE2). The second electrolyte particles (SE2) may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. The solid electrolyte included in the second solid electrolyte layer (SEL2) may be the same as or different from any one of the materials that may be included in the solid electrolyte included in the aforementioned positive electrode active material layer (120).

[0096] The second solid electrolyte layer (SEL2) of one embodiment may include a sulfide-based solid electrolyte. The sulfide-based solid electrolyte may be manufactured by processing starting materials, such as Li2S or P2S5, by a melt quenching method or a mechanical milling method. Additionally, heat treatment may be performed after such processing. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. Furthermore, the solid electrolyte may include sulfur (S), phosphorus (P), and lithium (Li) as at least constituent elements among the sulfide-based solid electrolyte materials described above, for example. For example, the solid electrolyte may be a material containing Li2S-P2S5. When using a sulfide-based solid electrolyte material containing Li2S-P2S5 to form the solid electrolyte, the molar ratio of Li2S to P2S5 is, for example, in the range of Li2S : P2S5 = 50 : 50 to 90 : 10.

[0097] Sulfide-based solid electrolytes are, for example, Li 7-x2 PS 6-x2 Cl x2 (0≤x2≤2), Li 7-x2 PS 6-x2 Br x2 (0≤x2≤2), and Li 7-x2 PS 6-x2 I x2 It may be a second argyrodite-type compound comprising one or more selected from (0≤x2≤2). In particular, the sulfide-based solid electrolyte may be a second argyrodite-type compound comprising one or more selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0098] Alternatively, sulfide-based solid electrolytes are Li 7-a2 M2 a2 PS 6-c2 X2 c2It may be a second argyrodite-type compound containing (0≤a2≤2, 0≤c2≤2). Here, X2 may be F, Br, Cl, or a combination thereof. M2 may be scandium (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. there is.

[0099] The density of the second azyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. By having a density of 1.5 g / cc or higher for the second azyrodite-type solid electrolyte, the internal resistance of the lithium metal battery is reduced, and defects such as penetration and short circuit of the solid electrolyte film due to lithium dendrite formation can be prevented. The elastic modulus of the solid electrolyte is, for example, 15 GPa to 35 GPa.

[0100] The second solid electrolyte layer (SEL2) may further include a binder. The binder included in the second solid electrolyte layer (SEL2) is, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited to these. The binder of the second solid electrolyte layer (SEL2) 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).

[0101] The thickness (TK2) of the second solid electrolyte layer (SEL2) may be 15㎛ to 100㎛. For example, the thickness (TK2) of the second solid electrolyte layer (SEL2) may be 15㎛ to 90㎛, 15㎛ to 80㎛, 15㎛ to 70㎛, 15㎛ to 60㎛, 15㎛ to 50㎛, 20㎛ to 50㎛, or 30㎛ to 40㎛.

[0102] The second solid electrolyte layer (SEL2) may have a fourth width (WL2) in the first direction (D1). For example, the fourth width (WL2) of the second solid electrolyte layer (SEL2) may be substantially the same as the first width (WI1) of the positive active material layer (120).

[0103] An adhesive film (ADF) may be disposed on the first solid electrolyte layer (SEL1). An adhesive film (ADF) may be disposed on the lower surface of the second solid electrolyte layer (SEL2). An adhesive film (ADF) may be disposed between the first solid electrolyte layer (SEL1) and the second solid electrolyte layer (SEL2).

[0104] The thickness (TKA) of the adhesive film (ADF) may be 0.01 μm to 20 μm. For example, the thickness (TKA) of the adhesive film (ADF) may be 0.01 μm to 15 μm, or 0.01 μm to 10 μm. For example, the thickness (TKA) of the adhesive film (ADF) may be about 0.01 μm, or about 0.1 μm, or about 1 μm, or about 10 μm. If the thickness (TKA) of the adhesive film (ADF) satisfies the range described above, the interface between the first solid electrolyte layer (SEL1) and the second solid electrolyte layer (SEL2) can be bonded, and the voids within the interface can be reduced. By doing so, the performance (resistance, etc.) of an all-solid-state battery including the adhesive film (ADF) according to the embodiments of the present invention can be improved.

[0105] The adhesive film (ADF) may have a fifth width (WA) in the first direction (D1). For example, the fifth width (WA) of the adhesive film (ADF) may be substantially the same as the third width (WL1) of the first solid electrolyte layer (SEL1). For example, the fifth width (WA) of the adhesive film (ADF) may be substantially the same as the fourth width (WL2) of the second solid electrolyte layer (SEL2). For example, the fifth width (WA) of the adhesive film (ADF), the third width (WL1) of the first solid electrolyte layer (SEL1), and the fourth width (WL2) of the second solid electrolyte layer (SEL2) may be substantially the same as each other.

[0106] Below, the adhesive film (ADF) is described in detail.

[0107]

[0108] Adhesive Film (ADF)

[0109] FIG. 3 is a schematic diagram illustrating an adhesive film (ADF) according to embodiments of the present invention. FIG. 3 is an enlarged view of the M region of FIG. 2. FIG. 4 is a schematic diagram illustrating a first linear polymer (LPL1). FIG. 5 is a schematic diagram illustrating a second linear polymer (LPL2).

[0110] Referring to FIG. 3, the adhesive film (ADF) may include a first linear polymer (LPL1) and a second linear polymer (LPL2). The adhesive film (ADF) may include a network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2).

[0111] For example, the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may include ionic bonds (INB) of the first linear polymer (LPL1) and the second linear polymer (LPL2). The adhesive film (ADF) may include the first linear polymer (LPL1) and the second linear polymer (LPL2) cross-linked by ionic bonds (INB).

[0112] For example, the weight-average molecular weight (Mw) of the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 5,000 to 10,000. For example, the weight-average molecular weight (Mw) of the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 5,000 or more, 5,500 or more, 6,000 or more, or 7,000 or more. For example, the weight-average molecular weight (Mw) of the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 10,000 or less, 9,500 or less, or 9,000 or less.

[0113] For example, the number average molecular weight (Mn) of the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 5,000 to 10,000. For example, the number average molecular weight (Mn) of the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 5,000 or more, 5,500 or more, or 6,000 or more. For example, the number average molecular weight (Mn) of the network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 10,000 or less, 9,500 or less, 9,000 or less, 8,000 or less, or 7,000 or less.

[0114] The weight ratio of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 2:1 to 1:2. For example, the weight ratio of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be 1:1.

[0115] Referring to FIG. 4, the first linear polymer (LPL1) may include a first main chain (MC1) and a first side chain (SC1).

[0116] The first main chain (MC1) may include a carbon skeleton. The carbon skeleton may refer to a skeletal structure composed of carbon (C) atoms. For example, the carbon skeleton may include 1 to 50, 1 to 40, 1 to 30, 1 to 20, or 1 to 10 carbon (C) atoms. For example, the carbon skeleton may mainly include carbon (C) atoms and may additionally include other types of atoms. For example, other types of atoms may include hydrogen (H), oxygen (O), etc., but are not limited to the examples described. For example, the first main chain (MC1) may include a carbon skeleton composed of carbon (C), oxygen (O), and hydrogen (H) atoms.

[0117] The carbon skeleton can be a straight chain or a branched chain.

[0118] A straight chain or branched chain may not contain a ring. A straight chain may have carbon (C) atoms or the aforementioned atoms bonded to each other to form a continuous chain. A branched chain may include a continuous chain and a side chain bonded to the continuous chain. A straight chain or branched chain may be an aliphatic hydrocarbon. For example, a straight chain or branched chain may include at least one of a saturated hydrocarbon or an unsaturated hydrocarbon. That is, a straight chain or branched chain may include at least one of a single bond, a double bond, and a triple bond.

[0119] For example, the first main chain (MC1) may comprise a form in which at least one hydrogen on the carbon skeleton is substituted. For example, the first main chain (MC1) may comprise a form in which at least one hydrogen on the carbon skeleton is substituted with one or more substituents selected from the group consisting of deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, oxy groups, thio groups, sulfinyl groups, sulfonyl groups, carbonyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon ring groups, aryl groups, and heterocyclic groups. Each of the exemplified substituents may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group or as a phenyl group substituted with a phenyl group.

[0120] For example, the first main chain (MC1) may include a form in which two hydrogens on the carbon skeleton are substituted with a cyano group and an alkyl group.

[0121] The first side chain (SC1) may include a plurality of first side chains. That is, the first linear polymer (LPL1) may include at least one first side chain (SC1).

[0122] The first side chain (SC1) can be represented by the following structural formula 1.

[0123] [Structural Formula 1]

[0124]

[0125] R1 and R2 may each independently be hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group. For example, R1 and R2 may each be a substituted or unsubstituted C1 to C5 alkyl group.

[0126] The above L1 may be a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group. For example, the above L1 may be a substituted or unsubstituted C1 to C5 alkylene group.

[0127] The first side chain (SC1) may have the property of attracting electrons. For example, a nitrogen (N) atom of the first side chain (SC1) may contribute to the first side chain (SC1) having the said property. As an example, the first side chain (SC1) may have a positive charge. The first linear polymer (LPL1) may be a cationic polymer.

[0128] For example, the weight-average molecular weight (Mw) of the first linear polymer (LPL1) may be 1,500 to 2,500. For example, the weight-average molecular weight (Mw) of the first linear polymer (LPL1) may be 2,000 to 2,500.

[0129] For example, the first linear polymer (LPL1) can be represented by the following structural formula 1-1.

[0130] [Structural Formula 1-1]

[0131]

[0132] L2 may include a carbon skeleton. The carbon skeleton may be a straight chain or a branched chain. For example, L2 may include a carbon skeleton composed of carbon (C) and hydrogen (H) atoms, and may comprise a form in which at least one hydrogen on the carbon skeleton is substituted with one or more substituents selected from the group consisting of deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, oxy groups, thio groups, sulfinyl groups, sulfonyl groups, carbonyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon rings, aryl groups, and heterocyclic rings. For example, L2 may include a carbon skeleton composed of carbon (C) and hydrogen (H) atoms, and may comprise a form in which at least one hydrogen on the carbon skeleton is substituted with a cyano group and an alkyl group.

[0133] Referring to FIG. 5, the second linear polymer (LPL2) may include a second main chain (MC2) and a second side chain (SC2).

[0134] The second main chain (MC2) may include a carbon skeleton. The carbon skeleton may refer to a skeletal structure composed of carbon (C) atoms. For example, the carbon skeleton may include 1 to 50, 1 to 40, 1 to 30, 1 to 20, or 1 to 10 carbon (C) atoms. For example, the carbon skeleton may mainly include carbon (C) atoms and may additionally include other types of atoms. For example, other types of atoms may include hydrogen (H), oxygen (O), etc., but are not limited to the examples described. For example, the second main chain (MC2) may include a carbon skeleton composed of carbon (C), oxygen (O), and hydrogen (H) atoms.

[0135] The carbon skeleton can be a straight chain or a branched chain.

[0136] A straight chain or branched chain may not contain a ring. A straight chain may have carbon (C) atoms or the aforementioned atoms bonded to each other to form a continuous chain. A branched chain may include a continuous chain and a side chain bonded to the continuous chain. A straight chain or branched chain may be an aliphatic hydrocarbon. For example, a straight chain or branched chain may include at least one of a saturated hydrocarbon or an unsaturated hydrocarbon. That is, a straight chain or branched chain may include at least one of a single bond, a double bond, and a triple bond.

[0137] For example, the second main chain (MC2) may comprise a form in which at least one hydrogen on the carbon skeleton is substituted. For example, the second main chain (MC2) may comprise a form in which at least one hydrogen on the carbon skeleton is substituted with one or more substituents selected from the group consisting of deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, oxy groups, thio groups, sulfinyl groups, sulfonyl groups, carbonyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon ring groups, aryl groups, and heterocyclic groups. Each of the exemplified substituents may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group or as a phenyl group substituted with a phenyl group.

[0138] For example, the second main chain (MC2) may include a form in which two hydrogens on the carbon skeleton are substituted with a cyano group and an alkyl group.

[0139] The second side chain (SC2) may include a plurality of second side chains. That is, the second linear polymer (LPL2) may include at least one second side chain (SC2).

[0140] The second side chain (SC2) can be represented by the following structural formula 2.

[0141] [Structural Formula 2]

[0142]

[0143] The above R3 may be hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group. For example, the above R3 may be a substituted or unsubstituted C1 to C5 alkyl group.

[0144] The second side chain (SC2) can provide electrons. For example, sulfur (S) atoms and / or oxygen (O) atoms of the second side chain (SC2) can contribute to the second side chain (SC2) having the above properties. As an example, the second side chain (SC2) can have a negative charge. The second linear polymer (LPL2) may be an anionic polymer.

[0145] The first side chain (SC1) and the second side chain (SC2) can be ionically bonded to each other (see INB in ​​FIG. 3). The first linear polymer (LPL1) and the second linear polymer (LPL2) can be ionically bonded (see INB in ​​FIG. 3). Thus, the first linear polymer (LPL1) and the second linear polymer (LPL2) can form a network structure (see NWS in FIG. 3). For example, a network structure containing ionic bonds (INB, NWS in FIG. 3) can be confirmed via NMR.

[0146] For example, the weight-average molecular weight (Mw) of the second linear polymer (LPL2) may be 1,500 to 2,500. For example, the weight-average molecular weight (Mw) of the second linear polymer (LPL2) may be 2,000 to 2,500.

[0147] For example, the second linear polymer (LPL2) can be represented by the following structural formula 2-1.

[0148] [Structural Formula 2-1]

[0149]

[0150] L2 may include a carbon skeleton. The carbon skeleton may be a straight chain or a branched chain. For example, L2 may include a carbon skeleton composed of carbon (C) and hydrogen (H) atoms, and may comprise a form in which at least one hydrogen on the carbon skeleton is substituted with one or more substituents selected from the group consisting of deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, oxy groups, thio groups, sulfinyl groups, sulfonyl groups, carbonyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon rings, aryl groups, and heterocyclic rings. For example, L2 may include a carbon skeleton composed of carbon (C) and hydrogen (H) atoms, and may comprise a form in which at least one hydrogen on the carbon skeleton is substituted with a cyano group and an alkyl group.

[0151] The adhesive film (ADF) according to the embodiments of the present invention may have adhesive properties. The adhesive film (ADF) according to the embodiments of the present invention may adhere to the interface between the first solid electrolyte layer (SEL1) and the second solid electrolyte layer (SEL2) and may reduce voids within the interface. By doing so, the performance (resistance, etc.) of an all-solid-state battery including the adhesive film (ADF) according to the embodiments of the present invention may be improved. For example, the solid electrolyte layer (300) according to the embodiments of the present invention may have an interfacial resistance of 300 Ω or less and an ionic conductivity of 0.02 mS / cm or more.

[0152]

[0153] Method for manufacturing an all-solid-state battery

[0154] FIGS. 6 and 9 are flowcharts for explaining a method for manufacturing an all-solid-state battery according to embodiments of the present invention. FIGS. 7, 8, and FIGS. 10 to 13 are schematic diagrams for explaining each step of the manufacturing method.

[0155] Referring to FIG. 6, a method for manufacturing an all-solid-state battery according to embodiments of the present invention may include forming a negative electrode laminate (S100); forming a positive electrode laminate (S300); forming an adhesive film (S500); and forming a composite (S900).

[0156]

[0157] Referring to FIG. 7, a cathode layer (200) and a first solid electrolyte layer (SEL1) can be stacked and pressed to form a cathode laminate (S100). The cathode layer (200) may include a cathode current collector (210) and a cathode coating layer (220). A cathode laminate can be formed by stacking the first solid electrolyte layer (SEL1) on the cathode layer (200) and then applying a first pressure.

[0158] Referring to FIG. 8, an anode layer (100) and a second solid electrolyte layer (SEL2) can be stacked and pressed to form an anode laminate (S300). The anode layer (100) may include an anode current collector (110) and an anode active material layer (120). An anode laminate can be formed by stacking a second solid electrolyte layer (SEL2) on the anode layer (100) and then applying a second pressure.

[0159] The present invention allows the first pressure and the second pressure to be controlled differently by manufacturing the anode laminate and the cathode laminate by applying an individual pressurization method. Through this, a relatively low pressure can be applied to the laminate among the anode laminate and the cathode laminate that has weak mechanical strength or severe structural imbalance, which may be damaged if pressurized at a high pressure.

[0160] The first pressure may be greater than the second pressure. For example, the first pressure may be defined as pressure applied toward the interior of the anode laminate from the upper and lower surfaces of the anode laminate. The second pressure may be defined as pressure applied toward the interior of the cathode laminate from the upper and lower surfaces of the cathode laminate.

[0161] Forming the above-mentioned anode laminate and cathode laminate may include a pressurization process in which a roll press is applied. However, this is not necessarily limited to this method, and any pressurization process applicable in the relevant technical field may be applied. For example, pressurization processes such as hydraulic plate press and warm isostatic press may be applied.

[0162] When a roll press is applied during the formation process of the anode laminate, the line pressure of the first pressure may be 1 ton / cm to 5 ton / cm. Specifically, the line pressure of the first pressure may be 1 ton / cm to 4 ton / cm, 1 ton / cm to 3 ton / cm, or 1 ton / cm to 2.5 ton / cm.

[0163] When a roll press is applied during the formation process of the above cathode laminate, the line pressure of the second pressure may be 1 ton / cm to 4 ton / cm. Specifically, the line pressure of the first pressure may be 1 ton / cm to 3 ton / cm, 1 ton / cm to 2.5 ton / cm, or 1 ton / cm to 2 ton / cm.

[0164] The above pressurization process may be carried out at a relatively high temperature. Specifically, the above pressurization process may be carried out at 60 to 150 ℃, at 80 to 130 ℃, and at 100 to 125 ℃.

[0165] Forming the anode laminate and the cathode laminate may include a preheating process prior to the pressurization process. Specifically, the anode laminate and the cathode laminate may be preheated to ±10°C and ±5°C of the temperature at which the pressurization process is performed. The preheating process can prevent damage to the anode laminate and the cathode laminate caused by rapid temperature changes during the high-temperature pressurization process.

[0166] The order of forming the cathode stack (S100) and forming the anode stack (S300) is not limited. For example, the cathode stack may be formed first (S100), and then the anode stack may be formed (S300). For another example, the anode stack may be formed first (S300), and then the cathode stack may be formed (S100).

[0167]

[0168] Referring to FIG. 9, forming an adhesive film (S500) may include: manufacturing a first linear polymer (S510); manufacturing a second linear polymer (S530); manufacturing a mixture of the first linear polymer, the second linear polymer, and a solvent (S550); forming the mixture into a film (S570); and heat-treating the film-formed mixture (S590).

[0169] The first linear polymer (see LPL1 in FIG. 4) can be prepared by a chemical reaction of the first reactant and the second reactant (S510).

[0170] The first reactant can be represented by the following structural formula 3.

[0171] [Structural Formula 3]

[0172]

[0173] L2 may include a carbon skeleton. The carbon skeleton may be a straight chain or a branched chain as described above. For example, L2 may include a carbon skeleton composed of carbon (C) and hydrogen (H) atoms, and at least one hydrogen on the carbon skeleton may be substituted with a cyano group and an alkyl group.

[0174] For example, x can be from 1 to 50. For example, y can be from 1 to 50. For example, z can be from 1 to 50.

[0175] For example, the first reactant can initiate polymerization. For example, the first reactant can initiate polymerization at a temperature of 40°C to 80°C.

[0176] The second reactant can be represented by the following structural formula 4.

[0177] [Structural Formula 4]

[0178]

[0179] The above R1 and the above R2 may each independently be hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0180] The above L1 may be a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylene group, or a substituted or unsubstituted C6 to C20 arylene group.

[0181] The second linear polymer (see LPL2 in FIG. 5) can be prepared by the chemical reaction of the first reactant and the third reactant (S530).

[0182] The first reactant can be represented by the structural formula 3 described above.

[0183] The third reactant can be represented by the following structural formula 5.

[0184] [Structural Formula 5]

[0185]

[0186] The above R3 may be hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

[0187] Referring to FIG. 10, a mixture (MXR) can be prepared by mixing a first linear polymer (LPL1), a second linear polymer (LPL2), and a solvent (S550).

[0188] The weight ratio of the first linear polymer (LPL1) and the second linear polymer (LPL2) in the mixture (MXR) may be 2:1 to 1:2. For example, the weight ratio of the first linear polymer (LPL1) and the second linear polymer (LPL2) in the mixture (MXR) may be 1:1.

[0189] The solvent may include at least one selected from the group consisting of dichloromethane (methylene chloride), acetonitrile, and tetrahydrofuran.

[0190] Mixing is generally not limited to any method that allows the components to be uniformly mixed with one another.

[0191] Referring to FIG. 11, the mixture (MXR) can be formed into a film (S570). The film formation can be performed by at least one method selected from the group consisting of casting, bar coating, spin coating, and dip coating.

[0192] For example, film formation can be performed by casting and bar coating methods. For example, a mixture (MXR) can be cast onto a substrate (SUB). The cast mixture (MXR) can be coated using a bar coater (CTR). In this way, a film-formed mixture (FMX) can be formed on the substrate (SUB).

[0193] Referring to FIG. 12, the film-formed mixture (FMX) can be heat-treated (S590).

[0194] Heat treatment can be performed using equipment (HTD) capable of heating the filmed mixture (FMX). The equipment (HTD) capable of heating is generally any equipment capable of heating the filmed mixture (FMX) and is not limited to it.

[0195] For example, the heat treatment may be performed at a temperature of 40°C to 180°C. For example, the heat treatment may be performed at a temperature of 40°C to 150°C, 40°C to 100°C, 40°C to 80°C, or 50°C to 70°C. When the heat treatment temperature satisfies the range described above, the first linear polymer (LPL1) and the second linear polymer (LPL2) within the filmed mixture (FMX) may be ionically bonded (INB). Thus, an adhesive film (ADF) comprising a network structure (NWS) of the first linear polymer (LPL1) and the second linear polymer (LPL2) may be formed.

[0196] For example, forming an adhesive film (ADF) (S500) may further include removing a substrate (SUB) after the heat treatment step (S590). That is, forming an adhesive film (ADF) (S500) may further include peeling the adhesive film (ADF) from the substrate (SUB).

[0197]

[0198] Referring to FIG. 13, an adhesive film (ADF) can be provided between a first solid electrolyte layer (SEL1) and a second solid electrolyte layer (SEL2), and the first solid electrolyte layer (SEL1), the adhesive film (ADF), and the second solid electrolyte layer (SEL2) can be pressed (S900). Thus, a combined body (all-solid-state battery of FIG. 1) in which an anode layer (100), a solid electrolyte layer (300), and a cathode layer (200) are combined can be manufactured.

[0199] The anode laminate, the cathode laminate, and the adhesive film (ADF) can be pressed by a third pressure. By doing so, the first solid electrolyte layer (SEL1) and the second solid electrolyte layer (SEL2) can be bonded to each other.

[0200] This step may include a pressurization process in which a hydraulic plate press is applied. However, it is not necessarily limited to this method, and any pressurization process applicable in the relevant technical field may be applied. For example, pressurization processes such as roll press and warm isostatic press may be applied. As an example, the third pressure may be defined as the pressure applied from the upper and lower surfaces of the assembly toward the interior of the assembly.

[0201] The third pressure may be 2 MPa or higher. Specifically, the third pressure may be 2.5 MPa or higher, 3 MPa or higher, or 3.5 MPa or higher. The third pressure may be 100 MPa or lower. Specifically, the third pressure may be 20 MPa or lower, 10 MPa or lower, 5 MPa or lower, or 4 MPa or lower.

[0202] For example, the pressurization process may be carried out at a relatively high temperature. For example, the pressurization process may be performed at a temperature of 40°C to 180°C. For example, the pressurization process may be performed at a temperature of 50°C to 170°C, or 60°C to 160°C. When the temperature satisfies the range described above, the unreacted first linear polymer (LPL1) and the unreacted second linear polymer (LPL2) within the adhesive film (ADF) can be ionically bonded. This allows the interface between the first solid electrolyte layer (SEL1) and the second solid electrolyte layer (SEL2) to be bonded, and the voids within the interface can be reduced. In addition, the performance (resistance, etc.) of the all-solid-state battery can be improved.

[0203]

[0204] The present invention will be explained in more detail below through examples. However, these examples are intended to illustrate the invention and the scope of the invention is not limited to these examples.

[0205]

[0206] Examples

[0207] Preparation Example 1: Preparation of the first linear polymer (LDL1)

[0208] A first linear polymer (LDL1) represented by the following structural formula 1-2 was prepared. The first linear polymer (LDL1) was prepared by mixing a first reactant and a second reactant in a weight ratio of 1:1 and chemically reacting them at a temperature of 60°C. The first reactant can be represented by the following structural formula 3-1. The second reactant can be represented by the following structural formula 4-2.

[0209] [Structural Formula 1-2]

[0210]

[0211] [Structural Formula 3-1]

[0212]

[0213] [Structural Formula 4-2]

[0214]

[0215]

[0216] Preparation Example 2: Preparation of the second linear polymer (LDL2)

[0217] A second linear polymer (LDL2) represented by the following structural formula 2-2 was prepared. The second linear polymer (LDL2) was prepared by mixing the first reactant and the third reactant in a weight ratio of 1:1 and chemically reacting them at a temperature of 60°C. The first reactant can be represented by the above structural formula 3-1. The third reactant can be represented by the following structural formula 5-2.

[0218] [Structural Formula 2-2]

[0219]

[0220] [Structural Formula 5-2]

[0221]

[0222]

[0223] Preparation Example 3: Preparation of Adhesive Film (ADF)

[0224] An adhesive film (ADF) comprising a network structure of a first linear polymer and a second linear polymer was prepared. The adhesive film (ADF) was prepared by the following method.

[0225] A mixture of the first linear polymer of Preparation Example 1, the second linear polymer of Preparation Example 2, and a solvent (dichloromethane, acetonitrile, tetrahydrofuran, etc.) was prepared. The first linear polymer and the second linear polymer were mixed in a weight ratio of 1:1. The mixture was cast onto a substrate and formed into a film using a bar coater. The film-formed mixture was heat-treated at a temperature of 60°C.

[0226]

[0227] Preparation Example 4: Preparation of the cathode layer

[0228] A SUS foil with a thickness of 10 μm was prepared as a cathode current collector. Additionally, carbon black (CB) with a primary particle size of approximately 30 nm and silver (Ag) particles with an average particle size (D50) of approximately 60 nm were prepared as cathode coating layer materials. 4 g of a mixed powder, prepared by mixing carbon black (CB) and silver (Ag) particles in a weight ratio of 3:1, was placed in a container, and 4 g of an NMP solution containing 7 wt% of PVDF binder (Kureha #9300) was added to prepare a mixed solution. Subsequently, a slurry was prepared by stirring the mixed solution while gradually adding NMP to it. The prepared slurry was applied to a Ni sheet using a bar coater and dried in air at 80°C for 10 minutes. The resulting laminate was vacuum dried at 40°C for 10 hours. The surface of the cathode coating layer of the laminate was flattened by cold rolling the dried laminate. The cathode layer was fabricated by the above process. The thickness of the cathode coating layer included in the cathode layer was approximately 7 μm. The area of ​​the cathode coating layer and the cathode current collector were the same.

[0229]

[0230] Preparation Example 5: Preparation of the anode layer

[0231] LiNi coated with Li2O-ZrO2 (LZO) as a cathode active material 0.8 Co 0.15 Mn 0.05O2 (NCM) was prepared. The LZO-coated cathode active material was prepared according to the method disclosed in Korean Patent Publication No. 10-2016-0064942. Li6PS5Cl, an argyrodite-type crystal (D50 = 0.5 μm, crystalline), was prepared as the solid electrolyte. Polytetrafluoroethylene (PTFE) binder was prepared as the binder. Carbon nanofiber (CNF) was prepared as the conductive agent. A slurry was formed by mixing these materials with a xylene solvent in a weight ratio of cathode active material : solid electrolyte : conductive agent : binder = 84 : 11.5 : 3 : 1.5, and then vacuum-dried at 40°C for 8 hours to produce a cathode sheet. Anode sheets manufactured were placed on the cross-section of an anode current collector made of carbon-coated aluminum foil on one side, and an anode layer was manufactured by a heated roll press at 85°C. The total thickness of the anode layer was approximately 120 μm. The thickness of the anode active material layer was approximately 107 μm, and the thickness of the carbon-coated (thickness 1 mm) aluminum foil was approximately 13 μm. The area of ​​the anode active material layer and the anode current collector were the same.

[0232]

[0233] Preparation Example 6: Preparation of a solid electrolyte layer (dry)

[0234] A mixture was prepared by adding 1 part by weight of a polytetrafluoroethylene (PTFE) first binder and 1 part by weight of a polyvinylidene fluoride (PVDF) second binder to an argyrodite-type crystal Li6PS5Cl sulfide-based solid electrolyte (D50 = 1~10 μm, crystalline) with respect to 98 parts by weight of the solid electrolyte into a grind mixer and mixing. The prepared mixture was added to a mortar heated to 80°C and stirred to prepare a dough. The prepared dough was passed through a roller and formed into a sheet shape to prepare a solid electrolyte film of uniform thickness. A solid electrolyte layer was manufactured by the above process. The above solid electrolyte layer was prepared as a solid electrolyte layer (SEL2) having substantially the same area as the anode layer and a solid electrolyte layer (SEL1) having substantially the same area as the cathode layer. The elastic modulus of the sulfide-based solid electrolyte was about 15 GPa to 30 GPa.

[0235]

[0236] Preparation Example 7: Preparation of an all-solid-state battery

[0237] An all-solid-state battery containing an adhesive film was prepared. The all-solid-state battery containing the adhesive film was manufactured by the following method.

[0238] An anode layer and a solid electrolyte layer (SEL2) were laminated and pressed using a roll press method. An anode laminate was manufactured by applying a linear pressure of 2.5 ton / cm at 120°C. A cathode layer and a solid electrolyte layer (SEL1) were laminated and pressed using a roll press method. A cathode laminate was manufactured by applying a linear pressure of 2.0 ton / cm at 120°C.

[0239] An adhesive film was provided between the anode laminate and the cathode laminate, and a composite was formed by applying pressure using a roll press method. The pressure was applied at a temperature of 160°C.

[0240]

[0241] Preparation Example 8: Preparation of a symmetrical cell

[0242] A cathode layer and a solid electrolyte layer (SEL1) were laminated and pressed using a roll press method. A cathode laminate was manufactured by applying a linear pressure of 2.0 ton / cm at 120°C.

[0243] A symmetric cell was manufactured by placing cathode laminates on both sides of an adhesive film (ADF) and applying pressure using a roll press method. The pressure was applied at a temperature of 160°C.

[0244]

[0245] Comparative example

[0246] A symmetric cell that does not contain an adhesive film (ADF) was prepared.

[0247] It was manufactured in the same manner as Example 1, except that an adhesive film (ADF) was not provided.

[0248]

[0249] Experimental Example 1: Analysis of Adhesive Film

[0250] The adhesive film according to Preparation Example 3 was a soft, off-white film. The thickness of the adhesive film was approximately 10 μm.

[0251] The molecular weights of the first linear polymer, the second linear polymer, and the components (network structure) of the adhesive film were analyzed by gel permeation chromatography. The results are shown in Table 1.

[0252]

[0253] Classification MnMwPDI First linear polymer 1,130 2,410 1.8 Second linear polymer 1,090 2,260 1.3 Network structure 6,342 8,970 1.41

[0254]

[0255] The structure of the components (network structure) of the adhesive film 1 It was confirmed by H NMR. The results were as follows.

[0256] 1H NMR (400 MHz, CDCl3): δ 4.03 (br m), 3.55 (br m), 3.47 (br s), 2.47-2.42 (br m), 2.12 (br s), 1.28 (br m)

[0257]

[0258] Experimental Example 2: Performance Analysis of All-Solid State Batteries

[0259] The interfacial resistance of the all-solid-state batteries according to the examples and comparative examples was measured using an impedance analyzer (Solartron 1260A Impedance / Gain-Phase Analyzer) according to the 2-probe method. The interfacial resistance was measured using a symmetric cell according to the examples and comparative examples. The interfacial resistance was measured under conditions of a temperature of 25°C, a frequency range of 0.1 Hz to 1 MHz, and a voltage bias of 10 mV.

[0260] The ionic conductivity of the all-solid-state battery according to the examples and comparative examples was evaluated at 25°C. The ionic conductivity was measured using a symmetric cell according to the examples and comparative examples. The ionic conductivity was calculated by substituting the resistance value obtained from the arc of the Nyquist plot according to the impedance analysis into the following equation.

[0261] [ceremony]

[0262] Ionic conductivity (σ) = I / (R A) (I: thickness of solid electrolyte layer, R: resistance, A: electrode area)

[0263] The results are shown in Table 2.

[0264]

[0265] Interface Resistance (Ω) Ionic Conductivity (mS / cm) Example 9 80.046 Comparative Example 5 050.009

[0266]

[0267] Referring to Table 2, the interfacial resistance of the symmetric cell according to the example was lower compared to the symmetric cell according to the comparative example. Thus, it was confirmed that the adhesive film can bond the interfaces of different solid electrolyte layers, reduce voids within the interfaces, and provide a solid electrolyte layer with low resistance and an all-solid-state battery.

[0268] In addition, the symmetric cell according to the example had excellent ion conductivity. Thus, it was confirmed that the adhesive film can improve the ion conductivity of the solid electrolyte layer and the all-solid-state battery.

[0269]

[0270] Although embodiments of the present invention have been described above with reference to the attached drawings, the present invention may be implemented in other specific forms without altering its technical concept or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

1. A network structure comprising a first linear polymer and a second linear polymer, wherein The first linear polymer comprises a first main chain and at least one first side chain represented by the following structural formula 1, and The second linear polymer comprises a second main chain and at least one second side chain represented by the following structural formula 2, and The first side chain and the second side chain are ionically bonded to each other. Adhesive film: [Structural Formula 1] The above R1 and the above R2 are each independently hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and The above L1 is a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group, and [Structural Formula 2] The above R3 is hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

2. In Paragraph 1, The weight ratio of the first linear polymer and the second linear polymer is 2:1 to 1:2, Adhesive film.

3. In Paragraph 1, The weight-average molecular weight of the network structure of the first linear polymer and the second linear polymer is 5,000 to 10,000, Adhesive film.

4. In Paragraph 1, The thickness of the adhesive film is 0.01㎛ to 20㎛, Adhesive film.

5. In Paragraph 1, The above first linear polymer is represented by the following structural formula 1-1, Adhesive film: [Structural Formula 1-1] The above L2 includes a carbon skeleton composed of carbon atoms and hydrogen atoms, and The carbon skeleton comprises a form in which at least one hydrogen on the carbon skeleton is substituted with one or more substituents selected from the group consisting of deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, oxy groups, thio groups, sulfinyl groups, sulfonyl groups, carbonyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon ring groups, aryl groups, and heterocyclic rings.

6. In Paragraph 1, In the first side chain above, R1 and R2 are each substituted or unsubstituted C1 to C5 alkyl groups, and The above L1 is a substituted or unsubstituted C1 to C15 alkylene group, Adhesive film.

7. In Paragraph 1, The above second linear polymer is represented by the following structural formula 2-1, Adhesive film: [Structural Formula 2-1] The above L2 includes a carbon skeleton composed of carbon atoms and hydrogen atoms, and The carbon skeleton comprises a form in which at least one hydrogen on the carbon skeleton is substituted with one or more substituents selected from the group consisting of deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, oxy groups, thio groups, sulfinyl groups, sulfonyl groups, carbonyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, alkynyl groups, hydrocarbon ring groups, aryl groups, and heterocyclic rings.

8. In Paragraph 1, In the second side chain above, the R3 is each a substituted or unsubstituted C1 to C5 alkyl group, Adhesive film.

9. A positive electrode layer, a negative electrode layer, and a solid electrolyte layer disposed between the positive electrode layer and the negative electrode layer, wherein The above solid electrolyte layer is: A first solid electrolyte layer comprising first electrolyte particles; An adhesive film on the first solid electrolyte layer; and It includes second electrolyte particles and a second solid electrolyte layer on the adhesive film, The above adhesive film is the adhesive film described in claim 1, All-solid-state battery.

10. In Paragraph 9, The weight ratio of the first linear polymer and the second linear polymer is 2:1 to 1:2, All-solid-state battery.

11. In Paragraph 9, The weight-average molecular weight of the network structure of the first linear polymer and the second linear polymer is 5,000 to 10,000, All-solid-state battery.

12. In Paragraph 9, The thickness of the adhesive film is 0.01㎛ to 20㎛, All-solid-state battery.

13. In Paragraph 9, The first electrolyte particle and the second electrolyte particle each contain an azirodite-type compound, and The above azirodite-type compound is Li 7-a M a PS 6-c X c Includes, The above X is Cl, Br, or a combination thereof, and Each of the above a and c is a real number between 0 and 2, All-solid-state battery.

14. In Paragraph 9, The above solid electrolyte layer has an interfacial resistance of 300 Ω or less and an ionic conductivity of 0.02 mS / cm or more, All-solid-state battery.

15. Forming a cathode laminate by stacking and pressing a cathode layer and a first solid electrolyte layer; Forming an anode laminate by stacking and pressing an anode layer and a second solid electrolyte layer; Forming an adhesive film; and The method comprises providing and pressing the adhesive film between the first solid electrolyte layer and the second solid electrolyte layer to form a composite, wherein Forming the above adhesive film is: Forming a mixture of a first linear polymer, a second linear polymer, and a solvent; Filming the above mixture; and The above-mentioned film-formed mixture includes heat treatment, The first linear polymer comprises a first main chain and at least one first side chain represented by the following structural formula 1, and The second linear polymer comprises a second main chain and at least one second side chain represented by the following structural formula 2, Method for manufacturing an all-solid-state battery: [Structural Formula 1] The above R1 and the above R2 are each independently hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group, and The above L1 is a single bond, a substituted or unsubstituted C1 to C5 alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkynylene group, or a substituted or unsubstituted C6 to C20 arylene group, and [Structural Formula 2] The above R3 is hydrogen, a cyano group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C2 to C20 alkenyl group, a substituted or unsubstituted C2 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C20 aryl group, or a substituted or unsubstituted C2 to C20 heteroaryl group.

16. In Paragraph 15, The weight ratio of the first linear polymer and the second linear polymer in the mixture is 2:1 to 1:2, Method for manufacturing an all-solid-state battery.

17. In Paragraph 15, The above film formation is performed by at least one method selected from the group consisting of casting, bar coating, spin coating, and dip coating, Method for manufacturing an all-solid-state battery.

18. In Paragraph 15, The above heat treatment is performed at a temperature of 40℃ to 180℃, Method for manufacturing an all-solid-state battery.

19. In Paragraph 15, Forming the above-mentioned assembly comprises at least one selected from the group consisting of roll pressing, heated hydrostatic pressing, and plate pressing. Method for manufacturing an all-solid-state battery.

20. In Paragraph 15, The formation of the above composite is performed at a temperature of 40°C to 180°C, Method for manufacturing an all-solid-state battery.

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