Solid electrolyte separator and all-solid-state battery comprising same

Abstract

Provided are a solid electrolyte separator and an all-solid-state battery comprising same, the solid electrolyte separator: comprising a solid electrolyte and an ion-conductive polymer; and having an embossed portion formed on at least one surface thereof.

Description

Solid electrolyte separator and all-solid-state battery including the same

[0001] This invention relates to a solid electrolyte separator and an all-solid-state battery containing the same.

[0002] Recently, driven by industrial demands, the development of batteries with high energy density and safety is actively underway. For example, lithium 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] Since lithium batteries use an electrolyte containing a flammable organic solvent, there is a possibility of overheating and fire if a short circuit occurs.

[0004] All-solid-state batteries using a solid electrolyte instead of a liquid electrolyte are being proposed.

[0005] By not using flammable organic solvents, all-solid-state batteries can significantly reduce the likelihood of fire or explosion in the event of a short circuit. These batteries can greatly enhance safety compared to lithium batteries that use liquid electrolytes.

[0006] Secondary batteries use sulfur-based materials as cathode active materials to increase capacity. Using sulfur-based materials allows for a higher theoretical energy capacity compared to lithium-ion batteries, and the low cost of sulfur-based materials can lower the manufacturing cost of secondary batteries.

[0007] Lithium-sulfur batteries using sulfur-based materials as cathode active materials undergo volume expansion and contraction due to the formation and decomposition of lithium sulfide (Li2S) during the charging and discharging process. This can lead to poor contact or mechanical stress at the electrode-electrolyte interface. Such volume changes can result in performance degradation and reduced lifespan of the all-solid-state battery.

[0008] One aspect is to provide a solid electrolyte separator capable of minimizing volume changes occurring during charging and discharging.

[0009] Another aspect is to provide an all-solid-state battery with improved performance and lifespan by minimizing volume changes during charging and discharging.

[0010] According to one embodiment, a solid electrolyte separator is provided, comprising a solid electrolyte and an ion-conducting polymer, wherein the solid electrolyte separator comprises an uneven surface on its upper surface.

[0011] According to another embodiment, an all-solid-state battery is provided, comprising an anode; a cathode; and the solid electrolyte separator described above, wherein the upper surface is a surface adjacent to the anode.

[0012] According to one aspect, by employing a solid electrolyte separator having an uneven surface on its upper surface, it is possible to provide an all-solid-state battery with improved performance and lifespan characteristics.

[0013] FIG. 1 is a cross-sectional view illustrating a solid electrolyte separator according to an exemplary embodiment.

[0014] FIG. 2 is a cross-sectional view illustrating a solid electrolyte separator according to another exemplary embodiment.

[0015] FIG. 3 is a cross-sectional view illustrating a solid electrolyte separator according to another exemplary embodiment.

[0016] Figure 4 is a top view of the solid electrolyte separator shown in Figure 3.

[0017] FIG. 5 is a cross-sectional view illustrating a solid electrolyte separator according to another exemplary embodiment.

[0018] FIG. 6 is a cross-sectional view illustrating an all-solid-state battery according to an exemplary embodiment.

[0019] Figure 7 is an enlarged schematic diagram showing area A of Figure 6.

[0020] FIG. 8 is a cross-sectional view illustrating an all-solid-state battery according to another exemplary embodiment.

[0021] The present inventive concept described below is subject to various modifications and may have various embodiments, and specific embodiments are illustrated in the drawings and described in detail. However, this is not intended to limit the present inventive concept to specific embodiments and should be understood to include all modifications, equivalents, or substitutions that fall within the scope of the description of the present inventive concept.

[0022] The terms used below are used merely to describe specific embodiments and are not intended to limit the creative concept. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the following, terms such as "comprising" or "having" are intended to indicate the existence of the features, numbers, steps, actions, components, parts, components, materials, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, components, materials, or combinations thereof. The " / " used below may be interpreted as "and" or "or" depending on the context.

[0023] In the drawings, thicknesses have been enlarged or reduced to clearly represent various layers and regions. Throughout the specification, the same reference numerals have been used for similar parts. Throughout the specification, when a part such as a layer, film, region, or plate is described as being "on" or "above" another part, this includes not only cases where it is directly above another part but also cases where there is another part in between. Throughout the specification, terms such as "first," "second," etc., may be used to describe various components, but the components should not be limited by these terms. In this specification and drawings, components having substantially the same functional configuration are referred to by the same reference numerals to avoid redundant descriptions.

[0024] In the present disclosure, the "size" of a particle is, for example, the "particle diameter" of the particle. The "particle diameter" of the particle represents the average diameter when the particle is spherical and represents the average major axis length when the particle is non-spherical. The particle diameter of the particle can be measured using a particle size analyzer (PSA). The "particle diameter" of the particle is, for example, the average particle diameter. The average particle diameter is, for example, the median particle diameter (D50). The median particle diameter (D50) is the particle size corresponding to the 50% cumulative volume calculated from the side of the particle having the smaller particle size in the particle size distribution measured, for example by laser diffraction.

[0025] In the present disclosure, “metal” includes both metals and metalloids such as silicon and germanium in an elemental or ionic state.

[0026] In this disclosure, "alloy" means a mixture of two or more metals.

[0027] In the present disclosure, "anode active material" refers to an anode material capable of undergoing lithiation and delithiation.

[0028] In the present disclosure, "anode active material" refers to an anode material capable of undergoing lithiation and delithiation.

[0029] In the present disclosure, "lithiation" and "to lithiate" refer to the process of adding lithium to a positive electrode active material or a negative electrode active material.

[0030] In the present disclosure, "delithiation" and "to delithiate" refer to the process of removing lithium from a positive electrode active material or a negative electrode active material.

[0031] In this disclosure, "charge" and "to charge" refer to the process of providing electrochemical energy to a battery.

[0032] In this disclosure, "anode" and "cathode" refer to electrodes where electrochemical reduction and lithiation occur during the discharge process.

[0033] In this disclosure, "cathode" and "anode" refer to electrodes where electrochemical oxidation and delithiation occur during the discharge process.

[0034] In the present disclosure, each of the phrases such as “A or B”, “at least one of A and B”, “at least one of A or B”, “A, B or C”, “at least one of A, B and C”, and “at least one of A, B, or C” may include any one of the items listed together in the corresponding phrase, or all possible combinations thereof.

[0035] In the present disclosure, "surface roughness (R z )" is expressed using Ten-point Average Roughness, which is calculated by adding the average of the top 5 peak heights and bottom 5 valley depths within the measurement range, and can be measured using a stylus profilometer, laser scanner, or atomic force microscope (AFM).

[0036] A solid electrolyte separator and an all-solid-state battery according to exemplary embodiments will be described in more detail below.

[0037] [Solid Electrolyte Membrane]

[0038] FIG. 1 is a cross-sectional view illustrating a solid electrolyte separator according to an exemplary embodiment. Referring to FIG. 1, the solid electrolyte separator (300) comprises a solid electrolyte (SE); and an ion-conducting polymer (ICP); and may include an uneven surface on its upper surface.

[0039] The solid electrolyte (SE) may include, for example, a sulfide-based solid electrolyte with excellent ionic conductivity characteristics.

[0040] Sulfide-based solid electrolytes are, for example, Li3PO4-Li2SO4, 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, Li2S-P2S5-Z m S n (In the above formula, m and n are positive numbers, and Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (In the above formula, p and q are positive numbers, and M is one of P, Si, Ge, B, Al, Ga, and In), Li + 12-n-x A n+ X 2- 6-x Y - x(In the above formula, A is one of P, As, Ge, Ga, Sb, Si, Sn, Al, In, Ti, V, Nb, or Ta, X is one of S, Se, or Te, Y is Cl, Br, I, F, CN, OCN, SCN, or N3, and 1≤n≤5, 0≤x≤2) Li 7-m M m PS 6-n X n (In the above formula, M is one of Na, K, Fe, Mg, Ca, Ag, Cu, Zr, Zn, Sc, Y, Ti, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Mn, Tc, Re, Bh, Ru, Os, Hs, Co, Rh, Ir, Mt, Ni, Pd, Pt, Ds, Au, Rg, Cd, Hg, or Cn, X is one of F, Cl, Br, or I, 0 <n≤2, 0<x≤2), Li 7-x PS 6-x Cl x (0 <x≤2), Li 7-x PS 6-x Br x (0 <x≤2), Li 7-x PS 6-x I x (0 <x≤2) 또는 이들의 조합을 포함할 수 있다.

[0041] Sulfide-based solid electrolytes can be manufactured by processing starting materials, such as Li2S or P2S5, using methods such as melt quenching or mechanical milling. Additionally, heat treatment may be performed after such processing. Sulfide-based solid electrolytes may be amorphous, crystalline, or a mixture thereof. Sulfide-based solid electrolytes may, for example, contain at least sulfur (S), phosphorus (P), and lithium (Li) as constituent elements. Sulfide-based solid electrolytes may, for example, contain Li2S-P2S5. When using a material containing Li2S-P2S5 as a sulfide-based solid electrolyte, the molar ratio of Li2S and P2S5 is, for example, in the range of Li2S : P2S5 = 20 : 80 to 90 : 10, 25 : 75 to 90 : 10, 30 : 70 to 70 : 30, and 40 : 60 to 60 : 40.

[0042] The sulfide-based solid electrolyte may be, for example, an argyrodite-type solid electrolyte. The density of the argyrodite-type solid electrolyte may be 1.5 to 2.0 g / cc. Since the argyrodite-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 penetration of the solid electrolyte separator by lithium can be suppressed more effectively.

[0043] The ion-conducting polymer (ICP) combines with the solid electrolyte (SE) to strengthen the mechanical strength of the solid electrolyte separator (300) and can absorb the volume change of the electrode during the charging and discharging process.Ionic conductive polymers (ICPs) include, for example, polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (PVDF-HFP), poly(styrene-b-ethylene oxide) block copolymer (PS-PEO), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-b-divinylbenzene) block copolymer, poly(styrene-ethylene oxide-styrene) block copolymer, polystyrene sulfonate (PSS), polyvinyl fluoride (PVF), poly(methylmethacrylate) (PMMA), polyethylene glycol (PEG), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyethylenedioxythiophene (PEDOT), polypyrrole (PPY), polyacrylonitrile (PAN), polyaniline, and polyacetylene. Nafion, Aquivion, Flemion, Gore, Aciplex, Morgane ADP, sulfonated poly(ether ether ketone) (SPEEK), sulfonated poly(arylene ether ketone ketone sulfone) (SPAEKKS), sulfonated poly(aryl ether ketone) (SPAEK), poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI), poly(styrene sulfonate) (PSS), lithium 9,10-diphenylatlasene-2-sulfonate (lithium 9,10-diphenylanthracene-2-sulfonate, DPASLi. + It may include ) or a combination thereof.

[0044] The weight ratio of the solid electrolyte (SE) and the ion-conducting polymer (ICP) in the solid electrolyte separator (300) may be, for example, 99:1 to 1:99, 90:10 to 10:90, or 80:20 to 20:80. By having the solid electrolyte (SE) and the ion-conducting polymer (ICP) have a weight ratio within this range, the solid electrolyte separator (300) can have excellent mechanical strength and ion conductivity.

[0045] According to one embodiment, the ion-conducting polymer (ICP) may be a polymer matrix that forms the frame of the solid electrolyte separator (300). The ion-conducting polymer (ICP), i.e., the polymer matrix, may have a porous structure. Particles of the solid electrolyte (SE) may be filled within the ion-conducting polymer (ICP), i.e., the polymer matrix.

[0046] The solid electrolyte separator (300) may include one surface and another surface opposite thereto. Referring to FIG. 1, the solid electrolyte separator (300) may include an uneven surface formed on at least one surface. By including such an uneven surface, the solid electrolyte separator (300) can increase the contact area between the electrode and the separator on the surface adjacent to the uneven surface.

[0047] Surface roughness (R) of the uneven surface a ) may be, for example, 0.1 μm to 50 μm, 1 μm to 30 μm, or 5 μm to 25 μm. The surface roughness (R) of the uneven portion within this range. a By having ), the contact area between the electrode and the separator on the surface adjacent to the uneven portion can be increased. Surface roughness (R) of the uneven portion a If ) is below the above range, the effect of increasing the contact area may be negligible, and if it exceeds the above range, the adhesion between the electrode and the separator may decrease. In this specification, surface roughness refers to the average roughness R a Measures based on the value. R aThe value is defined as the average of the absolute values ​​of surface height deviations and can be measured using stylus profilers, non-contact optical profilers, or atomic force microscopes (AFM). For example, when using a stylus profiler, a mechanical tip moves along the film surface to collect height data of irregularities, and the average surface roughness is calculated based on this. On the other hand, non-contact optical profilers use optical interferometry techniques to analyze the surface quickly and precisely, while AFM measures surface irregularities with nanometer-level resolution to provide high-precision R a The value is calculated. These methods can be selectively applied depending on the size and characteristics of the film's irregularities.

[0048] FIG. 2 is a cross-sectional view illustrating a solid electrolyte separator according to another exemplary embodiment. Referring to FIG. 2, the solid electrolyte separator (300) may further include an adhesive layer (ADL) disposed on the uneven portion. By further including the adhesive layer (ADL) disposed on the uneven portion, the solid electrolyte separator (300) can strengthen the adhesion between the electrode and the separator on the surface adjacent to the uneven portion.

[0049] The adhesive layer (ADL) may comprise, for example, polyurethane, epoxy resin, polyvinyl alcohol (PVA), polyacrylate, silicone, polyvinyl acetate (PVAc), polyester, polyimide, polycarbonate, nylon, polyurethane acrylate, polyolefin, or a combination thereof.

[0050] FIG. 3 is a cross-sectional view illustrating a solid electrolyte separator according to another exemplary embodiment, and FIG. 4 is a top view of the solid electrolyte separator illustrated in FIG. 3. Referring to FIG. 3 and FIG. 4, the solid electrolyte separator (300) may further include a flat portion (FLA) formed at the edge portion of the uneven portion (EMA). That is, the solid electrolyte separator (300) may further include a flat portion (FLA) formed at least at the edge portion of one surface. By the solid electrolyte separator (300) further including such a flat portion (FLA), the effect of the uneven portion described above can be selectively imparted to the electrode adjacent to the separator or other components. That is, components requiring increased contact area may be adjacent to the uneven portion, while other components may be adjacent to the flat portion. When the solid electrolyte separator (300) includes an uneven portion (EMA) and a flat portion (FLA), the area occupied by the uneven portion (EMA) in the total area of ​​the solid electrolyte separator (300) may be 80% or more, 85% or more, 90% or more, or 95% or more of the total area. When the solid electrolyte separator (300) includes an uneven portion (EMA) and a flat portion (FLA), the area occupied by the uneven portion (EMA) in the total area of ​​the solid electrolyte separator (300) may be less than 99% of the total area.

[0051] FIG. 5 is a cross-sectional view illustrating a solid electrolyte separator according to another exemplary embodiment. When the solid electrolyte separator (300) includes an uneven portion (EMA) and a flat portion (FLA), it may further include an adhesive layer (ADL) disposed on the uneven portion (EMA). Since the description regarding the uneven portion (EMA), the flat portion (FLA), and the adhesive layer (ADL) can be applied as described above with reference to FIG. 3 and FIG. 4, a redundant description will be omitted.

[0052] [All-solid-state battery]

[0053] FIG. 6 is a cross-sectional view illustrating an all-solid-state battery according to an exemplary embodiment. Referring to FIG. 6, an all-solid-state battery according to an exemplary embodiment comprises a positive electrode (100); a negative electrode (200); and the solid electrolyte separator (300) described above, wherein the uneven portion is adjacent to the positive electrode (100).

[0054] [All-solid-state battery: positive electrode]

[0055] The positive electrode (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).

[0056] The positive current collector (110) may 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 (SUS), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof. In another embodiment, the positive current collector (110) may be omitted. 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). The carbon layer may include amorphous carbon, crystalline carbon, etc.

[0057] The positive active material layer (120) may include a positive active material (CAD) and a solid electrolyte.

[0058] The cathode active material (CAD) is a lithium-containing metal oxide or lithium-containing sulfide-based cathode active material, and any material commonly used in the industry may be used without limitation.

[0059] The lithium-containing metal oxide may be one or more of the composite oxides of lithium and a metal selected from, for example, cobalt, manganese, nickel, and combinations thereof, and specific examples thereof include Li a A 1-b B b D2 (wherein 0.90≤a≤1, and 0≤b≤0.5); Li a E 1-b B b O 2-c D c (In the above formula, 0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05); LiE 2-b B b O 4-c D c (In the above formula, 0≤b≤0.5, 0≤c≤0.05); Li a Ni 1-b-c Co b B c D α (In the above formula, 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 (In the above formula, 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 F2(wherein 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 (In the above equation, 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(In the above formula, 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 F2(wherein 0.90≤a≤1, 0≤b ≤0.5, 0≤c≤0.05, 0<α<2); Li a Ni b E c G d O2(wherein 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(wherein the above formula, 0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1); Li a NiGbO2 (wherein the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a CoGbO2(wherein the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a MnGbO2(wherein the above formula, 0.90≤a≤1, 0.001≤b≤0.1); Li a Mn2GbO4 (wherein the above formula, 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) Compounds represented by any one of the chemical formulas of Fe2(PO4)3(0≤f≤2); LiFePO4 may be used.

[0060] In the chemical formula representing the compound described above, A is Ni, Co, Mn, or a combination thereof; B is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof; D is O, F, S, P, or a combination thereof; E is Co, Mn, or a combination thereof; F is F, S, P, or a combination thereof; G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof; Q is Ti, Mo, Mn, or a combination thereof; I is Cr, V, Fe, Sc, Y, or a combination thereof; and J is V, Cr, Mn, Co, Ni, Cu, or a combination thereof. A compound having a coating layer added to the surface of the compound described above may also be used, and a mixture of the compound described above and the compound having a coating layer added may also be used. The coating layer applied to the surface of the aforementioned compound comprises, for example, a coating element compound of an oxide, hydroxide, oxyhydroxide, oxycarbonate, or hydroxycarbonate of a coating element. The compound forming this coating layer is amorphous or crystalline. The coating elements included in the coating layer are Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. 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 coating method is, for example, spray coating or immersion. Since specific coating methods are well understood by those skilled in the art, a detailed explanation will be omitted.

[0061] The cathode active material is, for example, Li a Ni x Co y M z O 2-b A b(In the above equation, 1.0≤a≤1.2, 0≤b≤0.2, 0.8≤x<1, 0 <y≤0.3, 0<z≤0.3, 및 x+y+z=1이고, M은 망간(Mn), 니오븀(Nb), 바나듐(V), 마그네슘(Mg), 갈륨(Ga), 실리콘(Si), 텅스텐(W), 몰리브덴(Mo), 철(Fe), 크롬(Cr), 구리(Cu), 아연(Zn), 티타늄(Ti), 알루미늄(Al), 보론(B) 또는 이들의 조합이고, A는 F, S, Cl, Br 또는 이들의 조합), LiNi x Co y Mn z O2(wherein the above equation, 0.8≤x≤0.95, 0≤y≤0.2, 0 <z≤0.2 및 x+y+z=1), LiNi x Co y Al z O2(wherein the above equation, 0.8≤x≤0.95, 0≤y≤0.2, 0 <z≤0.2 및 x+y+z=1), LiNi x Co y Mn z Al w O2(wherein the above equation, 0.8≤x≤0.95, 0≤y≤0.2, 0 <z≤0.2, 0<w≤0.2, 및 x+y+z+w=1), Li a Co x M y O 2-b A b (In the above formula, 1.0≤a≤1.2, 0≤b≤0.2, 0.9≤x≤1, 0≤y≤0.1, and x+y=1, M is manganese (Mn), niobium (Nb), vanadium (V), magnesium (Mg), gallium (Ga), silicon (Si), tungsten (W), molybdenum (Mo), iron (Fe), chromium (Cr), copper (Cu), zinc (Zn), titanium (Ti), aluminum (Al), boron (B) or a combination thereof, and A is F, S, Cl, Br or a combination thereof), Li a Ni x Mn y M' z O 2-b A b(In the above formula, 1.0≤a≤1.2, 0≤b≤0.2, 0 <x≤0.3, 0.5≤y<1, 0<z≤0.3, 및 x+y+z=1이고, M'는 코발트(Co), 니오븀(Nb), 바나듐(V), 마그네슘(Mg), 갈륨(Ga), 실리콘(Si), 텅스텐(W), 몰리브덴(Mo), 철(Fe), 크롬(Cr), 구리(Cu), 아연(Zn), 티타늄(Ti), 알루미늄(Al), 보론(B) 또는 이들의 조합이고, A는 F, S, Cl, Br 또는 이들의 조합), Li a M1 x M2 y PO 4-b X b (In the above equation, 0.90≤a≤1.1, 0≤x≤0.9, 0≤y≤0.5, 0.9 <x+y<1.1, 0≤b≤2 이며, M1이 크롬(Cr), 망간(Mn), 철(Fe), 코발트(Co), 니켈(Ni), 구리(Cu), 지르코늄(Zr) 또는 이들의 조합이며, M2가 마그네슘(Mg), 칼슘(Ca), 스트론튬(Sr), 바륨(Ba), 티탄(Ti), 아연(Zn), 보론(B), 니오븀(Nb), 갈륨(Ga), 인듐(In), 몰리브덴(Mo), 텅스텐(W), 알루미늄(Al), 실리콘(Si), 크롬(Cr), 바나듐(V), 스칸듐(Sc), 이트륨(Y) 또는 이들의 조합이며, X가 O, F, S, P 또는 이들의 조합), Li a M3 z PO4 (wherein 0.90≤a≤1.1, 0.9≤z≤1.1, and M3 is chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zirconium (Zr), or a combination thereof).

[0062] A lithium-containing sulfide-based cathode active material is an electrode material in which lithium is added, for example, to a sulfur-based cathode active material. The lithium-containing sulfide-based cathode active material may include, for example, Li2S, a Li2S-containing composite, or a combination thereof. By including Li2S, a Li2S-containing composite, or a combination thereof having high capacity as the lithium-containing sulfide-based cathode active material, the use of lithium metal can be omitted during the manufacture of secondary batteries. Since lithium metal has high reactivity and great ductility, it can reduce mass producibility during battery manufacturing. Therefore, if the use of lithium metal is omitted during the manufacture of secondary batteries, the mass producibility of the secondary battery can be improved.

[0063] A Li2S-containing composite is, for example, a composite of Li2S and a conductive material. The conductive material is, for example, an ionic conductive material, an electronic conductive material, or a combination thereof.

[0064] The ionic conductivity of an ion-conducting material is, for example, 1.0 × 10⁻⁶ at 25°C. -5 S / m or more, 1.0X10 -4 S / m or more, or 1.0X10 -3 It is greater than S / m. The ion-conducting material may have pores. By having pores, Li2S can be contained within the pores, which can increase the contact area between Li2S and the ion-conducting material and increase the specific surface area of ​​Li2S. The form of the ion-conducting material may be, for example, particulate ion-conducting material, plate-shaped ion-conducting material, rod-shaped ion-conducting material, or a combination thereof, but is not necessarily limited to these.

[0065] An ion-conducting material according to one embodiment may include, for example, a metal salt compound. The metal salt compound may include a lithium salt compound. The lithium salt compound may include, for example, LiF, LiCl, LiBr, LiI, or a combination thereof. According to one embodiment, a Li2S-containing composite comprising a lithium salt compound may include, for example, Li2S-LiF, Li2S-LiCl, Li2S-LiBr, Li2S-LiI, or a combination thereof. The metal salt compound may further include a boron group metal halide salt. The boron group metal halide salt may include, for example, AlF3, AlCl3, AlBr3, AlI3GaF3, GaCl3, GaBr3, GaI3InF3, InCl3, InBr3, InI3T1F3, T1Cl3, T1Br3, T1I3, or a combination thereof. According to one embodiment, a Li2S-containing composite further comprising a boron group metal halide salt is, for example, Li2S-LiF-AlF3, Li2S-LiF-AlCl3, Li2S-LiF-AlBr3, Li2S-LiF-AlI3, Li2S-LiF-GaF3, Li2S-LiF-GaCl3, Li2S-LiF-GaBr3, Li2S-LiF-GaI3, Li2S-LiF-InF3, Li2S-LiF-InCl3, Li2S-LiF-InBr3, Li2S-LiF-InI3, Li2S-LiF-TlF3, Li2S-LiF-TlCl3, Li2S-LiF-TlBr3, Li2S-LiF-TlI3, Li2S-LiCl-AlF3, Li2S-LiCl-AlCl3, Li2S-LiCl-AlBr3, Li2S-LiCl-AlI3, Li2S-LiCl-GaF3, Li2S-LiCl-GaCl3, Li2S-LiCl-GaBr3, Li2S-LiCl-GaI3, Li2S-LiCl-InF3, Li2S-LiCl-InCl3, Li2S-LiCl-InBr3, Li2S-LiCl-InI3, Li2S-LiCl-TlF3, Li2S-LiCl-TlCl3, Li2S-LiCl-TlBr3, Li2S-LiCl-TlI3, Li2S-LiBr-AlF3,Li2S-LiBr-AlCl3, Li2S-LiBr-AlBr3, Li2S-LiBr-AlI3, Li2S-LiBr-GaF3, Li2S-LiBr-GaCl3, Li2S-LiBr-GaBr3, Li2S-LiBr-GaI3, Li2S-LiBr-InF3, Li2S-LiBr-InCl3, Li2S-LiBr-InBr3, Li2S-LiBr-InI3, Li2S-LiBr-TlF3, Li2S-LiBr-TlCl3, Li2S-LiBr-TlBr3, Li2S-LiBr-TlI3, Li2S-LiI-AlF3, Li2S-LiI-AlCl3, Li2S-LiI-AlBr3, Li2S-LiI-AlI3, Li2S-LiI-GaF3, Li2S-LiI-GaCl3, Li2S-LiI-GaBr3, It may include Li2S-LiI-GaI3, Li2S-LiI-InF3, Li2S-LiI-InCl3, Li2S-LiI-InBr3, Li2S-LiI-InI3, Li2S-LiI-TlF3, Li2S-LiI-TlCl3, Li2S-LiI-TlBr3, Li2S-LiI-TlI3 or a combination thereof.

[0066] The electronic conductivity of an electronically conductive material is, for example, 1.0 × 10⁻⁶ at 25°C. 3 S / m or more, 1.0X10 4 S / m or more, or 1.0X10 5It is S / m or greater. The form of the electronically conductive material is, for example, particulate electronically conductive material, plate-shaped electronically conductive material, rod-shaped electronically conductive material, or a combination thereof, but is not necessarily limited to these. The electronically conductive material may be, for example, carbon, metal powder, metal compound, etc. When carbon is included as the electronically conductive material, a secondary battery having a high energy density per unit mass can be realized because carbon has high electronic conductivity and is lightweight. The electronically conductive material may have pores. By having pores in the electronically conductive material, Li2S can be contained within the pores, which can increase the contact area between Li2S and the electronically conductive material and increase the specific surface area of ​​Li2S. The pore capacity is, for example, 0.1 cc / g to 20.0 cc / g, 0.5 cc / g to 10 cc / g, or 0.5 cc / g to 5 cc / g. The average pore diameter is, for example, 1 nm to 100 nm, 1 nm to 50 nm, or 1 nm to 20 nm. The BET specific surface area of ​​the electron-conducting material having pores is 200 m² when the average pore diameter is 15 nm or less. 2 / g to 4500 m 2 / g, and if the average pore diameter is greater than 15 nm, 100 m 2 / g to 2500 m 2 It is / g. BET specific surface area, pore diameter, pore capacity, and average pore diameter can be obtained, for example, using the nitrogen adsorption method.

[0067] An electronically conductive material according to one embodiment may include, for example, carbon. Carbon may be any material containing carbon atoms, for example, used as a conductive material in the art. Carbon may be, for example, crystalline carbon, amorphous carbon, or a combination thereof. Carbon may be, for example, a calcined product of a carbon precursor. Carbon may be, for example, a carbon nanostructure. The carbon nanostructure may be, for example, a one-dimensional carbon nanostructure, a two-dimensional carbon nanostructure, a three-dimensional carbon nanostructure, or a combination thereof. The carbon nanostructure may be, for example, a carbon nanotube (CNT), a carbon nanofiber (CNF), a carbon nanobelt, a carbon nanorod, graphene, graphene oxide (GO), reduced graphene oxide (rGO), a graphene ball (GB), or a combination thereof. Carbon may be, for example, porous carbon or non-porous carbon. Porous carbon may include, for example, periodic and regular two-dimensional or three-dimensional pores. Porous carbon may be, for example, carbon black such as Ketjen black, acetylene black, Denka black, thermal black, Channel black; graphite, activated carbon, or a combination thereof. The form of carbon may be, for example, particle form, sheet form, flake form, etc., but is not limited thereto, and any form used as carbon in the relevant technical field is possible. The method of manufacturing a composite of Li2S or a Li2S-containing composite and carbon may be a dry method, a wet method, or a combination thereof, but is not limited thereto, and the method of manufacturing a composite of Li2S, a Li2S-containing composite and carbon in the relevant technical field may be, for example, milling, heat treatment, deposition, etc., but is not necessarily limited thereto, and any method used in the relevant technical field is possible. According to one embodiment, a Li2S-containing composite containing carbon may include, for example, Li2S-CNT, Li2S-CNF, or a combination thereof.

[0068] A Li2S-containing composite according to one embodiment may include a composite of Li2S, an ion-conducting material, and an electronically conductive material. According to one embodiment, a Li2S-containing composite comprising a composite of Li2S, an ion-conducting material, and an electron-conducting material is, for example, Li2S-LiF-CNT, Li2S-LiCl-CNT, Li2S-LiBr-CNT, Li2S-LiI-CNT, Li2S-LiF-CNF, Li2S-LiCl-CNF, Li2S-LiBr-CNF, Li2S-LiI-CNF, Li2S-LiF-AlF3-CNT, Li2S-LiF-AlCl3-CNT, Li2S-LiF-AlBr3-CNT, Li2S-LiF-AlI3-CNT, Li2S-LiF-GaF3-CNT, Li2S-LiF-GaCl3-CNT, Li2S-LiF-GaBr3-CNT, Li2S-LiF-GaI3-CNT, Li2S-LiF-InF3-CNT, Li2S-LiF-InCl3-CNT, Li2S-LiF-InBr3-CNT, Li2S-LiF-InI3-CNT, Li2S-LiF-TlF3-CNT, Li2S-LiF-TlCl3-CNT, Li2S-LiF-TlBr3-CNT, Li2S-LiF-TlI3-CNT, Li2S-LiCl-AlF3-CNT, Li2S-LiCl-AlCl3-CNT, Li2S-LiCl-AlBr3-CNT, Li2S-LiCl-AlI3-CNT, Li2S-LiCl-GaF3-CNT, Li2S-LiCl-GaCl3-CNT, Li2S-LiCl-GaBr3-CNT, Li2S-LiCl-GaI3-CNT, Li2S-LiCl-InF3-CNT, Li2S-LiCl-InCl3-CNT, Li2S-LiCl-InBr3-CNT, Li2S-LiCl-InI3-CNT, Li2S-LiCl-TlF3-CNT, Li2S-LiCl-TlCl3-CNT, Li2S-LiCl-TlBr3-CNT, Li2S-LiCl-TlI3-CNT, Li2S-LiBr-AlF3-CNT, Li2S-LiBr-AlCl3-CNT, Li2S-LiBr-AlBr3-CNT, Li2S-LiBr-AlI3-CNT, Li2S-LiBr-GaF3-CNT,Li2S-LiBr-GaCl3-CNT, Li2S-LiBr-GaBr3-CNT, Li2S-LiBr-GaI3-CNT, Li2S-LiBr-InF3-CNT, Li2S-LiBr-InCl3-CNT, Li2S-LiBr-InBr3-CNT, Li2S-LiBr-InI3-CNT, Li2S-LiBr-TlF3-CNT, Li2S-LiBr-TlCl3-CNT, Li2S-LiBr-TlBr3-CNT, Li2S-LiBr-TlI3-CNT, Li2S-LiI-AlF3-CNT, Li2S-LiI-AlCl3-CNT, Li2S-LiI-AlBr3-CNT, Li2S-LiI-AlI3-CNT, Li2S-LiI-GaF3-CNT, Li2S-LiI-GaCl3-CNT, Li2S-LiI-GaBr3-CNT, Li2S-LiI-GaI3-CNT, Li2S-LiI-InF3-CNT, Li2S-LiI-InCl3-CNT, Li2S-LiI-InBr3-CNT, Li2S-LiI-InI3-CNT, Li2S-LiI-TlF3-CNT, Li2S-LiI-TlCl3-CNT, Li2S-LiI-TlBr3-CNT, Li2S-LiI-TlI3-CNT, Li2S-LiF-AlF3-CNF, Li2S-LiF-AlCl3-CNF, Li2S-LiF-AlBr3-CNF, Li2S-LiF-AlI3-CNF, Li2S-LiF-GaF3-CNF, Li2S-LiF-GaCl3-CNF, Li2S-LiF-GaBr3-CNF, Li2S-LiF-GaI3-CNF, Li2S-LiF-InF3-CNF, Li2S-LiF-InCl3-CNF, Li2S-LiF-InBr3-CNF, Li2S-LiF-InI3-CNF, Li2S-LiF-TlF3-CNF, Li2S-LiF-TlCl3-CNF, Li2S-LiF-TlBr3-CNF, Li2S-LiF-TlI3-CNF, Li2S-LiCl-AlF3-CNF, Li2S-LiCl-AlCl3-CNF, Li2S-LiCl-AlBr3-CNF, Li2S-LiCl-AlI3-CNF, Li2S-LiCl-GaF3-CNF, Li2S-LiCl-GaCl3-CNF, Li2S-LiCl-GaBr3-CNF,Li2S-LiCl-GaI3-CNF, Li2S-LiCl-InF3-CNF, Li2S-LiCl-InCl3-CNF, Li2S-LiCl-InBr3-CNF, Li2S-LiCl-InI3-CNF, Li2S-LiCl-TlF3-CNF, Li2S-LiCl-TlCl3-CNF, Li2S-LiCl-TlBr3-CNF, Li2S-LiCl-TlI3-CNF, Li2S-LiBr-AlF3-CNF, Li2S-LiBr-AlCl3-CNF, Li2S-LiBr-AlBr3-CNF, Li2S-LiBr-AlI3-CNF, Li2S-LiBr-GaF3-CNF, Li2S-LiBr-GaCl3-CNF, Li2S-LiBr-GaBr3-CNF, Li2S-LiBr-GaI3-CNF, Li2S-LiBr-InF3-CNF, Li2S-LiBr-InCl3-CNF, Li2S-LiBr-InBr3-CNF, Li2S-LiBr-InI3-CNF, Li2S-LiBr-TlF3-CNF, Li2S-LiBr-TlCl3-CNF, Li2S-LiBr-TlBr3-CNF, Li2S-LiBr-TlI3-CNF, Li2S-LiI-AlF3-CNF, Li2S-LiI-AlCl3-CNF, Li2S-LiI-AlBr3-CNF, Li2S-LiI-AlI3-CNF, Li2S-LiI-GaF3-CNF, Li2S-LiI-GaCl3-CNF, Li2S-LiI-GaBr3-CNF, Li2S-LiI-GaI3-CNF, Li2S-LiI-InF3-CNF, Li2S-LiI-InCl3-CNF, Li2S-LiI-InBr3-CNF, Li2S-LiI-InI3-CNF, Li2S-LiI-TlF3-CNF, Li2S-LiI-TlCl3-CNF, Li2S-LiI-TlBr3-CNF, 또는 Li2S-LiI-TlI3-CNF, 또는 이들의 임의의 조합을 포함할 수 있다.,

[0069] The positive active material layer (120) may include a solid electrolyte. The solid electrolyte included in the positive active material layer may include a sulfide-based solid electrolyte with excellent lithium ion conductivity characteristics. The sulfide-based solid electrolyte may be the same as or different from the sulfide-based solid electrolyte included in the aforementioned solid electrolyte separator (300). A detailed description of the sulfide-based solid electrolyte is omitted below, as the content regarding the sulfide-based solid electrolyte included in the aforementioned solid electrolyte separator (300) can be applied as is.

[0070] The positive active material layer (120) may further 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 active material and the solid electrolyte. The conductive material may include a carbon-based material. The conductive material may include, for example, at least one of graphite, carbon black, acetylene black, carbon nanofiber, or carbon nanotube. Meanwhile, the positive active material layer (120) may omit the conductive material.

[0071] The positive active material layer (120) may further include a binder. The binder included in the positive active material layer (120) is, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited to these and any binder used in the relevant technical field is possible. In another embodiment, the binder may be omitted.

[0072] [All-solid-state battery: Cathode]

[0073] The negative electrode (200) may include a negative electrode current collector (210). In one embodiment, the negative electrode (200) may have lithium metal and / or a lithium alloy deposited on the negative electrode current collector (210) by charging. In this case, the lithium metal and / or lithium alloy may act as a lithium reservoir. That is, the all-solid-state battery according to one embodiment may be a lithium metal battery.

[0074] The negative electrode (220) may include a negative electrode current collector (210) and a coating layer (220) disposed on the negative electrode current collector (210). The negative electrode current collector (210) may provide a reference surface on which a lithium metal layer (230) or a coating layer (220) is disposed. 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. The material constituting the negative electrode current collector (210) may include at least one metal selected from the group consisting of, for example, 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 to 20 μm, for example 5 to 15 μm, for example 7 to 10 μm.

[0075] 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) is, for example, in the form of a plate or foil. In another embodiment, the negative current collector (210) may be omitted.

[0076] The coating layer (220) may be configured to allow lithium metal to grow between the negative electrode current collector (210) and the coating layer (220) and / or within the coating layer (220) during charging of the all-solid-state battery. The coating layer (220) may serve as a protective layer for the lithium metal and simultaneously suppress the precipitation and growth of lithium dendrites. The coating layer (220) may include, for example, a metal-carbon composite.

[0077] The metal-carbon composite comprising the coating layer (220) is a negative electrode material capable of forming an alloy or compound with, for example, lithium. The metal-carbon composite has, for example, a particle form. The average particle size of the metal-carbon composite having a particle form is, for example, 4 μm or less, 3 μm or less, 2 μm or less, 1 μm or less, 500 nm or less, 300 nm or less, or 100 nm or less. The average particle size of the metal-carbon composite having a particle form is, for example, 10 nm to 4 μm, 10 nm to 3 μm, 10 nm to 2 μm, 10 nm to 1 μm, or 10 nm to 500 nm, 10 nm to 300 nm, or 10 nm to 100 nm. By having the average particle size of the metal-carbon composite within this range, reversible absorption and / or desorption of lithium during charging and discharging may be more facilitated. The average particle size of the metal-carbon composite is, for example, the median diameter (D50) measured using a laser particle size distribution meter.

[0078] A metal-carbon composite may include, for example, metal particles and a carbon-based material. The metal particles and the carbon-based material may each have a particle form, for example. A metal-carbon composite may be, for example, a simple mixture of metal particles and a carbon-based material. The metal particles in the metal-carbon composite may include gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), and zinc (Zn), or combinations thereof. However, this is not limited thereto, and any metal or metalloid used in the art to form alloys or compounds with lithium is acceptable. The carbon-based material in the metal-carbon composite may include, for example, amorphous carbon, crystalline carbon, porous carbon, or a combination thereof. The carbon-based material in the metal-carbon composite may be amorphous carbon. The carbonaceous material within the metal-carbon composite may include, for example, carbon black, acetylene black, furnace black, Kettjen black, graphene, or a combination thereof. Amorphous carbon may be carbon that does not have crystallinity or has very low crystallinity. The carbonaceous material within the metal-carbon composite may be, for example, porous carbon. The pore volume contained in the porous carbon may be, for example, 0.1 cc / g to 10.0 cc / g, 0.5 cc / g to 5 cc / g, or 0.1 cc / g to 1 cc / g. The average pore diameter contained in the porous carbon may be, for example, 1 nm to 50 nm, 1 nm to 30 nm, or 1 nm to 10 nm. The BET specific surface area of ​​the porous carbon is, for example, 100 m² 2 / g to 3,000 m 2It can be / g. The BET specific surface area of ​​porous carbon can be measured, for example, according to ISO 9277:2022.

[0079] The mixing ratio of the metal particles and carbon-based material included in the coating layer (220) may be, for example, 1:10 to 2:1, 1:5 to 1:1, or 1:4 to 1:2 by weight.

[0080] The metal-carbon composite may be, for example, a composite of metal particles and a carbon-based material. The carbon-based material may be, for example, a carbon-based support. The metal-carbon composite may include, for example, a carbon-based support and metal particles supported on the carbon-based support. By having such a structure, the localization of metal particles within the coating layer (220) is prevented and a uniform distribution can be obtained. Consequently, the cycle characteristics of the all-solid-state battery including the coating layer (220) can be further improved.

[0081] Metal particles supported on a carbon-based support may include, for example, a metal, a metal oxide, a composite of a metal and a metal oxide, or a combination thereof. The metal may include, for example, gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), tellurium (Te), and zinc (Zn). The metal oxide may include, for example, gold (Au) oxide, platinum (Pt) oxide, palladium (Pd) oxide, silicon (Si) oxide, silver (Ag) oxide, aluminum (Al) oxide, bismuth (Bi) oxide, tin (Sn) oxide, tellurium (Te) oxide, and zinc (Zn) oxide. The metal oxide may include, for example, Au x O y (0 <x≤2, 0<y≤3), Pt x O y (0 <x≤1, 0<y≤2), Pd x O y (0 <x≤1, 0<y≤1), Si x Oy (0 <x≤1, 0<y≤2), Ag x The y (0 <x≤2, 0<y≤1), Al x The y (0 <x≤2, 0<y≤3), Bi x The y (0 <x≤2, 0<y≤3), Sn x The y (0 <x≤1, 0<y≤2), Te x The y (0 <x≤1,0<y≤3), Zn x The y (0 <x≤1, 0<y≤1) 또는 이들의 조합을 포함할 수 있다. 금속과 금속 산화물의 복합체는 예를 들어 Au와 Au x The y (0 <x≤2, 0<y≤3)의 복합체, Pt와 Pt x The y (0 <x≤1, 0<y≤2)의 복합체, Pd와 Pd x The y (0 <x≤1, 0<y≤1)의 복합체, Si와 Si x The y (0 <x≤1, 0<y≤2)의 복합체, Ag 와 Ag x The y (0 <x≤2, 0<y≤1)의 복합체, Al과 Al x The y (0 <x≤2, 0<y≤3)의 복합체, Bi와 Bi x The y (0 <x≤2, 0<y≤3)의 복합체, Sn과 Sn x The y (0 <x≤1, 0<y≤2)의 복합체, Te과 Te x The y (0 <x≤1, 0<y≤3), Zn과 Zn x The y (0 <x≤1, 0<y≤1)의 복합체, 또는 이들의 조합을 포함할 수 있다.

[0082] A carbon-based support is, for example, amorphous carbon. Amorphous carbon is, for example, carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), graphene, activated carbon, carbon nanofiber (CNF), carbon nanotube (CNT), etc., but is not necessarily limited to these, and any carbon classified as amorphous carbon in the relevant technical field is acceptable. Amorphous carbon is carbon that does not have crystallinity or has very low crystallinity, and is distinguished from crystalline carbon or graphite-based carbon.

[0083] The coating layer (220) may optionally further include a binder. The binder included in the coating layer (220) may be, for example, styrene-butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, etc., but is not necessarily limited to these, and any binder used in the relevant technical field may be used. The binder may be composed of a single binder or a plurality of different binders.

[0084] The coating layer (220) may further include other additives in addition to the metal-carbon composite. The coating layer (220) may further include at least one additive selected from the group consisting of, for example, fillers, coating agents, dispersants, and ion-conducting aids.

[0085] The coating layer (220) may further include a solid electrolyte. The solid electrolyte may be a material selected from, for example, a solid electrolyte included in a solid electrolyte separator. The solid electrolyte included in the coating layer (220) may act as a reaction site where the formation of lithium metal begins within the coating layer (220), act as a space where the formed lithium metal is stored, or act as a pathway for transporting lithium ions. The solid electrolyte may be omitted.

[0086] [All-solid-state battery: inert component]

[0087] Referring to FIG. 6, the positive electrode (100) of an all-solid-state battery according to one embodiment further comprises a positive electrode current collector (110) and a positive electrode active material layer (120) disposed on the positive electrode current collector (110), and may further comprise an inactive member (400) disposed on one side of the positive electrode active material layer (120). The inactive member (400) is disposed on one side of the positive electrode active material layer (120) and may be disposed between a solid electrolyte separator (300) and a positive electrode current collector (110) facing the solid electrolyte separator (300).

[0088] By including an inert member (400), cracking of the solid electrolyte separator (300) is prevented during the manufacturing of the all-solid-state battery and / or during charging and discharging, thereby improving the cycle characteristics of the all-solid-state battery. In an all-solid-state battery that does not include an inert member (400), uneven pressure is applied to the solid electrolyte separator (300) in contact with the positive electrode (100) during the manufacturing of the all-solid-state battery and / or during charging and discharging, causing cracking in the solid electrolyte separator (300), and the likelihood of a short circuit occurring due to the growth of lithium metal through this increases.

[0089] In an all-solid-state battery, the thickness of the inert member (400) is greater than or equal to the thickness of the positive active material layer (120). Alternatively, in an all-solid-state battery, the thickness of the inert member (400) is substantially equal to the thickness of the positive electrode (100). Since the thickness of the inert member (400) is equal to the thickness of the positive electrode (100), a uniform pressure is applied between the positive electrode (100) and the solid electrolyte separator (300), and the positive electrode (100) and the solid electrolyte separator (300) are sufficiently in contact, thereby reducing the interfacial resistance between the positive electrode (100) and the solid electrolyte separator (300). Additionally, during the pressurized manufacturing process of the all-solid-state battery, the solid electrolyte separator (300) is sufficiently sintered, thereby reducing the internal resistance of the solid electrolyte separator (300) and the all-solid-state battery containing it.

[0090] The inert member (400) surrounds the side of the anode (100) and comes into contact with the solid electrolyte separator (300). By the inert member (400) surrounding the side of the anode (100) and coming into contact with the solid electrolyte separator (300), cracks in the solid electrolyte separator (300) that occur due to pressure differences during the pressing process in the solid electrolyte separator (300) that does not come into contact with the anode (100) can be effectively suppressed. The inert member (400) surrounds the side of the anode active material layer (120). The inert member (400) surrounds the side of the anode active material layer (120) and comes into contact with the solid electrolyte separator (300), and the anode (100) is separated from the cathode (200). Therefore, the possibility of a short circuit occurring due to physical contact between the anode (100) and the cathode (200) or due to overcharging of lithium is suppressed. For example, by placing an inert member (400) on one side of the positive active material layer (120), the possibility of a short circuit occurring due to contact between the positive current collector (110) and the negative electrode (200) is more effectively suppressed.

[0091] The area of ​​the solid electrolyte separator (300) in contact with the anode (200) is smaller than the area of ​​the solid electrolyte separator (300). An inert member (400) is arranged to surround the side of the anode active material layer (120) to compensate for the difference in area between the anode active material layer (120) and the solid electrolyte separator (300). By compensating for the difference in area between the anode active material layer (120) and the solid electrolyte separator (300) with the area of ​​the inert member (400), cracks in the solid electrolyte separator (300) caused by pressure differences during the pressing process are effectively suppressed. For example, the sum of the area of ​​the anode active material layer (120) and the area of ​​the inert member (400) is equal to the area of ​​the solid electrolyte separator (300).

[0092] In the present disclosure, "identical" area, length, width, thickness, and / or shape includes all cases having "substantially identical" area, length, width, thickness, and / or shape, except where the area, length, width, thickness, and / or shape are intentionally made different from one another. "Identical" area, length, width, and / or thickness includes a range in which the unintended difference in the area, length, width, and / or thickness of the objects being compared is, for example, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1%.

[0093] The inert member (400) may be a gasket. By using a gasket as the inert member (40), cracks in the electrolyte layer (30) caused by pressure differences during the pressurization process can be effectively suppressed.

[0094] The inert member (400) has, for example, a single-layer structure. Alternatively, although not shown in the drawings, the inert member (400) may have a multi-layer structure. In the inert member (400) having a multi-layer structure, each layer may have a different composition. The inert member having a multi-layer structure may have, for example, a two-layer structure, a three-layer structure, a four-layer structure, or a five-layer structure. The inert member (400) having a multi-layer structure may include, for example, one or more adhesive layers and one or more support layers. The adhesive layer effectively prevents separation between the anode (100) and the solid electrolyte separator (300) due to volume changes of the anode (100) occurring during the charging and discharging process of the all-solid-state battery, for example, and improves the film strength of the inert member (400) by providing a bonding force between the support layer and other layers. The support layer provides support to the inert member (400), prevents non-uniformity of pressure applied to the solid electrolyte separator (300) during the pressurization process or the charge / discharge process, and prevents deformation of the all-solid-state battery being manufactured.

[0095] The inert member (400) is, for example, a flame-retardant inert member. By providing flame retardancy, the flame-retardant inert member can prevent thermal runaway and the possibility of ignition of the all-solid-state battery. Consequently, the safety of the all-solid-state battery is further improved. By absorbing residual moisture within the all-solid-state battery, the flame-retardant inert member prevents the deterioration of the all-solid-state battery, thereby improving the lifespan characteristics of the all-solid-state battery.

[0096] The flame-retardant inert member includes a filler in addition to the matrix. The filler may be placed inside the matrix, on the surface of the matrix, or both inside and on the surface. The filler is, for example, an inorganic material. The filler included in the flame-retardant inert member is, for example, a moisture getter. The filler prevents the degradation of the all-solid-state battery by removing residual moisture within the all-solid-state battery through the adsorption of moisture, for example, at a temperature below 100°C. Furthermore, if the temperature of the all-solid-state battery rises above 150°C due to thermal runaway caused by the charging and discharging process or external impact, the filler can effectively suppress ignition of the all-solid-state battery by releasing the adsorbed moisture. That is, the filler is, for example, a flame retardant. The filler is, for example, a metal hydroxide having moisture adsorption properties. The metal hydroxide included in the filler is, for example, Mg(OH)2, Fe(OH)3, Sb(OH)3, Sn(OH)4, TI(OH)3, Zr(OH)4, Al(OH)3, or a combination thereof. The content of the filler included in the flame-retardant inert member is, for example, 10 to 80 parts by weight, 20 to 80 parts by weight, 30 to 80 parts by weight, 40 to 80 parts by weight, 50 to 80 parts by weight, 60 to 80 parts by weight, or 65 to 80 parts by weight, based on 100 parts by weight of the flame-retardant inert member (4).

[0097] The flame-retardant inert member may further include, for example, a binder. The binder may include, for example, a curable polymer or a non-curable polymer. A curable polymer is a polymer that is cured by heat and / or pressure. A curable polymer is, for example, a solid at room temperature. The flame-retardant inert member (400) includes, for example, a heat-pressure curable film and / or a cured product thereof. A heat-pressure curable polymer is, for example, Toray's TSA-66.

[0098] The flame-retardant inert material may additionally include other materials in addition to the aforementioned substrate, reinforcing material, filler, and binder. The flame-retardant inert material may further include one or more materials selected from, for example, paper, insulating polymers, ion-conducting polymers, insulating inorganic materials, oxide-based solid electrolytes, and sulfide-based solid electrolytes. The insulating polymer may be an olefin-based polymer such as, for example, polypropylene (PP) or polyethylene (PE).

[0099] The inert member (400) is a member that does not contain a material having electrochemical activity, such as an electrode active material. The electrode active material is a material that absorbs / releases lithium. The inert member (400) is a member made of a material other than the electrode active material, such as a material used in the relevant technical field.

[0100] [All-solid-state battery: Solid electrolyte separator]

[0101] As the above description can be applied as is to the composition included in the solid electrolyte separator (300), redundant descriptions will be omitted.

[0102] FIG. 6 is a cross-sectional view illustrating an all-solid-state battery according to an exemplary embodiment, and FIG. 7 is an enlarged schematic view illustrating area A of FIG. 6.

[0103] Referring to FIGS. 6 and 7, the uneven surface formed on at least one surface of the solid electrolyte separator (300) may be formed adjacent to the anode (100). Specifically, the uneven surface may be formed adjacent to the anode active material layer (120).

[0104] Referring to FIG. 7, the positive active material (CAM) contained in the positive active material layer (120) can be inserted into the groove of the uneven portion, and a void can be formed between the solid electrolyte separator (300) and the positive active material (CAM) due to morphological characteristics. This void can perform the role of absorbing and buffering the volume change of the electrode that occurs during the charging and discharging process. This can further improve the long-term performance and stability of an all-solid-state battery using a positive active material (CAM) that is sensitive to volume change depending on the charging and discharging process.

[0105] Referring to FIGS. 6 and 7, an all-solid-state battery according to one embodiment may further include an adhesive layer (ADL) disposed on an uneven portion adjacent to a positive electrode active material layer (120). That is, an all-solid-state battery according to one embodiment may further include an adhesive layer (ADL) between the uneven portion and the positive electrode. Details regarding the adhesive layer (ADL) will be omitted as the above-described details can be applied as is.

[0106] A solid electrolyte separator (300) included in an all-solid-state battery according to one embodiment may further include an uneven portion adjacent to the positive active material layer (120) and a flat portion formed at the edge portion of said uneven portion. That is, in an all-solid-state battery according to one embodiment, the solid electrolyte separator (300) may further include a flat portion formed at least on the edge portion of one surface. When the all-solid-state battery includes an inert member (400), the solid electrolyte separator (300) may include a flat portion on the surface adjacent to the inert member (400). By including an uneven portion between the positive active material layer (120) and the solid electrolyte separator (300), such a solid electrolyte separator (300) can absorb and buffer volume changes and, at the same time, improve adhesion with the inert member (400).

[0107] FIG. 8 is a cross-sectional view illustrating an all-solid-state battery according to another exemplary embodiment. Referring to FIG. 8, the all-solid-state battery according to one embodiment may further include a lithium metal layer (230) disposed between the coating layer (220) and the negative current collector (210).

[0108] The lithium metal layer (230) may be a component formed by charging the all-solid-state battery. Although not shown in the drawing, the all-solid-state battery may further include a lithium metal layer disposed inside the coating layer (220) by charging.

[0109] The lithium metal layer (230) may include lithium or a lithium alloy. Since the lithium metal layer (230) is a metal layer containing lithium, it can function as a lithium reservoir. The lithium alloy is, for example, Li-Al alloy, Li-Sn alloy, Li-In alloy, Li-Ag alloy, Li-Au alloy, Li-Zn alloy, Li-Ge alloy, Li-Si alloy, etc., but is not limited to these; any alloy used as a lithium alloy in the relevant technical field may be possible. The lithium metal layer (230) may be composed of one of these alloys or lithium, or may be composed of various types of alloys. The lithium metal layer (230) may be, for example, a plated layer. The lithium metal layer (230) may be deposited between the coating layer (220) and the negative current collector (210) during the charging process of an all-solid-state battery, for example.

[0110] In another embodiment, the lithium metal layer (230) within the negative electrode may be provided, for example, between the negative electrode current collector (210) and the coating layer (220) before assembly of the all-solid-state battery. When the lithium metal layer (230) is placed between the negative electrode current collector (210) and the coating layer (220) before assembly of the all-solid-state battery, the lithium metal layer (230) acts as a lithium reservoir because it is a metal layer containing lithium. For example, a lithium foil may be placed between the negative electrode current collector (210) and the negative electrode coating layer (220) before assembly of the all-solid-state battery.

[0111] When a lithium metal layer (230) is precipitated by charging after assembly of the all-solid-state battery, the energy density of the all-solid-state battery (10) can be increased because the lithium metal layer (230) is not included during assembly of the all-solid-state battery. When charging the all-solid-state battery, it can be charged beyond the charging capacity of the coating layer (220). That is, the coating layer (220) can be overcharged. Lithium can be absorbed in the coating layer (220) at the beginning of charging. When charging beyond the capacity of the coating layer (220), lithium can be precipitated, for example, between the coating layer (220) and the negative electrode current collector (210). A lithium metal layer (230) can be formed by the precipitated lithium.

[0112] The lithium metal layer (230) can be composed mainly of lithium (i.e., metallic lithium). During discharge, the lithium in the lithium metal layer (230) can be ionized and move to the positive electrode (100). In other words, lithium can be used as a negative electrode active material in a solid-state battery. In addition, since the coating layer (220) covers the lithium metal layer (230), the coating layer (220) can protect the lithium metal layer (230) and simultaneously suppress the precipitation growth of lithium dendrites. Therefore, the coating layer (220) can suppress short circuits and capacity degradation of the solid-state battery and improve the cycle characteristics of the solid-state battery.

[0113] When a lithium metal layer (230) is formed by charging after assembly of the all-solid-state battery, the negative electrode, i.e., the negative electrode current collector (210) and the coating layer (220) and the region between them may be a Li-free region that does not contain lithium (Li) in the initial state or after complete discharge of the all-solid-state battery (10).

[0114] The creative idea is explained in more detail through the following examples and comparative examples. However, the examples are intended to illustrate the creative idea and do not limit the scope of the creative idea to these examples alone.

[0115]

[0116] Example 1: Solid electrolyte separator with uneven surface

[0117] Manufacturing of anodes

[0118] Li2S, LiI, and AlI3 were mixed in a weight ratio of 40:5:15. The mixture was mechanically milled using a ball mill to prepare a Li2S-LiI-AlI3 composite. The milling conditions were 25°C and 450 rpm for 10 hours. The milling energy applied to the sample during milling was 20 G. The Li2S-LiI-AlI3 composite thus prepared was mixed with carbon nanofiber (CNF) in a weight ratio of 60:10. The mixture was mechanically milled using a ball mill to prepare a Li2S-LiI-AlI3-CNF composite. The milling conditions were 25°C and 450 rpm for 10 hours. The milling energy applied to the sample during milling was 20 G. The Li2S-LiI-AlI3-CNF composite thus prepared was used as the cathode active material.

[0119] Li6PS5Cl (D50 = 1.0 μm, crystalline), an argyrodite-type crystal, was prepared as the solid electrolyte. The positive active material and the solid electrolyte were prepared such that the weight ratio of the positive active material to the solid electrolyte was 70 to 30, respectively.

[0120] PTFE was prepared as a binder. An anode mixture was prepared by mixing the anode active material, solid electrolyte, and binder. The mixing ratio of the anode mixture was prepared such that the anode active material : solid electrolyte : binder = 70 : 30 : 1.2. The anode mixture was obtained by dry mixing using a mixer.

[0121] An anode was prepared by placing the anode composite on one side of an anode current collector made of aluminum foil coated with carbon on one side and plate pressing at a pressure of 200 MPa for 10 minutes. The thickness of the anode was approximately 120 μm. The thickness of the anode active material layer was approximately 100 μm, and the thickness of the carbon-coated aluminum foil was approximately 20 μm. The area of ​​the anode active material layer and the anode current collector were the same.

[0122] Manufacturing of the cathode

[0123] A SUS foil with a thickness of 10 μm was prepared as a cathode current collector. As a metal-carbon composite, carbon black (CB) with a primary particle size of about 30 nm and silver (Ag) particles with an average particle diameter of about 60 nm were prepared.

[0124] 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 a PVDF binder (Kureha # 9300) was added to prepare a mixed solution. A slurry was prepared by stirring the mixed solution while gradually adding NMP to it. The prepared slurry was applied to a SUS sheet using a bar coater, dried in air at 80°C for 10 minutes, and then vacuum dried at 40°C for 10 hours to prepare a laminate. The prepared laminate was cold-roll-pressed to flatten the surface, thereby preparing a cathode having a coating layer / cathode current collector structure. The thickness of the coating layer was approximately 15 μm. The surface area of ​​the cathode coating layer and the cathode current collector were the same.

[0125] Manufacturing of solid electrolyte membranes

[0126] To manufacture a solid electrolyte membrane, a Li6PS5Cl crystalline solid electrolyte (D 50 A Li6PS5Cl solid electrolyte (=3.0 μm) was prepared. A mixture was prepared in which 10 parts by weight (wt%) of polyethylene oxide (PEO) ion-conducting polymer was added to the Li6PS5Cl solid electrolyte, which accounted for 90 parts by weight (wt%) of the total weight. A homogeneous slurry was formed by adding N,N-dimethylformamide (DMF) as a solvent to the prepared mixture. The prepared slurry was applied onto a 15 μm thick nonwoven fabric placed on a 75 μm thick PET substrate. The applied laminate was dried in air at 80°C for 10 minutes to form a base laminate.

[0127] Subsequently, a sandblasting technique was used to form the irregularities. The particles used in the sandblasting technique were alumina (Al2O₃) abrasives with an average particle size of 5 μm, and were sprayed with 2 bar of compressed air for 10 seconds. Through this process, irregularities were formed on the surface of the laminate.

[0128] Manufacturing of inert components

[0129] A flame-retardant inert member was manufactured by mixing cellulose fiber, glass fiber, aluminum hydroxide (Al(OH)3), an acrylic binder, and a solvent, forming the mixture into a gasket shape, and then removing the solvent.

[0130] The weight ratio of cellulose fiber, glass fiber, aluminum hydroxide (Al(OH)3), and acrylic binder was 20:8:70:2.

[0131] Before placing the manufactured flame-retardant inert material on a solid electrolyte membrane, it was vacuum heat-treated at 80°C for 5 hours to remove moisture and other substances from the flame-retardant inert material.

[0132] Manufacturing of all-solid-state batteries

[0133] The previously fabricated cathode, a solid electrolyte separator on the cathode, and an anode on the solid electrolyte separator were sequentially arranged and laminated so that the uneven surface of the solid electrolyte separator came into contact with the anode. A gasket was placed around the anode to surround it and contact the solid electrolyte separator, thereby preparing a laminate. The flame-retardant inert material was used as the gasket. The prepared laminate was subjected to plate pressing at 85°C and a pressure of 500 MPa for 30 minutes. This pressurization process sintered the solid electrolyte separator, thereby improving battery characteristics. The thickness of the sintered solid electrolyte layer was approximately 45 μm. The area of ​​the solid electrolyte layer was equal to the area of ​​the cathode layer.

[0134] An all-solid-state battery was manufactured by placing a pressurized laminate into a pouch and vacuum sealing it. Parts of the positive and negative current collectors were extended outside the sealed battery to serve as the positive and negative terminals.

[0135] Example 2: Solid electrolyte separator with an adhesive layer formed on the uneven surface

[0136] A solid electrolyte separator and an all-solid-state battery were fabricated in the same manner as in Example 1, except that a slurry was prepared by mixing PVDF and NMP solvents in a 1:9 ratio on the uneven surface, an adhesive layer was uniformly applied to the uneven surface using a bar coater, the applied adhesive layer was dried in air at 80°C for 10 minutes to remove the solvent and stabilize the adhesive layer, and after the first drying, the adhesive layer was heat-treated in a vacuum oven at 120°C for 2 hours to increase the structural strength of the adhesive layer and completely cure the adhesive layer to form the adhesive layer.

[0137] Example 3: Solid electrolyte separator with an uneven portion and a flat portion formed at the edge of the uneven portion

[0138] A solid electrolyte separator and an all-solid-state battery were fabricated in the same manner as in Example 1, except that before using the sandblaster technique, a masking tape was used to cover the edge portion of the solid electrolyte separator, covering 10% of the total area, and after applying the sandblaster technique, the masking tape was removed.

[0139] Example 4: Separator having an adhesive layer formed on the uneven portion and no adhesive layer formed on the flat portion

[0140] A solid electrolyte separator and an all-solid-state battery were fabricated using the same method as in Example 1, except that the adhesive layer application method of Example 2 was applied only to the uneven portion of the solid electrolyte separator fabricated according to Example 3.

[0141] Comparative Example 1: Solid electrolyte separator

[0142] A solid electrolyte separator and an all-solid-state battery were fabricated in the same manner as in Example 1, except that no uneven parts were formed.

[0143] Evaluation Example: Battery Performance Evaluation

[0144] The charge and discharge characteristics of the all-solid-state batteries prepared in Examples 1 to 4 and Comparative Example 1 were evaluated by the following charge and discharge test.

[0145] The charge and discharge test was performed by placing the all-solid-state battery in a constant temperature bath at 45°C. Charging was carried out in CC mode. The battery was charged at 0.05 C until the voltage reached 2.8 V, and discharge was carried out in CC mode at 0.05 C until it reached 1.0 V.

[0146] The discharge capacity of the first cycle was set as the standard capacity. The standard capacity is expressed as the specific capacity in Table 1 below. The initial efficiency is expressed by Equation 1 below.

[0147] <Mathematical Formula 1>

[0148] Initial efficiency [%] = [1st cycle discharge capacity / 1st cycle charge capacity] × 100

[0149] The cycles after the second cycle were charged and discharged under the same conditions as the first cycle. The SOH was measured after each cycle, and the charge-discharge test was repeated until the SOH reached 80%. The number of cycles in which the SOH reached 80% is indicated as the number of cycles in Table 1 below.

[0150] The high-rate characteristics of the all-solid-state batteries prepared in Examples 1 to 4 and Comparative Example 1 were evaluated by the following high-rate charge / discharge test.

[0151] The high-rate charge / discharge test was performed by placing the all-solid-state battery in a constant temperature bath at 45°C. Charging was carried out in CC mode. Charging was performed at 1 C until the battery voltage reached 2.8 V, and discharging was carried out in CC mode at 0.1 C until it reached 1.0 V. The high-rate characteristic (%) was calculated by dividing the discharge capacity in the high-rate charge / discharge test by the charge capacity in the high-rate charge / discharge test to determine the percentage (%), and is shown in Table 1 below.

[0152] The results of the charge / discharge test are summarized in Table 1 below.

[0153] Initial Efficiency [%] Specific Capacity [mAh / g] Number of Cycles [cycles, @SOH = 80%] High Rate Characteristics [%] Example 19 1895 10095 Example 29 0883 15394.5 Example 3 89.5882 19594.3 Example 4 89.58842 4594.2 Comparative Example 18 5750 1025

[0154] As shown in Table 1, the all-solid-state batteries of Examples 1 to 4 exhibited improved charge-discharge characteristics compared to the all-solid-state battery of Comparative Example 1. The charge-discharge characteristics of the all-solid-state batteries of Examples 1 to 4 were improved by applying a solid electrolyte separator having an uneven surface formed on the side adjacent to the positive electrode active material layer. In the all-solid-state secondary battery of Comparative Example 1, the charge-discharge characteristics deteriorated due to the volume change of the positive electrode that occurred during the charge-discharge process.

[0155] Although an exemplary embodiment has been described in detail above with reference to the attached drawings, the present creative idea is not limited to such examples. It is obvious that a person skilled in the art to which the present creative idea belongs can derive various variations or modifications within the scope of the technical idea described in the patent claims, and these also naturally fall within the technical scope of the present creative idea.

Claims

1. Solid electrolyte; and Includes an ion-conducting polymer; A solid electrolyte separator comprising an uneven surface formed on at least one surface.

2. In Paragraph 1, The above solid electrolyte includes a sulfide-based solid electrolyte, and The above sulfide-based solid electrolytes are 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, Z is one of Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, 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), Li 7-x PS 6-x I x (0 <x≤2) 또는 이들의 조합을 포함하는, 고체 전해질 분리막.

3. In Paragraph 1, The above ion-conducting polymer is polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene (PVDF-HFP), poly(styrene-b-ethylene oxide) block copolymer (PS-PEO), poly(styrene-butadiene), poly(styrene-isoprene-styrene), poly(styrene-b-divinylbenzene) block copolymer, poly(styrene-ethylene oxide-styrene) block copolymer, polystyrene sulfonate (PSS), polyvinyl fluoride (PVF), poly(methylmethacrylate) (PMMA), polyethylene glycol (PEG), polyacrylonitrile (PAN), polytetrafluoroethylene (PTFE), polyethylenedioxythiophene (PEDOT), polypyrrole (PPY), polyacrylonitrile (PAN), polyaniline, polyacetylene, Nafion, Aquivion, Flemion, Gore, Aciplex, Morgane ADP, sulfonated poly(ether ether ketone) (SPEEK), sulfonated poly(arylene ether ketone ketone sulfone) (SPAEKKS), sulfonated poly(aryl ether ketone) (SPAEK), poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI), poly(styrene sulfonate) (PSS), lithium 9,10-diphenylatlasene-2-sulfonate (lithium 9,10-diphenylanthracene-2-sulfonate, DPASLi + A solid electrolyte separator comprising ) or a combination thereof.

4. In Paragraph 1, A solid electrolyte separator having a weight ratio of the solid electrolyte to the ion-conducting polymer of 99:1 to 1:

99.

5. In Paragraph 1, Surface roughness (R) of the above uneven portion a ) is a solid electrolyte separator with a thickness of 0.1 μm to 50 μm.

6. In Paragraph 1, A solid electrolyte separator further comprising an adhesive layer disposed on the above-mentioned uneven portion.

7. In Paragraph 6, The above adhesive layer comprises a solid electrolyte separator comprising polyvinylidene fluoride (PVDF), polyurethane, epoxy resin, polyvinyl alcohol (PVA), polyacrylate, silicone, polyvinyl acetate (PVAc), polyester, polyimide, polycarbonate, nylon, polyurethane acrylate, polyolefin, or a combination thereof.

8. In Paragraph 1, A solid electrolyte separator further comprising a flat portion formed on the edge portion of at least one surface.

9. Anode; cathode; and It includes a solid electrolyte separation membrane according to claim 1, The above-mentioned uneven portion is an all-solid-state battery adjacent to the above-mentioned positive electrode.

10. In Paragraph 9, A solid-state battery further comprising an adhesive layer between the above-mentioned uneven portion and the above-mentioned anode.

11. In Paragraph 9, The above positive electrode further comprises a positive current collector and a positive active material layer disposed on the positive current collector; A solid-state battery further comprising an inactive member disposed on one side of the positive active material layer.

12. In Paragraph 9, The above solid electrolyte separator further comprises a flat portion formed at the edge portion of at least one surface, in an all-solid-state battery.

13. In Paragraph 9, The above positive electrode further comprises a positive current collector and a positive active material layer on the positive current collector; The above-mentioned positive active material layer comprises a sulfide-based positive active material, in an all-solid-state battery.

14. In Paragraph 13, The above-mentioned sulfide-based cathode active material comprises Li2S, a Li2S-containing composite, or a combination thereof, in an all-solid-state battery.

15. In Paragraph 14, The above Li2S-containing composite is an all-solid-state battery further comprising a lithium salt compound.

16. In Paragraph 15, The above Li2S-containing composite is an all-solid-state battery further comprising a boron group metal salt.

17. In Paragraph 9, The above-mentioned cathode further comprises a cathode current collector and a coating layer disposed on the cathode current collector, in an all-solid-state battery.

18. In Paragraph 17, The above coating layer comprises metal particles and carbon-based materials, in an all-solid-state battery.

19. In Paragraph 18, The above carbon-based material includes amorphous carbon, crystalline carbon, porous carbon, or a combination thereof, and The above metal particles comprise gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), or a combination thereof, in an all-solid-state battery.

20. In Paragraph 17, A solid-state battery further comprising a lithium metal layer disposed between the coating layer and the negative current collector.

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