All-solid-state battery

Abstract

The present invention relates to an all-solid-state battery and, more specifically, to an all-solid-state battery comprising: a plurality of unit structures; and an elastic pad disposed between adjacent unit structures among the plurality of unit structures. Each of the plurality of unit structures includes a first bi-cell and a second bi-cell that are adjacent to each other, the first bi-cell includes a lithium deposition-type first anode layer, and the second bi-cell includes a lithium-impregnated second anode layer.

Description

All-solid-state batteries

[0001] The present invention relates to an all-solid-state battery.

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

[0003] Recently, all-solid-state batteries, which replace the electrolyte with a solid electrolyte, have been proposed. By eliminating the use of flammable organic dispersion media, all-solid-state batteries significantly reduce the risk of fire or explosion in the event of a short circuit. Therefore, these all-solid-state batteries can significantly improve safety compared to lithium-ion batteries that use electrolytes.

[0004] The problem to be solved by the present invention is to provide an all-solid-state battery having a high energy density while alleviating volume expansion.

[0005] An all-solid-state battery according to one embodiment of the present invention comprises: a plurality of unit structures; and an elastic pad disposed between adjacent ones of the plurality of unit structures; wherein each of the plurality of unit structures includes a first bi-cell and a second bi-cell adjacent to each other, the first bi-cell including a first negative electrode layer of a lithium precipitation type, and the second bi-cell including a second negative electrode layer of a lithium absorption type.

[0006] According to another embodiment of the present invention, an all-solid-state battery comprises a plurality of unit structures arranged side by side, each of the plurality of unit structures comprising: a pair of first bicelles; and a second bicell between the pair of first bicelles; wherein each of the pair of first bicelles comprises a first negative electrode layer, and the second bicelles comprises a second negative electrode layer, and one of the first negative electrode layer and the second negative electrode layer may be a lithium precipitation-type negative electrode layer, and the other of the first negative electrode layer and the second negative electrode layer may be a lithium absorption-type negative electrode layer.

[0007] A stack cell of an all-solid-state battery according to one embodiment of the present invention can have a high energy density while simultaneously alleviating volume expansion.

[0008] FIG. 1 is a cross-sectional view of a monocell of an all-solid-state battery according to one embodiment of the present invention.

[0009] FIG. 2 is a cross-sectional view of a first bicell of an all-solid-state battery according to one embodiment of the present invention.

[0010] FIG. 3 is a plan view of the first bicell of the all-solid-state battery according to FIG. 2.

[0011] Fig. 4 is a cross-sectional view of the first bi-cell of the all-solid-state battery according to Fig. 2 during charging.

[0012] FIG. 5 is a cross-sectional view of a second bicell of an all-solid-state battery according to one embodiment of the present invention.

[0013] FIG. 6 is a plan view of the second bicell of the all-solid-state battery according to FIG. 5.

[0014] Figure 7 is a cross-sectional view of a stack cell of an all-solid-state battery according to one embodiment of the present invention.

[0015] Figure 8 is a cross-sectional view of a unit structure according to one embodiment of the present invention.

[0016] FIGS. 9, 10, 11, and 12 are each a cross-sectional view of a stack cell of an all-solid-state battery according to different embodiments of the present invention.

[0017] FIG. 13 and FIG. 14 are cross-sectional views of stack cells of all-solid-state batteries according to comparative examples of the present invention, respectively.

[0018] To fully understand the structure and effects of the present invention, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms and subject to various modifications. However, the description of these embodiments is provided solely to ensure a complete disclosure of the present invention and to fully inform those skilled in the art of the invention of the scope of the invention.

[0019] In this specification, when a component is referred to as being on another component, it means that it can be formed directly on the other component, or a third component may be interposed between them. Furthermore, in the drawings, the thicknesses of the components are exaggerated for the sake of clarity. Parts designated by the same reference numerals throughout the specification represent the same components.

[0020] Embodiments described herein will be described with reference to cross-sectional and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of films and regions are exaggerated for the purpose of effectively explaining the technical contents. Accordingly, the regions illustrated in the drawings have a schematic nature, and the shapes of the regions illustrated in the drawings are intended to illustrate specific shapes of regions of the device and are not intended to limit the scope of the invention. Although terms such as first, second, and third are used to describe various components in various embodiments of the present specification, these components should not be limited by such terms. These terms are used only to distinguish one component from another. The embodiments described and illustrated herein also include complementary embodiments thereof.

[0021] The terminology used herein is for the purpose of describing embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise. As used herein, the words "comprises" and / or "comprising" do not exclude the presence or addition of one or more other components.

[0022]

[0023] FIG. 1 and FIG. 2 to FIG. 6 are each cross-sectional views illustrating an all-solid-state battery according to embodiments of the present invention.

[0024] Referring to FIG. 1, a mono-cell (MNC) of an all-solid-state battery according to one embodiment of the present invention is illustrated. The mono-cell (MNC) may include a positive electrode layer (100), a negative electrode layer (200) facing the positive electrode layer (100), and a solid electrolyte layer (300) disposed between the positive electrode layer (100) and the negative electrode layer (200). However, the present invention is not limited thereto, and the mono-cell (MNC) may further include an additional functional layer, such as an adhesion enhancing layer, disposed between the positive electrode layer (100) and the solid electrolyte layer (300) or between the negative electrode layer (200) and the solid electrolyte layer (300).

[0025] The positive electrode layer (100) of one embodiment includes a positive electrode current collector (110) and a positive electrode active material layer (120) disposed on the positive electrode current collector (110). The positive electrode active material layer (120) may include a positive electrode active material, a solid electrolyte, a conductive material, and a binder.

[0026] The cathode current collector (110) can provide a reference surface on which the cathode active material layer (120) is arranged. The cathode current collector (110) can include a plate or foil including, for example, indium (In), copper (Cu), magnesium (Mg), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), zinc (Zn), aluminum (Al), germanium (Ge), lithium (Li), or an alloy thereof.

[0027] Meanwhile, unlike that illustrated in FIG. 1, in one embodiment of the present invention, the positive electrode current collector (110) may be omitted. Although not illustrated, a carbon layer having a thickness of 0.1 μm to 4 μm may be additionally disposed between the positive electrode current collector (110) and the positive electrode active material layer (120) to increase the bonding strength between the positive electrode current collector (110) and the positive electrode active material layer (120).

[0028] A cathode active material is a material that can reversibly absorb and desorb lithium ions. The cathode active material may include, but is not necessarily limited to, lithium transition metal oxides such as lithium cobalt oxide (LCO), lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium manganate, and lithium iron phosphate, nickel sulfide, copper sulfide, lithium sulfide, iron oxide, or vanadium oxide. The cathode active materials may be used alone or as a mixture of two or more.

[0029] Lithium transition metal oxides include, for example, Li a A 1-b B b D2(0.90≤a≤1, 0≤b≤0.5), Li a E 1-b B b O 2-c Dc (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05), LiE 2-b B b O 4-c D c (0≤b≤0.5, 0≤c≤0.05), Li a Ni 1-b-c Co b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Co b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni 1-b-c Mr b B c D α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α≤2), Li a Ni 1-b-c Mr b B c O 2-α F α (0.90≤a≤1, 0≤b≤0.5, 0≤c≤0.05, 0<α<2), Li a Ni b HAVE BEEN c G d O2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0.001≤d≤0.1), Li a Ni b Co c Mr d GeO2(0.90≤a≤1, 0≤b≤0.9, 0≤c≤0.5, 0≤d≤0.5, 0.001≤e≤0.1), Li a NiG b O2(0.9≤a≤1, 0.001≤b≤0.1), Li a CoG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li a MnG b O2(0.90≤a≤1, 0.001≤b≤0.1), Li aMn2GbO4(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 A compound represented by any one of Fe2(PO4)3(0≤f≤2), LiFePO4. In these compounds, the capital letter “A” is Ni, Co, Mn, or a combination thereof, the capital letter “B” is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof, the capital letter “D” is O, F, S, P, or a combination thereof, the capital letter “E” is Co, Mn, or a combination thereof, the capital letter “F” is F, S, P, or a combination thereof, the capital letter “G” is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or a combination thereof, the capital letter “Q” is Ti, Mo, Mn, or a combination thereof, the capital letter “I” is Cr, V, Fe, Sc, Y, or a combination thereof, and the capital letter “J” is V, Cr, Mn, Co, Ni, Cu, or a combination thereof.

[0030] The cathode active material may include, for example, a lithium salt of a transition metal oxide having a layered rock salt type structure among the lithium transition metal oxides described above. The "layered rock salt type structure" is, for example, a cubic rock salt type structure. <111> It is a structure in which oxygen atomic layers and metal atomic layers are alternately and regularly arranged in a direction, and thereby each atomic layer forms a two-dimensional plane. The "cubic rock salt structure" refers to the sodium chloride type (NaCl type) structure, which is a type of crystal structure, and specifically refers to a structure in which the face-centered cubic lattice (fcc) formed by each cation and anion is arranged with a displacement of half of the ridge of the unit lattice. Lithium transition metal oxides having this layered rock salt structure include, for example, LiNi x Co y Al z O2(NCA) or LiNi x Co y Mn z O2(NCM) (0 <x<1,0<y<1, 0<z<1, x+y+z=1) 등의 삼원계 리튬전이금속산화물일 수 있다. 양극활물질이 층상암염형 구조를 갖는 삼원계 리튬전이금속산화물을 포함하는 경우, 모노셀(MNC)의 에너지 밀도가 커지고 열안정성이 향상될 수 있다.

[0031] The above-described compound included in the positive electrode active material may be covered by a coating layer (not shown). The positive electrode active material may also be a mixture of the above-described compound and a compound to which a coating layer is added. Meanwhile, the coating layer added to the surface of the positive electrode active material may include, for example, an oxide, a hydroxide, an oxyhydroxide, an oxycarbonate, or a hydroxycarbonate of the coating elements below. The compound forming the coating layer may be amorphous or crystalline. The coating elements included in the coating layer may include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof. The coating layer may include, for example, Li2O-ZrO2 (LZO). The method of forming the coating layer is selected within a range that does not adversely affect the physical properties of the positive electrode active material. The method of forming the coating layer includes, for example, spray coating, dipping, etc.

[0032] When the cathode active material is a ternary lithium transition metal oxide such as NCA or NCM and contains nickel (Ni), it is possible to increase the capacity density of the monocell (MNC) and reduce metal dissolution of the cathode active material in a charged state. As a result, the cycle characteristics of the monocell (MNC) in a charged state are improved. Meanwhile, the “cycle characteristics” are characteristics indicating the degree to which the monocell (MNC) deteriorates due to charge / discharge of the monocell (MNC). A monocell (MNC) with high cycle characteristics may have a small degree of deterioration due to charge / discharge, and a monocell (MNC) with low cycle characteristics may have a large degree of deterioration due to charge / discharge.

[0033] The shape of the cathode active material may include particle shapes such as a sphere or an ellipsoid, for example. The particle size and content of the cathode active material are not particularly limited.

[0034] The solid electrolyte may include a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. Examples of the sulfide-based solid electrolyte include Li2S-P2S5, Li2S-P2S5-LiX (X is a halogen element), Li2S-P2S5-Li2O, Li2S-P2S5-Li2O-LiI, Li2S-SiS2, Li2S-SiS2-LiI, Li2S-SiS2-LiBr, Li2S-SiS2-LiCl, Li2S-SiS2-B2S3-LiI, Li2S-SiS2-P2S5-LiI, Li2S-B2S3, Li2S-P2S5-Z. m S n (m, n are positive numbers, capital letter “Z” represents Ge, Zn or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p, q are positive numbers, capital letter “M” is one of P, Si, Ge, B, Al, Ga In), Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may include at least one selected from (0≤x≤2).

[0035] Sulfide-based solid electrolytes include, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound including at least one selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0036] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X c It may be an argyrodite-type compound containing (0≤a≤2, (0≤c≤2)), where X may be F, Br, Cl, or a combination thereof. M is candium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof. Can be.

[0037] The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. Since the argyrodite-type solid electrolyte has a density of 1.5 g / cc or more, the internal resistance of the all-solid-state battery is reduced, and the defect of the solid electrolyte membrane being penetrated and short-circuited due to the formation of lithium dendrites can be prevented. The elastic modulus of the solid electrolyte may be, for example, 15 GPa to 35 GPa.

[0038] The solid electrolyte included in the positive electrode active material layer (120) may have a smaller median particle size (D50) than the solid electrolyte included in the solid electrolyte layer (300). For example, the median particle size (D50) of the solid electrolyte included in the positive electrode active material layer (120) may be 90% or less, 80% or less, 70% or less, 60% or less, 50% or less, 40% or less, 30% or less, or 20% or less of the median particle size (D50) of the solid electrolyte included in the solid electrolyte layer (300). Meanwhile, the median particle size (D50) may be a median diameter measured using a laser particle size distribution meter.

[0039] The cathode active material layer (120) may include a conductive material. The conductive material may be conductive without causing chemical changes in the mono-cell (MNC), thereby increasing the conductivity of the cathode active material and the solid electrolyte. The conductive material may include a carbon-based material. For example, the conductive material may include one or more selected from graphite, carbon black, acetylene black, carbon nanofibers, and carbon nanotubes.

[0040] The positive electrode active material layer (120) may further include a binder. The binder may include a material for binding the positive electrode active material, solid electrolyte, and conductive material included in the positive electrode active material layer (120) and improving bonding strength with the positive electrode current collector (110). The binder may include, for example, polyvinylidene fluoride, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, and polymethyl methacrylate.

[0041] Based on 100 parts by weight of the total of the positive electrode active material, the solid electrolyte, the conductive material, and the binder, the positive electrode active material layer (120) may include 85 parts by weight or more and 92 parts by weight or less of the positive electrode active material. Based on 100 parts by weight of the total of the positive electrode active material, the solid electrolyte, the conductive material, and the binder, the positive electrode active material layer (120) may include 0.5 parts by weight or more and 1.5 parts by weight or less of the binder.

[0042] Based on 100 parts by weight of the solid electrolyte, the positive electrode active material layer (120) may include 1 part by weight or more and 50 parts by weight or less of a conductive material. If the conductive material is included in the positive electrode active material layer (120) in an amount of less than 1 part by weight based on 100 parts by weight of the solid electrolyte, the proportion of the conductive material may decrease, thereby lowering the electrical conductivity of the positive electrode active material layer (120). If the conductive material is included in the positive electrode active material layer (120) in an amount of more than 50 parts by weight based on 100 parts by weight of the solid electrolyte, the proportion of the conductive material may be excessively high, so that a covering layer covering the surface of the solid electrolyte may not be properly formed.

[0043] The cathode active material layer (120) may further include additives such as fillers, coating agents, dispersants, and ion conductive aids in addition to the cathode active material, solid electrolyte, conductive agent, and binder described above.

[0044] The solid electrolyte layer (300) is disposed between the positive electrode layer (100) and the negative electrode layer (200) and includes a sulfide-based solid electrolyte having excellent lithium ion conductivity characteristics. The solid electrolyte included in the solid electrolyte layer (300) may be the same as or different from any one of the materials that may be included in the solid electrolyte included in the positive electrode active material layer (120) described above.

[0045] The solid electrolyte layer (300) of one embodiment may include a sulfide-based solid electrolyte. The sulfide-based solid electrolyte may be manufactured by treating starting materials such as Li2S and P2S5 by a melting rapid cooling method or a mechanical milling method. In addition, a heat treatment may be performed after the treatment. The solid electrolyte may be amorphous, crystalline, or a mixture thereof. In addition, the solid electrolyte may include, for example, at least sulfur (S), phosphorus (P), and lithium (Li) as constituent elements among the above-described sulfide-based solid electrolyte materials. For example, the solid electrolyte may be a material including Li2S-P2S5. When using a sulfide-based solid electrolyte material including Li2S-P2S5 to form the solid electrolyte, the mixing molar ratio of Li2S and P2S5 is, for example, in the range of Li2S:P2S5=50:50 to 90:10.

[0046] Sulfide-based solid electrolytes include, for example, Li 7-x PS 6-x Cl x (0≤x≤2), Li 7-x PS 6-x Br x (0≤x≤2), and Li 7-x PS 6-x I x It may be an argyrodite-type compound including at least one selected from (0≤x≤2). In particular, the sulfide-based solid electrolyte may be an argyrodite-type compound including at least one selected from Li6PS5Cl, Li6PS5Br, and Li6PS5I.

[0047] Alternatively, the sulfide-based solid electrolyte is Li 7-a M a PS 6-c X cIt may be an argyrodite-type compound containing (0≤a≤2, (0≤c≤2)), where X may be F, Br, Cl, or a combination thereof. M is candium (Sc), yttrium (Y), titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), mercury (Hg), aluminum (Al), gallium (Ga), indium (In), thallium (Tl), silicon (Si), germanium (Ge), tin (Sn), lead (Pb), arsenic (As), antimony (Sb), bismuth (Bi), or a combination thereof. Can be.

[0048] The density of the argyrodite-type solid electrolyte may be 1.5 g / cc to 2.0 g / cc. When the argyrodite-type solid electrolyte has a density of 1.5 g / cc or more, the internal resistance of the all-solid-state battery is reduced, and the defect of the solid electrolyte membrane being penetrated and short-circuited due to the formation of lithium dendrites can be prevented. The elastic modulus of the solid electrolyte is, for example, 15 GPa to 35 GPa.

[0049] The solid electrolyte layer (300) may further include a binder. The binder included in the solid electrolyte layer (300) may be, for example, styrene butadiene rubber (SBR), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, etc., but is not limited thereto. The binder of the 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 active material layer (220).

[0050] The negative electrode layer (200) includes a negative electrode current collector (210) and a negative electrode active material layer (220) disposed on the negative electrode current collector (210). The negative electrode active material layer (220) may include a negative electrode active material and a binder.

[0051] The negative electrode current collector (210) can provide a reference surface on which the negative electrode active material layer (220) is arranged. The negative electrode current collector (210) can include, for example, a material that does not react with lithium, i.e., does not form an alloy or compound with lithium. The material constituting the negative electrode current collector (210) is not necessarily limited to, for example, copper (Cu), stainless steel, titanium (Ti), iron (Fe), cobalt (Co), and nickel (Ni), and any material that can be used as an electrode current collector can be used. The thickness of the negative electrode current collector can be 1 to 20 μm, for example, 5 to 15 μm, for example, 7 to 10 μm.

[0052] The negative electrode current collector (210) may be composed of one of the above-described metals, or may include an alloy or coating material of two or more metals. The negative electrode current collector (210) is, for example, in the form of a plate or foil. Meanwhile, in one embodiment, the negative electrode current collector (210) may be omitted.

[0053] The negative electrode active material included in the negative electrode active material layer (220) may have a particle form. The median particle size average particle diameter (D50) of the negative electrode active material having a particle form may be, for example, 4 μm or less, 2 μm or less, 1 μm or less, or 900 nm or less. The median particle size average particle diameter (D50) of the negative electrode active material may be, for example, 10 nm to 4 μm, 10 nm to 2 μm, or 10 nm to 900 nm. When the negative electrode active material has a median particle size average diameter (D50) in this range, reversible absorption and / or desorption of lithium may be facilitated during charge and discharge. Meanwhile, the median particle size average diameter (D50) may be a median diameter measured using a laser particle size distribution meter.

[0054] The negative electrode active material may include, for example, at least one selected from a carbon-based negative electrode active material and a metal or metalloid negative electrode active material.

[0055] The carbon-based negative electrode active material may be amorphous carbon, in particular. Examples of amorphous carbon include, but are not limited to, carbon black (CB), acetylene black (AB), furnace black (FB), ketjen black (KB), and graphene. Amorphous carbon is carbon that has no crystallinity or very low crystallinity, and is distinguished from crystalline carbon or graphitic carbon.

[0056] The metal or metalloid negative electrode active material includes, but is not necessarily limited to, one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), zinc oxide (ZnO), magnesium (Mg), copper (Cu), nickel (Ni), silicon (Si), bismuth (Bi), gallium (Ga), germanium (Ge), lead (Pb), thallium (Tl), antimony (Sb), and indium (In), and may be a metal negative electrode active material or a metalloid negative electrode active material that forms an alloy or compound with lithium. On the other hand, nickel (Ni) does not form an alloy with lithium and therefore is not a metal negative electrode active material.

[0057] The negative electrode active material layer (220) may include one type of negative electrode active material among these negative electrode active materials, or may include a mixture of a plurality of different negative electrode active materials. For example, the negative electrode active material layer (220) may include only amorphous carbon, or may include at least one selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), magnesium (Mg), copper (Cu), nickel (Ni), silicon (Si), bismuth (Bi), gallium (Ga), germanium (Ge), lead (Pb), thallium (Tl), antimony (Sb), and indium (In).

[0058] In one embodiment, the negative electrode active material layer (220) may include a mixture of amorphous carbon and one or more selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), magnesium (Mg), zinc (Zn), zinc oxide (ZnO), copper (Cu), nickel (Ni), silicon (Si), bismuth (Bi), gallium (Ga), germanium (Ge), lead (Pb), thallium (Tl), antimony (Sb), and indium (In). The mixing ratio of the mixture of amorphous carbon and gold (Au) or the like may be, for example, 10:1 to 1:2, 5:1 to 1:1, or 4:1 to 2:1 by weight, but is not necessarily limited to this range and may be selected depending on the characteristics of the required all-solid-state battery (10). By having the negative active material having this composition, the cycle characteristics of the all-solid-state battery (10) can be further improved.

[0059] The binder included in the negative electrode active material layer (220) includes, for example, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, vinylidene fluoride / hexafluoropropylene copolymer, polyacrylonitrile, polymethyl methacrylate, etc., but is not necessarily limited thereto. The binder may include a single binder or a plurality of different binders.

[0060] Since the negative electrode active material layer (220) includes a binder, the negative electrode active material layer (220) can be stably formed on the negative electrode current collector (210). That is, the bonding strength between the negative electrode active material layer (220) and the negative electrode current collector (210) can be increased. In addition, cracking of the negative electrode active material layer (220) is suppressed despite changes in the volume and / or relative positions of the negative electrode active material layer (220) during the charge and discharge process. If the negative electrode active material layer (220) does not include a binder, the negative electrode active material layer (220) can be easily separated from the negative electrode current collector (210). As the negative electrode active material layer (220) is detached from the negative electrode current collector (210), the negative electrode current collector (210) can come into contact with the solid electrolyte layer at the exposed portion, thereby increasing the possibility of a short circuit occurring.

[0061] The negative electrode active material layer (220) is manufactured, for example, by providing a mixture in which the materials constituting the negative electrode active material layer (220) are dispersed onto the negative electrode current collector (210). Since a binder is included in the materials constituting the negative electrode active material layer (220), stable dispersion of the negative electrode active material in the mixture is possible. For example, when applying the mixture onto the negative electrode current collector (210) by screen printing, it is possible to suppress clogging of the screen (e.g., clogging by aggregates of the negative electrode active material) by the binder.

[0062] The negative electrode active material layer (220) may further include other additives in addition to the negative electrode active material and binder. The negative electrode active material layer (220) may further include, for example, fillers, coating agents, dispersants, ion conductive additives, etc.

[0063] The negative electrode active material layer (220) may have a smaller thickness than the positive electrode active material layer (120). The thickness of the negative electrode active material 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 active material layer (220) may be, for example, 1 μm to 20 μm, 2 μm to 10 μm, or 3 μm to 7 μm. If the thickness of the negative electrode active material layer (220) is too thin, lithium dendrites formed between the negative electrode active material layer (220) and the negative electrode current collector (210) may collapse the negative electrode active material layer (220), thereby deteriorating the cycle characteristics of the monocell (MNC). If the thickness of the negative electrode active material layer (220) increases excessively, the energy density of the monocell (MNC) may decrease and the internal resistance of the monocell (MNC) due to the negative electrode active material layer (220) may increase, thereby deteriorating the cycle characteristics of the monocell (MNC).

[0064] If the thickness of the negative electrode active material layer (220) decreases, the charge capacity of the negative electrode active material layer (220) may also decrease, for example. The charge capacity of the negative electrode active material layer (220) is, for example, 50% or less, 40% or less, 30% or less, 20% or less, 10% or less, 5% or less, or 2% or less than the charge capacity of the positive electrode active material layer (120). The charge capacity of the negative electrode active material layer (220) is, for example, 0.1% to 50%, 0.1% to 40%, 0.1% to 30%, 0.1% to 20%, 0.1% to 10%, 0.1% to 5%, or 0.1% to 2% than the charge capacity of the positive electrode active material layer (120). If the charge capacity of the negative electrode active material layer (220) is excessively small, the thickness of the negative electrode active material layer (220) becomes very thin, and the same defects as the defects described above that occur when the thickness of the negative electrode active material layer (220) becomes excessively thin may occur. If the charge capacity of the negative electrode active material layer (220) increases excessively, the same defects as the defects described above that occur when the thickness of the negative electrode active material layer (220) increases excessively may occur.

[0065] The charge capacity of the positive electrode active material layer (120) can be obtained by multiplying the charge capacity density (mAh / g) of the positive electrode active material by the mass of the positive electrode active material of the positive electrode active material layer (120). When the positive electrode active material layer (120) includes several types of positive electrode active materials, the [charge capacity density Х mass] value is calculated for each positive electrode active material, and the sum of these values ​​of the positive electrode active materials is the charge capacity of the positive electrode active material layer (120). The charge capacity of the negative electrode active material layer (220) can also be calculated in the same way. That is, the charge capacity of the negative electrode active material layer (220) is obtained by multiplying the charge capacity density (mAh / g) of the negative electrode active material by the mass of the negative electrode active material in the negative electrode active material layer (220). When the negative electrode active material layer (220) includes several types of negative electrode active materials, the [charge capacity density Х mass] value is calculated for each negative electrode active material, and the sum of these values ​​of the negative electrode active materials is the capacity of the negative electrode active material layer (220). Here, the charge capacity density of the positive electrode active material and the negative electrode active material may be an estimated capacity using an all-solid-state half-cell using lithium metal as a counter electrode. The charge capacity of the positive electrode active material layer (120) and the negative electrode active material layer (220) can be directly measured by measuring the charge capacity using the all-solid-state half-cell. The charge capacity density can be obtained by dividing the measured charge capacity by the mass of each active material. Meanwhile, in the present specification, the “charge capacity” of the positive electrode active material layer (120) and the negative electrode active material layer (220) means the initial charge capacity measured at the time of the first cycle charge.

[0066] Meanwhile, although not shown, a carbon layer may be further included to improve adhesion between the negative electrode active material layer (220) and the solid electrolyte layer (300).

[0067] Referring to FIGS. 2 to 4, a first bi-cell (BIC1) of an all-solid-state battery according to one embodiment of the present invention is illustrated. The first bi-cell (BIC1) may include a first cathode layer (201), a first solid electrolyte layer (300a) on the first cathode layer, a cathode layer (100) on the first solid electrolyte layer, a second solid electrolyte layer (300b) on the cathode layer, and a second cathode layer (205) on the second solid electrolyte layer.

[0068] Each of the first and second negative electrode layers (201, 205) may include a negative electrode current collector (210) and a negative electrode active material layer (220) on the negative electrode current collector (210). The negative electrode current collector (210) may be the same as the negative electrode current collector (210) described above with reference to FIG. 1.

[0069] For example, the negative electrode active material layer (220) may include a carbon-based negative electrode active material and a metal or metalloid negative electrode active material.

[0070] For example, the carbon-based negative electrode active material may include at least one selected from the group consisting of carbon black, carbon nanotubes, acetylene black, furnace black, ketjen black, and graphene.

[0071] For example, the metal or metalloid negative electrode active material may include at least one selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), zinc oxide (ZnO), magnesium (Mg), copper (Cu), nickel (Ni), silicon (Si), bismuth (Bi), gallium (Ga), germanium (Ge), lead (Pb), thallium (Tl), antimony (Sb), and indium (In).

[0072] Each of the first and second solid electrolyte layers (300a, 300b) may be identical to the solid electrolyte layer (300) described with reference to FIG. 1. Each of the first and second solid electrolyte layers (300a, 300b) may have the same composition or different compositions.

[0073] The positive electrode layer (100) may include a first positive electrode active material layer (120a), a second positive electrode active material layer (120b), and a positive electrode current collector (110) interposed between the first and second positive electrode active material layers (120a, 120b). Each of the first and second positive electrode active material layers (120a, 120b) may have the same composition or different compositions.

[0074] Referring to FIGS. 2 and 3, the first bicelle (BIC1) may have a first cell dimension defined by a first width (W1) along a first direction (D1), a first height (H1) along a third direction (D3), and a first length (T1) along a second direction (D2).

[0075] Referring to FIG. 4, a cross-section of the first bi-cell (BIC1) of FIGS. 2 and 3 when charged is illustrated. The first and second negative electrode layers (201, 205) of the first bi-cell (BIC1) may be precipitation-type negative electrode layers. When the all-solid-state battery is charged, lithium ions released from the positive electrode may be deposited in the form of lithium metal on the negative electrode current collector (210). That is, a lithium deposition layer (LDL) may be provided between the negative electrode current collector (210) and the negative electrode active material layer (220). Accordingly, when the all-solid-state battery is charged, the volume of the first bi-cell (BIC1) may expand. For example, when the first bi-cell (BIC1) is charged, it may expand in the third direction (D3) to increase the first height (H1').

[0076] Meanwhile, although not shown, the first bi-cell (BIC1) of FIGS. 2 to 4 may include a bi-cell in which the positive electrode layer and the negative electrode layer are laminated opposite each other. For example, the first bi-cell (BIC1) may include a first positive electrode layer, a first solid electrolyte layer on the first positive electrode layer, a negative electrode layer on the first solid electrolyte layer, a second solid electrolyte layer on the negative electrode layer, and a second positive electrode layer on the second solid electrolyte layer. The negative electrode layer may include two negative electrode active material layers and a negative electrode current collector interposed between the two negative electrode active material layers. The negative electrode active material layer is as described above with reference to FIGS. 2 to 4.

[0077] Referring to FIGS. 5 and 6, a second bi-cell (BIC2) of an all-solid-state battery according to one embodiment of the present invention is illustrated. The second bi-cell (BIC2) may include a third cathode layer (201'), a first solid electrolyte layer (300a) on the third cathode layer, a cathode layer (100) on the first solid electrolyte layer, a second solid electrolyte layer (300b) on the cathode layer, and a fourth cathode layer (205') on the second solid electrolyte layer.

[0078] Each of the third and fourth negative electrode layers (201', 205') may include a negative electrode current collector (210) and a negative electrode active material layer (220') on the negative electrode current collector (210). The negative electrode current collector (210) may be the same as the negative electrode current collector (210) described above with reference to FIG. 1.

[0079] For example, the negative electrode active material layer (220') may be a silicon-based compound, a composite of a silicon-based compound and a carbon-based material, or silicon oxide (SiOx(0 <x<2)), 리튬 함유 티타늄 복합 산화물(LTO)로 이루어진 군으로부터 선택된 적어도 하나를 포함할 수 있다.

[0080] By 'silicon-based' is meant at least about 50 wt% silicon (Si), for example at least about 60 wt%, 70 wt%, 80 wt%, or 90 wt% Si, or 100 wt% Si.

[0081] For example, the silicon-based compound may include silicon particles, and the average diameter of the silicon particles may be 200 nm or less.

[0082] For example, the silicon-based compound may include a material selected from Si, a Si-Z alloy (wherein Z is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, or a combination thereof, but is not Si), and combinations thereof. The element Z may be selected from the group consisting of Mg, Ca, Sr, Ba, Ra, Sc, Y, La, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof. In addition, the silicon-based compound such as Si, a Si-Z alloy, etc. may include a substantially crystalline (including a single crystal, a polycrystalline), an amorphous, or a mixed form thereof.

[0083] For example, the carbonaceous compound may be crystalline carbon, amorphous carbon, or a mixture thereof. The crystalline carbon may be graphite, such as natural graphite or artificial graphite in the form of an amorphous, plate-like, flake-like, spherical, or fiber-like form, and the amorphous carbon may be soft carbon (low-temperature calcined carbon) or hard carbon, mesophase pitch carbide, calcined coke, or the like.

[0084] For example, the composite of a silicon-based compound and a carbon-based material may be a composite having a structure in which silicon nanoparticles are arranged on top of the carbon-based compound, a composite in which silicon particles are included on the surface and inside of the carbon-based compound, or a composite in which silicon particles are coated with the carbon-based compound and included inside the carbon-based compound. The composite of a silicon-based compound and a carbon-based material may be an active material obtained by dispersing silicon nanoparticles having an average particle diameter of about 200 nm or less on carbon-based compound particles and then coating them with carbon, an active material in which silicon particles are present on and inside graphite, etc. The average particle diameter of the secondary particles of the composite of a silicon-based compound and a carbon-based compound is 5 um to 20 um, and the average particle diameter of the silicon nanoparticles may be 200 nm or less, 150 nm or less, 100 nm or less, 50 nm or less, 20 nm or less, or 10 nm or less. For example, the average particle diameter of the silicon nanoparticles may be 100 nm to 150 nm. These composites are available under the trade names SCN1 (Si particle on graphite) and SCN2 (Si particle inside as well as on graphite). SCN1 is an active material in which silicon particles with an average particle size of approximately 150 nm are dispersed on graphite particles and then coated with carbon. SCN2 is an active material in which silicon particles with an average particle size of approximately 150 nm are present on and inside graphite.

[0085] For example, the capacity of the composite of the silicon-based compound and the carbon-based compound may be 300 mAh / g to 700 mAh / g. For example, the capacity of the composite of the silicon-based compound and the carbon-based compound may be 400 mAh / g to 600 mAh / g.

[0086] Each of the third and fourth negative electrode layers (201', 205') of the second bi-cell (BIC2) may be a storage type negative electrode layer. That is, when the all-solid-state battery is charged, lithium ions released from the positive electrode may be stored in the negative electrode active material layer (220') of each of the third and fourth negative electrode layers (201', 205'). Unlike the first bi-cell (BIC1), in the second bi-cell (BIC2), a lithium deposition layer may not be formed on the negative electrode current collector (210). Accordingly, when the all-solid-state battery is charged, the volume of the second bi-cell (BIC2) may not substantially change or may change less than that of the first bi-cell (BIC1).

[0087] The second bicell (BIC2) may have a second cell dimension defined by a second width (W2) along the first direction (D1), a second height (H2) along the third direction (D3), and a second length (T2) along the second direction (D2).

[0088] Meanwhile, although not shown, the second bi-cell (BIC2) of FIGS. 5 and 6 may include a bi-cell in which the positive electrode layer and the negative electrode layer are laminated opposite each other. For example, the second bi-cell (BIC2) may include a third positive electrode layer, a first solid electrolyte layer on the third positive electrode layer, a negative electrode layer on the first solid electrolyte layer, a second solid electrolyte layer on the negative electrode layer, and a fourth positive electrode layer on the second solid electrolyte layer. The negative electrode layer may include two negative electrode active material layers and a negative electrode current collector interposed between the two negative electrode active material layers. The negative electrode active material layer is as described above with reference to FIGS. 5 and 6.

[0089]

[0090] FIGS. 7 and 8 are each a cross-sectional view illustrating a stack cell of an all-solid-state battery according to one embodiment of the present invention. FIG. 8 is an enlarged cross-sectional view of the unit structure of FIG. 7.

[0091] Referring to FIG. 7, a stack cell (STC) of an all-solid-state battery may include a plurality of unit structures (UNS) and an elastic pad (EPD).

[0092] An elastic pad (EPD) can be placed between adjacent unit structures (UNS) among a plurality of unit structures (UNS). The elastic pad (EPD) can alleviate stress generated due to volume changes in the first bicell (BIC1) or the second bicell (BIC2) during charging and discharging.

[0093] The elastic pad (EPD) may be composed of elastically deformable members, and more specifically, may be composed of a material having a lower elastic modulus than the positive and negative current collectors described above.

[0094] For example, the elastomeric pad (EPD) may include an insulating material. Examples of the elastomeric pad (EPD) include, but are not limited to, epoxy resin, acrylic resin, polyimide resin, polyester resin, polypropylene resin, polyamide resin, polystyrene resin, polyvinyl chloride resin, polycarbonate resin, fluororesin such as PTFE, silicone rubber, etc.

[0095] Referring to FIG. 8, each of the plurality of unit structures (UNS) may include a first bicell (BIC1) and a second bicell (BIC2). The first bicell (BIC1) and the second bicell (BIC2) may be adjacent to each other. When charging the all-solid-state battery, the second bicell (BIC2) may alleviate the volume expansion of the first bicell (BIC1).

[0096] For example, the first cell dimension of the first bicell (BIC1) may be different from the second cell dimension of the second bicell (BIC2). That is, at least one of the first width (W1), the first height (H1), and the first length (T1) may be different from at least one of the second width (W2), the second height (H2), and the second length (T2).

[0097] For example, the second cell dimension may be larger than the first cell dimension. For example, the second width (W2) may be larger than the first width (W1). For example, the second height (H2) may be larger than the first height (H1). For example, the second length (T2) may be larger than the first length (T1). As a result, the second bicell (BIC2) may further alleviate the volume expansion of the first bicell (BIC1).

[0098] Within the stack cell structure, the total number of first bicelles (BIC1) and second bicelles (BIC2) may be provided as 2n to 3n. n may be an integer greater than or equal to 2. For example, the number of first bicelles may be n to 2n, and the number of second bicelles may be n to 2n. The number of first bicelles and the number of second bicelles may be the same as or different from each other. Within the stack cell structure, the number of elastic pads may be provided as 1 to n-1.

[0099] For example, referring back to FIG. 7, the first bicelles (BIC1) may be provided in n numbers, the second bicelles (BIC2) may be provided in n numbers, and the elastic pads may be provided in n-1 numbers. Here, n may be 5.

[0100]

[0101] The stack cell (STC) of the all-solid-state battery according to embodiments of the present invention may have the following characteristics by having the above-described structure.

[0102] A stack cell composed solely of a first bicell (BIC1) and an elastic pad (EPD) may include fewer elastic pads (EPD). For example, if a stack cell composed solely of a first bicell (BIC1) and an elastic pad (EPD) includes n elastic pads, a stack cell of an all-solid-state battery according to embodiments of the present invention may include 1 to n-1 elastic pads.

[0103] It can have a higher energy density than a stack cell composed only of the first bi-cell (BIC1) and the elastic pad (EPD). For example, when a stack cell composed only of the first bi-cell (BIC1) and the elastic pad (EPD) has an energy density of 480 Wh / L (see FIG. 13 described later), the stack cell of the all-solid-state battery according to embodiments of the present invention can have an energy density of 490 Wh / L to 795 Wh / L. For example, the energy density of the stack cell of the all-solid-state battery illustrated in FIG. 7 can be about 600 Wh / L.

[0104]

[0105] FIGS. 9 to 12 are cross-sectional views illustrating stack cells of all-solid-state batteries according to different embodiments of the present invention. For convenience of explanation, the description of the same details as those described with reference to FIGS. 7 and 8 will be omitted, and the differences will be described in detail.

[0106] Referring to FIG. 9, each second bicell (BIC2) of the plurality of unit structures (UNS) may include a pair of second bicells. The first bicell (BIC1) may be positioned between the pair of second bicells.

[0107] Accordingly, the stack cell (STC) of the all-solid-state battery may include n first bi-cells (BIC1), 2n second bi-cells (BIC2), and n-1 elastic pads (EPD). For example, in FIG. 9, n may be 4, and thus the stack cell (STC) may include 4 first bi-cells (BIC1), 8 second bi-cells (BIC2), and 3 elastic pads (EPD). The energy density of the stack cell (STC) of the all-solid-state battery may be about 640 Wh / L.

[0108] Referring to FIG. 10, each first bicell (BIC1) of the plurality of unit structures (UNS) may include a pair of first bicells. A second bicell (BIC2) may be positioned between the pair of first bicells.

[0109] Accordingly, the stack cell (STC) of the all-solid-state battery may include 2n first bicells (BIC1), n ​​second bicells (BIC2), and n-1 elastic pads (EPD). The energy density of the stack cell (STC) of the all-solid-state battery may be about 680 Wh / L.

[0110] Referring to FIG. 11, each of the plurality of unit structures (UNS) may include a first bicell (BIC1) of a plurality of first bicelles, and each of the second bicelles (BIC2) may include a plurality of second bicelles. The plurality of first bicelles and the plurality of second bicelles may be arranged alternately.

[0111] Accordingly, the stack cell (STC) of the all-solid-state battery can include one elastic pad (EPD). The energy density of the stack cell (STC) of the all-solid-state battery can be about 705 Wh / L.

[0112] Referring to FIG. 12, a stack cell (STC) of an all-solid-state battery according to an embodiment of the present invention may include a plurality of unit structures (UNS) arranged side by side. That is, the plurality of unit structures (UNS) may be adjacent to each other. Each of the plurality of unit structures may include a pair of first bicelles (BIC1) and a second bicelle (BIC2). The second bicelle (BIC2) may be disposed between the pair of first bicelles (BIC1).

[0113] Each of the pair of first bi-cells (BIC1) may include a first negative electrode layer, and the second bi-cell (BIC2) may include a second negative electrode layer. One of the first negative electrode layer and the second negative electrode layer may be the lithium precipitation type negative electrode layer described above. The other of the first negative electrode layer and the second negative electrode layer may be the lithium absorption type negative electrode layer described above. For example, the first negative electrode layer may be a lithium precipitation type negative electrode layer, and the second negative electrode layer may be a lithium absorption type negative electrode layer.

[0114] The plurality of unit structures may include a first unit structure (UNS1) and a second unit structure (UNS2) that are adjacent to each other. Any one of the two first bi-cells (BIC1) of the first unit structure (UNS1) may be adjacent to any one of the two first bi-cells (BIC1) of the second unit structure (UNS2). That is, the stack cell (STC) of the all-solid-state battery according to the present embodiment may include the first bi-cells (BIC1) that are adjacent to each other.

[0115] Accordingly, the stack cell (STC) of the all-solid-state battery may not include an elastic pad (EPD). The energy density of the stack cell (STC) of the all-solid-state battery may be about 795 Wh / L. The stack cell (STC) of the all-solid-state battery according to FIG. 12 may be lower than the energy density of the stack cell (STC) of the all-solid-state battery according to FIG. 14, which will be described later.

[0116]

[0117] FIG. 13 and FIG. 14 are cross-sectional views illustrating a stack cell of an all-solid-state battery according to comparative examples of the present invention.

[0118] Referring to FIG. 13, the stack cell (STC) of the all-solid-state battery according to the comparative example of the present invention may have a structure in which the first bi-cell (BIC1) and the elastic pad (EPD) are alternately arranged. That is, the stack cell (STC) of the all-solid-state battery according to the comparative example of the present invention may be composed only of the first bi-cell (BIC1) and the elastic pad (EPD).

[0119] Accordingly, the stack cell (STC) of the all-solid-state battery according to the comparative example of the present invention can include more elastic pads (EPDs) than the stack cells (STC, see FIGS. 7, 9 to 12) of the all-solid-state battery according to the embodiments of the present invention. For example, the stack cell (STC) of the all-solid-state battery can include seven elastic pads (EPDs).

[0120] Additionally, the stack cell (STC) of the all-solid-state battery according to the comparative example of the present invention may have a lower energy density than the stack cells (STC, see FIGS. 7, 9 to 12) of the all-solid-state battery according to the embodiments of the present invention. For example, the energy density of the stack cell (STC) of the all-solid-state battery may be about 480 Wh / L.

[0121] Referring to Fig. 14, the stack cell (STC) of the all-solid-state battery according to a comparative example of the present invention may include only the first bi-cell (BIC1). Accordingly, the energy density of the stack cell (STC) of the all-solid-state battery may be approximately 800 Wh / L.

[0122]

[0123] While embodiments of the present invention have been described with reference to the attached drawings, the present invention may be implemented in other specific forms without altering the technical spirit or essential features thereof. Therefore, it should be understood that the embodiments described above are exemplary in all respects and are not limiting.

Claims

1. Multiple unit structures; and An elastic pad disposed between adjacent ones of the above plurality of unit structures; including: Each of the above plurality of unit structures includes a first bicell and a second bicell that are adjacent to each other, The above first bicell includes a first negative electrode layer of lithium precipitation type, The second bicell includes a second negative electrode layer that is a lithium-storage type. All-solid-state battery.

2. In paragraph 1, The first cathode layer includes a carbon-based cathode active material and a metal or metalloid cathode active material, The above carbon-based negative electrode active material comprises at least one selected from the group consisting of carbon black, carbon nanotubes, acetylene black, furnace black, ketgen black, and graphene. The above metal or metalloid negative electrode active material comprises at least one selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), zinc oxide (ZnO), magnesium (Mg), copper (Cu), nickel (Ni), silicon (Si), bismuth (Bi), gallium (Ga), germanium (Ge), lead (Pb), thallium (Tl), antimony (Sb), and indium (In). All-solid-state battery.

3. In paragraph 1, The second cathode layer is a silicon-based compound, a composite of a silicon-based compound and a carbon-based material, silicon oxide (SiOx(0) <x<2)), 리튬 함유 티타늄 복합 산화물(LTO)로 이루어진 군으로부터 선택된 적어도 하나를 포함하는, All-solid-state battery.

4. In paragraph 1, The first bicell has a first cell dimension defined by a first width, a first height, and a first length, The second bicell has a second cell dimension defined by a second width, a second height, and a second length, The first cell dimension and the second cell dimension are different from each other, All-solid-state battery.

5. In paragraph 4, The above second cell dimension is larger than the above first cell dimension, All-solid-state battery.

6. In paragraph 1, The second bicelle above buffers the volume expansion of the first bicelle, All-solid-state battery.

7. In paragraph 1, Energy density is 490Wh / L to 795Wh / L, All-solid-state battery.

8. In paragraph 1, Each of the second bicelles of the plurality of unit structures includes a pair of second bicelles, The first bicell is placed between the pair of second bicelles, All-solid-state battery.

9. In paragraph 1, Each of the first bicelles of the plurality of unit structures includes a pair of first bicelles, The second bicell is placed between the pair of first bicelles, All-solid-state battery.

10. In paragraph 1, Each of the first bicelles of the plurality of unit structures includes a plurality of first bicelles, Each of the second bicelles of the plurality of unit structures includes a plurality of second bicelles, The first bicelles and the second bicelles are arranged alternately, All-solid-state battery.

11. Containing a plurality of unit structures arranged in parallel, Each of the above multiple unit structures: a pair of first bicelles; and A second bicell between the pair of first bicelles; Each of the above pair of first bicelles comprises a first cathode layer, The second bicelle includes a second cathode layer, One of the first cathode layer and the second cathode layer is a lithium precipitation type cathode layer, The other of the first negative electrode layer and the second negative electrode layer is a lithium-storage negative electrode layer, All-solid-state battery.

12. In paragraph 11, The above plurality of unit structures include a first unit structure and a second unit structure adjacent to each other, One of the pair of first bicelles of the first unit structure is adjacent to one of the pair of first bicelles of the second unit structure, All-solid-state battery.

13. In paragraph 11, The above lithium precipitation type negative electrode layer includes a carbon-based negative electrode active material and a metal or metalloid negative electrode active material, The above carbon-based negative electrode active material comprises at least one selected from the group consisting of carbon black, carbon nanotubes, acetylene black, furnace black, ketgen black, and graphene. The above metal or metalloid negative electrode active material comprises at least one selected from the group consisting of gold (Au), platinum (Pt), palladium (Pd), silicon (Si), silver (Ag), aluminum (Al), bismuth (Bi), tin (Sn), zinc (Zn), zinc oxide (ZnO), magnesium (Mg), copper (Cu), nickel (Ni), silicon (Si), bismuth (Bi), gallium (Ga), germanium (Ge), lead (Pb), thallium (Tl), antimony (Sb), and indium (In). All-solid-state battery.

14. In paragraph 11, The above lithium absorption type negative electrode layer is a silicon-based compound, a composite of a silicon-based compound and a carbon-based material, silicon oxide (SiOx(0) <x<2)), 리튬 함유 티타늄 복합 산화물(LTO)로 이루어진 군으로부터 선택된 적어도 하나를 포함하는, All-solid-state battery.

15. In paragraph 11, The first bicell has a first cell dimension defined by a first width, a first height, and a first length, The second bicell has a second cell dimension defined by a second width, a second height, and a second length, The first cell dimension and the second cell dimension are different from each other, All-solid-state battery.

16. In paragraph 15, The above second cell dimension is larger than the above first cell dimension, All-solid-state battery.

17. In paragraph 11, The second bicelle above buffers the volume expansion of the first bicelle, All-solid-state battery.

18. In paragraph 11, The energy density is 795Wh / L, All-solid-state battery.

Images