All-solid-state rechargeable battery and method for manufacturing all-solid-state rechargeable battery

Abstract

The invention relates to an all-solid-state rechargeable battery and a manufacturing method of the all-solid-state rechargeable battery. The all-solid-state rechargeable battery includes: a first electrode powder layer; a solid electrolyte powder layer disposed on the first electrode powder layer; and a second electrode powder layer disposed on the solid electrolyte powder layer.

Description

Technical Field

[0001] This application relates to all-solid-state rechargeable batteries and methods for manufacturing all-solid-state rechargeable batteries. Background Technology

[0002] Because batteries using liquid electrolytes pose a risk of explosion, all-solid-state rechargeable batteries were developed. In all-solid-state rechargeable batteries, all materials are solid, including the electrolyte. These batteries are safe because there is no risk of explosion due to electrolyte leakage. All-solid-state rechargeable batteries also have the advantage of being easy to manufacture into thin batteries.

[0003] A typical all-solid-state rechargeable battery consists of a negative electrode, a positive electrode, and a solid electrolyte layer. Summary of the Invention

[0004] It offers all-solid-state rechargeable batteries with improved battery capacity and performance, while the metal layers do not crack even when the metal layers are laminated into a thin film.

[0005] One aspect is to provide an all-solid-state rechargeable battery comprising: a first electrode powder layer; a solid electrolyte powder layer disposed on the first electrode powder layer; and a second electrode powder layer disposed on the solid electrolyte powder layer.

[0006] The first electrode powder layer may include: a metal powder layer; and a functional powder layer disposed on the metal powder layer.

[0007] The metal powder layer can contact the functional powder layer and form an interface between the metal powder layer and the functional powder layer, which includes protrusions and depressions.

[0008] The thickness of the metal powder layer can be approximately 1 μm to approximately 8 μm.

[0009] The functional powder layer may include an anolyte powder layer.

[0010] The functional powder layer may include an anodized powder layer.

[0011] The metal powder layer is a first metal powder layer, and the first electrode powder layer may further include a second metal powder layer disposed between the functional powder layer and the solid electrolyte powder layer.

[0012] The second electrode powder layer may include: a metal powder layer disposed on the solid electrolyte powder layer; and a cathode active material powder layer disposed between the metal powder layer and the solid electrolyte powder layer.

[0013] The metal powder layer can contact the cathode active material powder layer and form an interface between the metal powder layer and the cathode active material powder layer, which includes protrusions and depressions.

[0014] The metal powder layer may be a first metal powder layer, and the second electrode powder layer may further include a second metal powder layer disposed between the cathode active material powder layer and the solid electrolyte powder layer.

[0015] One aspect is a method for manufacturing an all-solid-state rechargeable battery, the method comprising: stacking a first electrode powder layer; stacking a solid electrolyte powder layer on the first electrode powder layer; stacking a second electrode powder layer on the solid electrolyte powder layer; and pressing the first electrode powder layer, the solid electrolyte powder layer, and the second electrode powder layer in a stacking direction.

[0016] The first electrode powder layer, the solid electrolyte powder layer, and the second electrode powder layer can be stacked in the recessed portion of the tray.

[0017] Pressing the first electrode powder layer, the solid electrolyte powder layer, and the second electrode powder layer in the stacking direction can be performed by a pressing device corresponding to the recessed portion of the tray.

[0018] The pressing device may include a pressing plate corresponding to the recessed portion.

[0019] The pressing device may include a pressing roller corresponding to the recessed portion.

[0020] The manufacturing method of an all-solid-state rechargeable battery may further include cutting a pressed first electrode powder layer, a solid electrolyte powder layer, and a second electrode powder layer into multiple cutting units, and stacking the multiple cutting units in the stacking direction.

[0021] The manufacturing method of all-solid-state rechargeable batteries may further include pressing multiple cut cells in the stacking direction.

[0022] The pressing of the first electrode powder layer, the solid electrolyte powder layer, and the second electrode powder layer can be carried out in an inert atmosphere.

[0023] The stacked first electrode powder layer may include: stacked metal powder layer; and stacked functional powder layer on metal powder layer.

[0024] The stacking of the second electrode powder layer may include: stacking a cathode active material powder layer on a solid electrolyte powder layer; and stacking a second metal powder layer on a cathode active material powder layer.

[0025] According to the example, an all-solid-state rechargeable battery is provided, which has improved battery capacity and battery performance, does not crack when the metal lamination is made into a thin film, and a method for manufacturing the all-solid-state rechargeable battery may also be provided. Attached Figure Description

[0026] Figure 1A cross-sectional view of an all-solid-state rechargeable battery.

[0027] Figure 2 This is a cross-sectional view of an all-solid-state rechargeable battery including a deposited negative electrode.

[0028] Figure 3 This is a cross-sectional view of an all-solid-state rechargeable battery based on an example.

[0029] Figure 4 This is a cross-sectional view of an all-solid-state rechargeable battery based on another example.

[0030] Figure 5 This is a cross-sectional view of an all-solid-state rechargeable battery according to yet another example.

[0031] Figure 6 This is a flowchart illustrating a method for manufacturing an all-solid-state rechargeable battery according to an example.

[0032] Figure 7 A method for manufacturing an all-solid-state rechargeable battery according to yet another example is shown.

[0033] Figure 8 A pressing apparatus is shown that can be used in a method for manufacturing an all-solid-state rechargeable battery according to another example.

[0034] <Symbol Description>

[0035] First electrode powder layer 100, solid electrolyte powder layer 200, second electrode powder layer 300 Detailed Implementation

[0036] Hereinafter, various examples of this disclosure will be described in detail with reference to the accompanying drawings, enabling those skilled in the art to readily implement this disclosure. As will be appreciated by those skilled in the art, the described examples can be modified in various different ways without departing from the spirit or scope of this disclosure.

[0037] Additionally, unless there is an explicit description to the contrary, the word “comprise” and its variations (such as “comprises” or “comprising”) shall be understood to imply the inclusion of elements of the narrative, but not to exclude any other elements.

[0038] To clearly illustrate the multiple layers and regions in the accompanying drawings, dimensions (e.g., thicknesses) are enlarged and shown. Throughout the specification, the same reference numerals denote the same elements. It will be understood that when an element (such as a layer, film, region, or substrate) is referred to as being "on" another element (such as a layer, film, region, or substrate), it may be directly on the other element (such as a layer, film, region, or substrate), or an intervening element may be present. In contrast, when an element (such as a layer, film, region, or substrate) is referred to as being "directly on" another element (such as a layer, film, region, or substrate), no intervening element is present.

[0039] Furthermore, the term "layer" includes not only shapes formed across the entire surface when viewed in a plan view, but also shapes formed on a portion of the surface. Here, "or" is not interpreted as exclusive, and, for example, "A or B" is interpreted as including A, B, A+B, etc.

[0040] The positive electrode of an all-solid-state rechargeable battery

[0041] The positive electrode for an all-solid-state rechargeable battery comprises a positive electrode current collector layer and a positive electrode active material layer located on the positive electrode current collector layer. The positive electrode active material layer comprises a positive electrode active material and optionally comprises at least one of a sulfide-based solid electrolyte, a binder, and a conductive material. However, this disclosure is not limited to this configuration, and the positive electrode for an all-solid-state rechargeable battery may comprise more or fewer components than those described above. The positive electrode for an all-solid-state rechargeable battery can be manufactured by applying a positive electrode composition comprising a positive electrode active material and optionally at least one of a sulfide-based solid electrolyte, a binder, and a conductive material to the positive electrode current collector layer, followed by drying and rolling.

[0042] Positive electrode active material

[0043] Any positive electrode active material typically used in all-solid-state rechargeable batteries may be used as the positive electrode active material according to this disclosure. For example, the positive electrode active material may be a compound capable of reversibly inserting and deintercalating lithium, and may include compounds represented by any of the following chemical formulas.

[0044] Li a A 1-b X b D2 (0.90≤a≤1.8, 0≤b≤0.5);

[0045] Li a A 1-b X b O 2-c D c (0.90≤a≤1.8, 0≤b≤0.5, 0≤c≤0.05);

[0046] Li a HAVE BEEN 1-b X b O 2-c D c (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05);

[0047] Li a HAVE BEEN 2-b X b O 4-c D c (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05);

[0048] Li a Ni 1-b-c Co b X c D α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.5,0<α≤2);

[0049] Li a Ni 1-b-c Co b X c O 2-α T α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α<2);

[0050] Li a Ni 1-b-c Co b X c O 2-α T2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α<2);

[0051] Li a Ni 1-b-c Mr b X c D α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α≤2);

[0052] Li a Ni 1-b-c Mr b X c O 2-α T α (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α<2);

[0053] Li a Ni 1-b-c Mrb X c O 2-α T2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α<2);

[0054] The a Nor b E c G d O2 (0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0.001≤d≤0.1);

[0055] The a Nor b Co c Mn d G e O2 (0.90≤a≤1.8,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5,0.001≤e≤0.1);

[0056] The a NiG b O2(0.90≤a≤1.8,0.001≤b≤0.1);

[0057] The a CoG b O2(0.90≤a≤1.8,0.001≤b≤0.1);

[0058] The a Mn 1-b G b O2(0.90≤a≤1.8,0.001≤b≤0.1);

[0059] The a Mn2G b O4(0.90≤a≤1.8,0.001≤b≤0.1);

[0060] The a Mn 1-g G g PO4 (0.90≤a≤1.8,0≤g≤0.5);

[0061] QO2;QS2;LiQS2;

[0062] V2O5;LiV2O5;

[0063] LiZO2:

[0064] LiNiVO4;

[0065] The (3-f) J2(PO4)3(0≤f≤2);

[0066] Li (3-f) Fe2(PO4)3 (0≤f≤2);

[0067] Li a FePO4 (0.90≤a≤1.8).

[0068] In the above chemical formulas, A is selected from Ni, Co, Mn and combinations thereof; X is selected from Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and combinations thereof; D is selected from O, F, S, P and combinations thereof; E is selected from Co, Mn and combinations thereof; T is selected from F, S, P and combinations thereof; G is selected from Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and combinations thereof; Q is selected from Ti, Mo, Mn and combinations thereof; Z is selected from Cr, V, Fe, Sc, Y and combinations thereof; and J is selected from V, Cr, Mn, Co, Ni, Cu and combinations thereof.

[0069] The active material for the positive electrode can be, for example, lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel cobalt oxide (LNCO), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium nickel manganese oxide (LNMO), lithium manganese oxide (LMO), or lithium iron phosphate (LFP) compounds.

[0070] The positive electrode active material may include lithium nickel oxides represented by the following chemical formula 1, lithium cobalt oxides represented by the following chemical formula 2, lithium iron phosphate compounds represented by the following chemical formula 3, or combinations thereof.

[0071] [Chemical Formula 1]

[0072] Li a1 Ni x1 M 1 y1 M 2 1-x1-y1 O2

[0073] In chemical formula 1, 0.9 ≤ a1 ≤ 1.8, 0.3 ≤ x1 ≤ 1, 0 ≤ y1 ≤ 0.7, and M 1 and M 2 Each element is independently selected from one or more elements selected from Al, B, Ba, Ca, Ce, Co, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W, Y, and Zr.

[0074] [Chemical Formula 2]

[0075] Li a2 Co x2 M 3 1-x2 O2

[0076] In chemical formula 2, 0.9 ≤ a² ≤ 1.8, 0.6 ≤ x² ≤ 1, and M 3 It is one or more elements selected from Al, B, Ba, Ca, Ce, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W, Y, and Zr.

[0077] [Chemical Formula 3]

[0078] Li a3 Fe x3 M 4 1-x3 PO4

[0079] In chemical formula 3, 0.9 ≤ a³ ≤ 1.8, 0.6 ≤ x³ ≤ 1, and M 4 It is one or more elements selected from Al, B, Ba, Ca, Ce, Co, Cr, Cu, F, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W, Y, and Zr.

[0080] The average particle size (D) of the positive electrode active material 50 The particle size can be 1 μm to 25 μm, for example, 3 μm to 25 μm, 5 μm to 25 μm, 5 μm to 20 μm, 8 μm to 20 μm, or 10 μm to 18 μm. Positive electrode active materials with average particle sizes within these ranges can be thoroughly mixed with other components in the positive electrode active material layer and provide high capacity and high energy density in all-solid-state rechargeable batteries.

[0081] The positive electrode active material can take the form of secondary particles obtained by aggregating multiple primary particles, or it can take the form of a single particle. In addition, the particles of the positive electrode active material can be spherical or nearly spherical, or they can be polyhedral or amorphous.

[0082] Sulfide solid electrolytes

[0083] Sulfide solid electrolytes may include, for example, Li₂S-P₂S₅, Li₂S-P₂S₅-LiX (where X is a halogen element, such as I or Cl), 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(where m and n are integers, and Z is Ge, Zn, or Ga), Li2S-GeS2, Li2S-SiS2-Li3PO4, Li2S-SiS2-Li p MO q (p and q are integers, and M is P, Si, Ge, B, Al, Ga, or In) or a combination thereof.

[0084] Sulfide-based solid electrolytes can be obtained by, for example, mixing Li₂S and P₂S₅ in a molar ratio of 50:50 to 90:10 or 50:50 to 80:20, and optionally heat-treating the mixture. Within these mixing ratio ranges, sulfide-based solid electrolytes with excellent ionic conductivity can be prepared. Here, SiS₂, GeS₂, B₂S₃, etc., can be further included as other components to further improve ionic conductivity.

[0085] Mechanical grinding or solution processing can be used as mixing methods for sulfur-containing raw materials used in the preparation of sulfide-based solid electrolytes. Mechanical grinding involves mixing the starting material, grinding balls for a ball mill, etc., in a reactor and vigorously stirring the mixture to form microparticles. In solution processing, the starting material can be mixed in a solvent to obtain a solid electrolyte as a precipitate. Furthermore, if heat treatment is performed after mixing, the crystals of the solid electrolyte can become more rigid, and the ionic conductivity can be improved. As an example, sulfide-based solid electrolytes can be manufactured by mixing sulfur-containing raw materials and heat-treating the mixture two or more times. In this case, sulfide-based solid electrolytes with high ionic conductivity and high rigidity can be prepared.

[0086] As an example, sulfide-based solid electrolyte particles may include argillium-germanium sulfides. Arillium-germanium sulfides can be formed from chemical formulas such as Li... a M b P c S d A e (where a, c, and d are all greater than 0 and 12 or less, b and e are all 0 or greater and 12 or less, M is a metal other than Li or a combination of metals other than Li, and A is F, Cl, Br, or I) and, as a specific example, it can be represented by the chemical formula Li 7-x PS 6-x A x (where x is 0.2 or greater and 1.8 or less, and A is F, Cl, Br, or I). Specifically, sulfides of the silver-germanium sulfide type can be Li3PS4 or Li7P3S. 11 , Li7PS6, Li6PS5Cl, Li6PS5Br, Li 5.8 PS 4.8 Cl1.2 Li 6.2 PS 5.2 Br 0.8 wait.

[0087] Sulfide solid electrolyte particles containing this type of sulfide, silver-germanium sulfide, exhibit high ionic conductivity, approaching approximately 10. -4 S / cm ~ Approximately 10 -2 S / cm is the ionic conductivity of a typical liquid electrolyte at room temperature. Therefore, using these sulfide-based solid electrolyte particles, a tight bond can be formed between the positive electrode active material and the solid electrolyte. Furthermore, a tight interface can be formed between the electrode layer and the solid electrolyte layer without degrading the ionic conductivity. All-solid-state rechargeable batteries incorporating this positive electrode active material can exhibit improved battery performance, such as rate capability, coulombic efficiency, and lifespan.

[0088] A sulfide-based solid electrolyte of the silver-germanium sulfide type can be prepared, for example, by mixing lithium sulfide, phosphorus sulfide, and optionally a lithium halide. After mixing the components, heat treatment can be performed. The heat treatment may include, for example, two or more heat treatment steps.

[0089] Based on the average particle size (D) of the example sulfide solid electrolyte particles 50 The particle size can be 5.0 μm or smaller, for example, 0.1 μm to 5.0 μm, 0.1 μm to 4.0 μm, 0.1 μm to 3.0 μm, 0.5 μm to 2.0 μm, or 0.1 μm to 1.5 μm. Alternatively, depending on the application or purpose, sulfide solid electrolyte particles can have an average particle size (D0). 50 Small particles with an average particle size (D) of 0.1 μm to 1.0 μm. 50 Large particles (1.5 μm to 5.0 μm) are present. Sulfide-based solid electrolyte particles within this size range can effectively permeate between solid particles in the battery. These sulfide-based solid electrolyte particles also exhibit excellent contact characteristics with electrode active materials and good connectivity between solid electrolyte particles. The average particle size of sulfide-based solid electrolyte particles can be measured using microscopic images. For example, the particle size distribution can be obtained by measuring the size of approximately 20 particles in a scanning electron microscope image, and D can be calculated from the particle size distribution. 50 .

[0090] The amount of solid electrolyte in the positive electrode of an all-solid-state rechargeable battery can be 0.5 wt% to 35 wt%, for example, 1 wt% to 35 wt%, 5 wt% to 30 wt%, 8 wt% to 25 wt%, or 10 wt% to 20 wt%. These amounts are relative to the total weight of the components in the positive electrode, and specifically, relative to the total weight of the active material layer of the positive electrode.

[0091] In the example, relative to a 100wt% positive electrode active material layer, the positive electrode active material layer may comprise 50wt% to 99.35wt% of positive electrode active material, 0.5wt% to 35wt% of a sulfide-based solid electrolyte, 0.1wt% to 10wt% of a fluorinated resin binder, and 0.05wt% to 5wt% of vanadium oxide. When these ranges are met, the positive electrode for all-solid-state rechargeable batteries maintains high adhesion and also keeps the viscosity of the positive electrode composition at an appropriate level, while achieving high capacity and high ionic conductivity. As a result, processability is easier.

[0092] adhesive

[0093] The binder bonds the positive electrode active material particles together and to the positive electrode current collector. Examples of binders include, but are not limited to, polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, etc.

[0094] conductive materials

[0095] The positive electrode active material layer may further include a conductive material. The conductive material is used to provide electrode conductivity and may include, for example, carbon-based materials (such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, and carbon nanotubes); metallic materials in the form of metal powders or metal fibers containing copper, nickel, aluminum, silver, etc.; conductive polymers (such as polyphenylene derivatives); or combinations thereof.

[0096] The conductive material may be included in an amount of 0.1 wt% to 5 wt% or 0.1 wt% to 3 wt% relative to the total weight of each component of the positive electrode for an all-solid-state rechargeable battery, and specifically relative to the total weight of the active material layer of the positive electrode. Within these ranges, the conductive material can improve conductivity without causing a decrease in battery performance.

[0097] When the positive electrode active material layer further includes a conductive material, relative to 100 wt% of the positive electrode active material layer, the positive electrode active material layer may include 45 wt% to 99.25 wt% of the positive electrode active material, 0.5 wt% to 35 wt% of the sulfide solid electrolyte, 0.1 wt% to 10 wt% of the fluorine resin binder, 0.05 wt% to 5 wt% of the vanadium oxide, and 0.1 wt% to 5 wt% of the conductive material.

[0098] In addition to the above solid electrolyte, the positive electrode for the all-solid-state rechargeable battery may further include an oxide-based inorganic solid electrolyte. The oxide-based inorganic solid electrolyte may include, for example, Li 1+x Ti 2-x Al(PO4)3 (LTAP) (0 ≤ x ≤ 4), Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (0 < x < 2, 0 ≤ y < 3), BaTiO3, Pb(Zr,Ti)O3 (PZT), Pb 1-x La x Zr 1- y Ti y O3 (PLZT) (0 ≤ x < 1, 0 ≤ y < 1), Pb(Mg 1 / 3 Nb 2 / 3 )O3 - PbTiO3 (PMN - PT), HfO2, SrTiO3, SnO2, CeO2, Na2O, MgO, NiO, CaO, BaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, SiO2, lithium phosphate (Li3PO4), lithium titanium phosphate (Li x Ti[[ID=3十二条]] y (PO4)3, 0 < x < 2, 0 < y < 3), Li 1+x+y (Al,Ga) x (Ti,Ge) 2-x Si y P 3-y O 12 (0 ≤ x ≤ 1, 0 ≤ y ≤ 1), lithium lanthanum titanate (Li<eighty thousand one hundred and forty-two>La<00001​​​​​​​​​​​​​​Cross-sectional view of a all-solid-state rechargeable battery. Reference Figure 1 , the all-solid-state rechargeable battery 1000 may have a structure in which electrode assemblies are stacked: a negative electrode 40 including a negative electrode current collector layer 41 and a negative electrode active material layer 43; a solid electrolyte layer 30; and a positive electrode 20 including a positive electrode active material layer 23 and a positive electrode current collector layer 21. The all-solid-state rechargeable battery 1000 may be stored in a housing (such as a pouch). The all-solid-state rechargeable battery 1000 may further include an elastic layer 50 on the outer side of at least one of the positive electrode 20 and the negative electrode 40. Although Figure 1 illustrates one electrode assembly, the all-solid-state rechargeable battery may be made by stacking two or more electrode assemblies.

[0102] negative electrode

[0103] The negative electrode for the all-solid-state rechargeable battery may include, as an example, a negative electrode current collector layer and a negative electrode active material layer formed on the negative electrode current collector layer. The negative electrode active material layer includes a negative electrode active material and may further include a binder, a conductive material, and / or a solid electrolyte.

[0104] The negative electrode active material may include a material capable of reversibly inserting / extracting lithium ions, lithium metal, an alloy of lithium metal, a material capable of doping and dedoping lithium, or a transition metal oxide.

[0105] The material capable of reversibly inserting / extracting lithium ions is a carbon-based negative electrode active material and may include, for example, crystalline carbon, amorphous carbon, or a combination thereof. Examples of crystalline carbon may include graphite (such as amorphous, plate-like, flaky, spherical, or fibrous natural graphite or artificial graphite), and examples of amorphous carbon may include soft carbon or hard carbon, mesophase pitch carbide, calcined coke, etc. <00004​​​​​​​​(0 < x ≤ 2, such as SnO2), Sn-R alloys (where R is an element selected from the group consisting of: alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements (excluding Sn), Group 15 elements, Group 16 elements, transition metals, rare earth elements, and combinations thereof), etc., and at least one of them can be mixed with SiO2. Elements Q and R can be selected from the group consisting of: Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn (R does not include Sn), In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.

[0108] The silicon-carbon composite can be a silicon-carbon composite including the following: for example, including a core of crystalline carbon and silicon particles and an amorphous carbon coating on the surface of the core. The crystalline carbon can be artificial graphite, natural graphite, or a combination thereof. As the amorphous carbon precursor, coal tar pitch, mesophase pitch, petroleum pitch, petroleum oil, petroleum heavy oil, or polymer resins (such as phenolic resin, furan resin, and polyimide resin) can be used. Herein, relative to the total weight of the silicon-carbon composite, the amount of silicon can be 10 wt% to 50 wt%. Additionally, relative to the total weight of the silicon-carbon composite, the amount of crystalline carbon can be 10 wt% to 70 wt%, and relative to the total weight of the silicon-carbon composite, the amount of amorphous carbon can be 20 wt% to 40 wt%. Additionally, the thickness of the amorphous carbon coating can be 5 nm to 100 nm.

[0109] The average particle diameter (D 50 ) can be 10 nm to 20 µm, and for example, 10 nm to 500 nm. The silicon particles can exist in an oxidized form, and the Si:O atomic content ratio in the silicon particles showing the degree of oxidation can be 99:1 to 33:67. The silicon particles can be SiO x particles where the x range is greater than 0 and less than or equal to 2. Herein, the average particle diameter (D 50 ) can be measured by a particle size analyzer using the laser diffraction method, and D 50 refers to the diameter of the particles with a cumulative volume of 50% by volume in the particle size distribution.

[0110] The Si-based negative electrode active material or the Sn-based negative electrode active material can be mixed with the carbon-based negative electrode active material. The mixing ratio of the Si-based negative electrode active material or the Sn-based negative electrode active material to the carbon-based negative electrode active material can be 1:99 to 90:10 by weight ratio.

[0111] The amount of negative electrode active material in the negative electrode active material layer can be 95wt%~99wt% relative to the total weight of the negative electrode active material layer.

[0112] In one embodiment, the negative electrode active material layer further includes a binder and optionally a conductive material. The amount of binder in the negative electrode active material layer may be 1 wt% to 5 wt% relative to the total weight of the negative electrode active material layer. Alternatively, when a conductive material is included, the negative electrode active material layer may include 90 wt% to 98 wt% of negative electrode active material, 1 wt% to 5 wt% of binder, and 1 wt% to 5 wt% of conductive material.

[0113] The binder is used to bond the negative electrode active material particles together and also to bond the negative electrode active material to the negative electrode current collector. The binder may include a non-water-soluble binder, a water-soluble binder, or a combination thereof.

[0114] Non-water-soluble adhesives may include, for example, polyvinyl chloride, carboxylated polyvinyl chloride, polyvinylidene fluoride, ethylene oxide-containing polymers, ethylene propylene copolymers, polystyrene, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamide-imide, polyimide, or combinations thereof.

[0115] Water-soluble adhesives may include rubber-based adhesives or polymeric resin adhesives. Rubber-based adhesives may be selected from styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acryloyl rubber, butyl rubber, fluororubber, and combinations thereof. Polymeric resin adhesives may be selected from polyethylene oxide, polyvinylpyrrolidone, polyepoxychloropropane, polyphosphazene, polyacrylonitrile, ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resins, acrylic resins, phenolic resins, epoxy resins, polyvinyl alcohol, and combinations thereof.

[0116] When a water-soluble binder is used as a binder in the negative electrode active material layer, a viscosity-imparting thickener may be used simultaneously, and the thickener may include, for example, a cellulose compound. Cellulose compounds may include carboxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, their alkali metal salts, or combinations thereof. As an alkali metal, Na, K, or Li may be used. The amount of thickener used may be 0.1 to 3 parts by weight relative to 100 parts by weight of the negative electrode active material.

[0117] Conductive materials are used to impart conductivity to electrodes and may include, for example, carbon-based materials (such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, and carbon nanotubes); metallic materials, including copper, nickel, aluminum, silver, etc., in the form of metal powders or metal fibers; conductive polymers (such as polyphenylene derivatives); or mixtures thereof.

[0118] As the negative electrode current collector, copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, polymer substrates coated with conductive metal, and combinations thereof can be used.

[0119] As another example, the negative electrode for an all-solid-state rechargeable battery can be a deposition-type negative electrode. A deposition-type negative electrode refers to a negative electrode in which no negative electrode active material is present during battery assembly, but lithium metal or the like is deposited during battery charging and used as the negative electrode active material.

[0120] Figure 2 This is a cross-sectional view of an all-solid-state rechargeable battery including a deposited negative electrode. (Reference) Figure 2 The deposition-type negative electrode 40' may include a negative electrode current collector 41 and a negative electrode coating layer 45 formed on the negative electrode current collector 41. In an all-solid-state rechargeable battery having a deposition-type negative electrode 40', initial charging begins without an anode active material, and during charging, high-density lithium metal or the like is deposited between the negative electrode current collector 41 and the negative electrode coating layer 45 to form a lithium metal layer 44, which can be used as an anode active material. Accordingly, in an all-solid-state rechargeable battery that has been charged at least once, the deposition-type negative electrode 40' may include a negative electrode current collector 41, a lithium metal layer 44 formed on the negative electrode current collector 41, and a negative electrode coating layer 45 formed on the lithium metal layer 44. The lithium metal layer 44 refers to the layer in which lithium metal or the like is deposited during battery charging, and may be referred to as a metal layer, a negative electrode active material layer, etc.

[0121] The negative electrode coating 45 may include a metal, a carbon material, or a combination thereof used as a catalyst.

[0122] Metals may include, for example, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or combinations thereof, and may be formed from one class of these metals or from alloys of multiple classes. When the metal exists in particulate form, the average particle size (D) 50 The size can be about 4 μm or smaller, for example, 10 nm to 4 μm.

[0123] Carbon materials can be, for example, crystalline carbon, amorphous carbon, or combinations thereof. Crystalline carbon can be, for example, natural graphite, artificial graphite, mesophase carbon microspheres, or combinations thereof. Amorphous carbon can be, for example, carbon black, activated carbon, acetylene black, superconducting acetylene black, Ketjen black, or combinations thereof.

[0124] When the negative electrode coating layer 45 comprises both metal and carbon materials, the mixing ratio between the metal and carbon materials can be 1:10 to 2:1 by weight. In this case, lithium metal deposition can be effectively promoted, and the characteristics of the all-solid-state rechargeable battery can be improved. The negative electrode coating layer 45 may include, for example, carbon materials supported on catalytic metals, or a mixture comprising metal particles and carbon material particles.

[0125] The negative electrode coating 45 may include metal and amorphous carbon, for example. In this case, lithium metal deposition can be effectively promoted.

[0126] The negative electrode coating layer 45 may further include a binder, and the binder may be a conductive binder. Additionally, the negative electrode coating layer 45 may further include common additives such as fillers, dispersants, and ionic conductive agents.

[0127] The negative electrode coating layer 45 may have a thickness of, for example, 100 nm to 20 μm, 500 nm to 10 μm, or 1 μm to 5 μm.

[0128] The deposited negative electrode 40' may further include a thin film on the surface of the negative electrode current collector 41 (i.e., between the negative electrode current collector 41 and the negative electrode coating layer 45). This thin film may include elements capable of forming alloys with lithium. Elements capable of forming alloys with lithium may be gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, etc., and may be formed from one type of these metals or from an alloy of multiple types. This thin film may further planarize the deposited morphology of the lithium metal layer 44 and may further improve the characteristics of the all-solid-state rechargeable battery. This thin film may be formed by methods such as vacuum deposition, sputtering, and plating. The thin film may have a thickness of, for example, 1 nm to 500 nm.

[0129] solid electrolyte layer

[0130] The solid electrolyte layer 30 may include sulfide-based solid electrolytes, oxide-based inorganic solid electrolytes, etc. Detailed descriptions of sulfide-based solid electrolytes and oxide-based inorganic solid electrolytes are as described above.

[0131] In the example, the solid electrolyte included in the positive electrode 20 and the solid electrolyte layer 30 may include the same compound or different compounds. When both the positive electrode 20 and the solid electrolyte layer 30 include sulfide-type solid electrolytes such as argillacene sulfide, the overall performance of the all-solid-state rechargeable battery can be improved. Furthermore, when both the positive electrode 20 and the solid electrolyte layer 30 include the aforementioned oxide-type inorganic solid electrolytes, the all-solid-state rechargeable battery can exhibit excellent initial efficiency and lifetime characteristics, while also possessing high capacity and high energy density.

[0132] The average particle size (D) of the solid electrolyte included in the positive electrode 20 50 The particle size can be smaller than the average particle size (D) of the solid electrolyte included in the solid electrolyte layer 30. 50 In this configuration, lithium-ion mobility increases, maximizing the energy density of the all-solid-state rechargeable battery and thus improving overall performance. For example, the average particle size (D) of the solid electrolyte included in the positive electrode 20... 50The particle size can be 0.1 μm to 1.0 μm or 0.1 μm to 0.8 μm, and the average particle size (D) of the solid electrolyte included in the solid electrolyte layer 30 is... 50 The particle size can be 1.5 μm to 5.0 μm, 2.0 μm to 4.0 μm, or 2.5 μm to 3.5 μm. When the particle size range is met, lithium-ion transport is facilitated, maximizing the energy density of the all-solid-state rechargeable battery while suppressing resistance. Therefore, the overall performance of the all-solid-state rechargeable battery can be improved. In this paper, the average particle size (D...) of the solid electrolyte is... 50 The particle size distribution (D) can be measured using a particle size analyzer employing laser diffraction. Alternatively, approximately 20 or slightly more particles can be randomly selected from a microscopic photograph obtained using a scanning electron microscope or similar instrument, and the particle size can be measured to obtain the particle size distribution, from which D can be calculated. 50 value.

[0133] In addition to the solid electrolyte, the solid electrolyte layer may further include a binder. As a binder, styrene-butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, acrylate polymers, or combinations thereof may be used. However, this disclosure is not limited to the examples, and any other binder used in the art may be used herein. Acrylate polymers may be, for example, butyl acrylate, polyacrylate, polymethacrylate, or combinations thereof.

[0134] A solid electrolyte layer can be formed by adding a solid electrolyte to an adhesive solution, coating the substrate film with the solution, and drying. The solvent used in the adhesive solution can be isobutylisobutyric acid, xylene, toluene, benzene, hexane, or a combination thereof. Because the process for forming the solid electrolyte layer is well known in the art, its detailed description will be omitted.

[0135] The solid electrolyte layer can have a thickness of, for example, 10 μm to 150 μm.

[0136] The solid electrolyte layer may further include alkali metal salts, ionic liquids, and / or conductive polymers.

[0137] The alkali metal salt can be, for example, a lithium salt. The amount of lithium salt in the solid electrolyte layer can be 1 M or greater, and for example, 1 M to 4 M. In this case, the lithium salt can improve the ionic conductivity by improving the lithium ion mobility of the solid electrolyte layer.

[0138] Lithium salts may include, for example, LiSCN, LiN(CN)2, Li(CF3SO2)3C, LiC4F9SO3, LiN(SO2CF2CF3)2, LiCl, LiF, LiBr, LiI, LiB(C2O4)2, LiBF4, LiBF3(C2F5), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalate)borate (LiDFOB), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, LiN(SO2CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI, LiN(SO2F)2), LiCF3SO3, LiAsF6, LiSbF6, LiClO4, or mixtures thereof.

[0139] Additionally, lithium salts can be imides. For example, imide lithium salts may include lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, LiN(SO2CF3)2) and lithium bis(fluorosulfonyl)imide (LiFSI, LiN(SO2F)2). Lithium salts can maintain or improve ionic conductivity by appropriately preserving their chemical reactivity with ionic liquids.

[0140] Because the melting point of ionic liquids is equal to or lower than room temperature, ionic liquids are liquid at room temperature and refer to salts formed solely by ions or molten salts at room temperature.

[0141] Ionic liquids may be compounds including: a) one or more cations selected from ammonium cations, pyrrolidineonium cations, pyridinium cations, pyrimidineonium cations, imidazolium cations, piperidinium cations, pyrazolium cations, oxazolium cations, pyridazineonium cations, phosphonium cations, thioonium cations, and triazolium cations; and b) compounds selected from BF4. - PF6 - AsF6 - SbF6 - AlCl4 - HSO4 - ClO4 - CH3SO3 - CF3CO2 - Cl - ,Br - I - BF4 - SO4 2- CF3SO3 - (FSO2)2N - (C2F5SO2)2N - (C2F5SO2)(CF3SO2)N - and (CF3SO2)2N - One or more anions in it.

[0142] The ionic liquid may be one or more of, for example, N-methyl-N-propylpyrrolidone bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidone bis(3-trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide and 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide.

[0143] In the solid electrolyte layer, the weight ratio between the solid electrolyte and the ionic liquid can be 0.1:99.9 to 90:10, and for example, 10:90 to 90:10, 20:80 to 90:10, 30:70 to 90:10, 40:60 to 90:10, or 50:50 to 90:10. Solid electrolyte layers within these ranges can increase the electrochemical contact area with the electrodes to maintain or improve ionic conductivity. Accordingly, the energy density, discharge capacity, rate characteristics, etc., of all-solid-state rechargeable batteries can be improved.

[0144] All-solid-state rechargeable batteries can be cell cells with a positive electrode / solid electrolyte layer / negative electrode structure, dual cells with a positive electrode / solid electrolyte layer / negative electrode / solid electrolyte layer / positive electrode structure, or stacked cells with a repeating cell cell structure.

[0145] There are no particular limitations on the shape of all-solid-state rechargeable batteries, and they can be in shapes such as coin, button, sheet, stacked, cylindrical, and flat. Furthermore, all-solid-state rechargeable batteries can also be used as large batteries for electric vehicles, etc. For example, all-solid-state rechargeable batteries can also be used in hybrid vehicles, such as plug-in hybrid electric vehicles (PHEVs). Additionally, all-solid-state rechargeable batteries can be used in applications requiring large amounts of energy storage, such as electric bicycles and power tools.

[0146] refer to Figure 3 This will describe an all-solid-state rechargeable battery according to an embodiment. Figure 3 This is a cross-sectional view of an all-solid-state rechargeable battery based on an example. (Reference) Figure 3 All-solid-state rechargeable batteries can be rechargeable batteries capable of being repeatedly charged and discharged. In the following description, the positive electrode includes a cathode, and the negative electrode includes an anode.

[0147] The all-solid-state rechargeable battery 1000 includes a first electrode powder layer 100, a solid electrolyte powder layer 200, and a second electrode powder layer 300. The all-solid-state rechargeable battery 1000 includes an electrode assembly in which the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are stacked. However, this disclosure is not limited in this respect, and the all-solid-state rechargeable battery 1000 may further include various known configurations of all-solid-state rechargeable batteries, such as pouches, casings, etc.

[0148] The first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 can each be formed into a layer by pressing the powder of their respective layers. The particle size of the powder can be 10 nm to 10 mm, but this disclosure is not limited thereto.

[0149] The first electrode powder layer 100 may be the negative electrode contained in the aforementioned all-solid-state rechargeable battery, but this disclosure is not limited in this respect. For example, the first electrode powder layer 100 may be formed into a layer by pressing the powder forming the negative electrode together.

[0150] The first electrode powder layer 100 may include a first metal powder layer 110 and a functional powder layer 120 disposed on the first metal powder layer 110.

[0151] The first metal powder layer 110 can be formed into a layer by pressing metal powder, which includes the material contained in the negative electrode current collector layer, or metal powder including various known metal materials. The first metal powder layer 110 is in contact with the functional powder layer 120. The interface between the first metal powder layer 110 and the functional powder layer 120 may have protrusions and depressions. For example, since the first metal powder layer 110 and the functional powder layer 120 are each formed into a layer by pressing their respective powders, the interface between the first metal powder layer 110 and the functional powder layer 120 may have protrusions and depressions. Because the first metal powder layer 110 is formed into a layer by pressing powder, even if the first metal powder layer 110 is pressed multiple times, the first metal powder layer 110 can be formed into a thin film that will not break in the pressing direction. In a specific example, the first metal powder layer 110 may have a thickness of 1 μm to 8 μm. In another specific example, the thickness of the first metal powder layer 110 may be 2 μm or less.

[0152] The functional powder layer 120 may include an anodic active material powder layer 121.

[0153] The anodic active material powder layer 121 can be formed into a layer by pressing an active material powder, including the material contained in the aforementioned negative electrode active material layer, or various known negative electrode active materials. The anodic active material powder layer 121 is in contact with the first metal powder layer 110. The interface between the anodic active material powder layer 121 and the first metal powder layer 110 may have a raised and recessed shape. For example, since the anodic active material powder layer 121 and the first metal powder layer 110 are each formed into a layer by pressing their respective layer powders, the interface between the anodic active material powder layer 121 and the first metal powder layer 110 may have a raised and recessed shape. Because each of the anodic active material powder layer 121 and the first metal powder layer 110 is formed into a layer by pressing their respective layer powders, even if the anodic active material powder layer 121 and the first metal powder layer 110 are pressed multiple times in the stacking direction, the anodic active material powder layer 121 and the first metal powder layer 110 can be formed into a thin film that will not break in the stacking direction (i.e., the pressing direction).

[0154] Pressing along the stacking direction may include, but is not limited to, pressing along the thickness direction of each layer.

[0155] A solid electrolyte powder layer 200 may be disposed on the first electrode powder layer 100. The solid electrolyte powder layer 200 may be disposed between the first electrode powder layer 100 and the second electrode powder layer 300. The solid electrolyte powder layer 200 may be formed into a layer by pressing solid electrolyte powder, including materials contained in the aforementioned solid electrolyte layer, or various known solid electrolyte materials. The solid electrolyte powder layer 200 is in contact with the first electrode powder layer 100 and the second electrode powder layer 300. The interfaces between the solid electrolyte powder layer 200 and the first electrode powder layer 100, and between the solid electrolyte powder layer 200 and the second electrode powder layer 300, may have protrusions and depressions. For example, because the powder of the solid electrolyte powder layer 200, the powder of the first electrode powder layer 100, and the powder of the second electrode powder layer 300 are pressed, the interfaces between the solid electrolyte powder layer 200 and the first electrode powder layer 100, and between the solid electrolyte powder layer 200 and the second electrode powder layer 300, may have protrusions and depressions. Because each of the solid electrolyte powder layer 200, the first electrode powder layer 100, and the second electrode powder layer 300 is formed into a layer by pressing the powder of its respective layer, even if the solid electrolyte powder layer 200, the first electrode powder layer 100, and the second electrode powder layer 300 are pressed multiple times along the stacking direction, the solid electrolyte powder layer 200, the first electrode powder layer 100, and the second electrode powder layer 300 can be formed into a thin film that will not break in the stacking direction.

[0156] The second electrode powder layer 300 is disposed on the solid electrolyte powder layer 200.

[0157] The second electrode powder layer 300 may be the positive electrode included in the aforementioned all-solid-state rechargeable battery, but this disclosure is not limited in this respect. For example, the second electrode powder layer 300 may be formed in a layered form by pressing the powder forming the positive electrode together.

[0158] The second electrode powder layer 300 may include a second metal powder layer 310 disposed on the solid electrolyte powder layer 200 and a cathode active material powder layer 320 disposed between the second metal powder layer 310 and the solid electrolyte powder layer 200.

[0159] The second metal powder layer 310 can be formed into a layer by pressing metal powder or various known metal materials included in the positive electrode current collector layer. The second metal powder layer 310 is in contact with the cathode active material powder layer 320, and the interface between the second metal powder layer 310 and the cathode active material powder layer 320 may have protrusions and depressions. For example, since the second metal powder layer 310 and the cathode active material powder layer 320 are each formed into a layer by pressing their respective layers of powder, the interface between the second metal powder layer 310 and the cathode active material powder layer 320 may have protrusions and depressions. Because the second metal powder layer 310 is formed into a layer by pressing the powder included therein, even if the second metal powder layer 310 is pressed multiple times, the second metal powder layer 310 can be formed into a thin film that does not break along the pressing direction. In a specific example, the thickness of the second metal powder layer 310 may be 1 μm to 8 μm. In another specific example, the thickness of the second metal powder layer 310 may be 2 μm or less.

[0160] The cathode active material powder layer 320 can be formed into a layer by pressing active material powder, which includes the material contained in the positive electrode active material layer, or various known positive electrode active materials. The cathode active material powder layer 320 is in contact with the second metal powder layer 310 and the solid electrolyte powder layer 200. The interface between the cathode active material powder layer 320 and the second metal powder layer 310, and the interface between the cathode active material powder layer 320 and the solid electrolyte powder layer 200, may have protrusions and depressions. For example, since the cathode active material powder layer 320, the second metal powder layer 310, and the solid electrolyte powder layer 200 are each formed into a layer by pressing their respective powders, the interface between the cathode active material powder layer 320 and the second metal powder layer 310, and the interface between the cathode active material powder layer 320 and the solid electrolyte powder layer 200, may have protrusions and depressions. Because the cathode active material powder layer 320, the second electrode powder layer 300, and the solid electrolyte powder layer 200 are each formed into a layer by pressing their respective powders, even if the cathode active material powder layer 320, the second electrode powder layer 300, and the solid electrolyte powder layer 200 are pressed multiple times in the stacking direction, the cathode active material powder layer 320, the second electrode powder layer 300, and the solid electrolyte powder layer 200 can still be formed into a thin film that will not break in the stacking direction.

[0161] The all-solid-state rechargeable battery 1000 can be formed in various known stacked structures. For example, the all-solid-state rechargeable battery 1000 can be a single cell having a positive electrode / solid electrolyte layer / negative electrode, a dual cell having a negative electrode / solid electrolyte layer / positive electrode / solid electrolyte layer / negative electrode structure, or a stacked cell having a repeating single cell structure. However, this disclosure is not limited to these examples.

[0162] The all-solid-state rechargeable battery 1000 may include multiple all-solid-state rechargeable batteries 1000 stacked together. Various known elastic layers may be disposed between the all-solid-state rechargeable batteries 1000 stacked in the stacking direction. Each elastic layer may be formed by pressing powder containing various known elastic materials in the stacking direction.

[0163] In conventional all-solid-state rechargeable batteries, when the electrode current collector is formed from a metal plate or foil, the electrode active material layer and the solid electrolyte layer need to be bonded to the electrode current collector, and the electrode current collector, electrode active material layer, and solid electrolyte layer need to be pressed in the lamination direction. Because the electrode current collector in conventional all-solid-state rechargeable batteries is formed from a metal plate or foil, there are almost no protrusions or depressions at the interface between the electrode current collector and the electrode active material layer. Furthermore, when the electrode current collector, electrode active material layer, and solid electrolyte layer are pressed multiple times, the metal plate or foil may crack in the lamination direction. In addition, in conventional all-solid-state rechargeable batteries, due to the problem of electrode current collector cracking, it is difficult to press the electrode current collector, electrode active material layer, and solid electrolyte layer multiple times in the lamination direction, making it difficult to form the electrode current collector, electrode active material layer, and solid electrolyte layer into a thin film.

[0164] In contrast, in the all-solid-state rechargeable battery 1000 according to this disclosure, since each of the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 is formed into a layer by pressing the powder of its respective layer, the interface between each of the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 can have protrusions and depressions, thereby improving the battery capacity and battery performance of the all-solid-state rechargeable battery 1000. Furthermore, the powder of each of the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 is pressed and formed into a layer. Therefore, even when the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are pressed multiple times in the stacking direction, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are formed into a thin film, while preventing the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 from cracking, thereby improving the battery capacity and battery performance relative to the overall battery volume. Thus, the all-solid-state rechargeable battery 1000 has improved battery capacity and battery performance by pressing them into a thin film, and suppresses the cracking of the metal layers (i.e., the first electrode powder layer 100 and the second electrode powder layer 300).

[0165] Reference Figure 4 The description is based on another example of an all-solid-state rechargeable battery. The differences from the example above will be described below.

[0166] Figure 4 This is a cross-sectional view of an all-solid-state rechargeable battery based on another example. (Reference) Figure 4 According to another example, the all-solid-state rechargeable battery 1000 includes a first electrode powder layer 100, a solid electrolyte powder layer 200, and a second electrode powder layer 300.

[0167] The first electrode powder layer 100 may include the above-described deposited negative electrode. The first electrode powder layer 100 may include a first metal powder layer 110 and a functional powder layer 120 disposed on the first metal powder layer 110.

[0168] The functional powder layer 120 may include an anode-coated powder layer 122. The anode-coated powder layer 122 is formed by pressing together the material contained in the aforementioned negative electrode coating layer or the negative electrode coating powders included in various known negative electrode coating layers. The anode-coated powder layer 122 is in contact with the first metal powder layer 110, and the interface between the anode-coated powder layer 122 and the first metal powder layer 110 may have protrusions and depressions. Because the powders of each of the anode-coated powder layer 122 and the first metal powder layer 110 are pressed to form a layer, the interface between the anode-coated powder layer 122 and the first metal powder layer 110 may have a protruding and recessed shape. Because the powder of each of the anode-coated powder layer 122 and the first metal powder layer 110 is pressed to form a layer, even when the anode-coated powder layer 122 and the first metal powder layer 110 are pressed multiple times in the stacking direction, the anode-coated powder layer 122 and the first metal powder layer 110 can be formed into a thin film, while suppressing the cracking of the anode-coated powder layer 122 and the first metal powder layer 110 in the stacking direction.

[0169] In the all-solid-state rechargeable battery 1000, initial charging begins without an anode active material. During charging, lithium metal or the like is deposited between the first metal powder layer 110 and the anode-coated powder layer 122 to form a lithium metal layer. This lithium metal layer can be used as the anode active material.

[0170] In another example of an all-solid-state rechargeable battery 1000, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are each formed into layers by pressing the powder of their respective layers. Therefore, the interface between the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 can have protrusions and depressions, which improves the battery capacity and battery performance of the all-solid-state rechargeable battery 1000. In the all-solid-state rechargeable battery 1000, since the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are each formed into a layer by pressing their respective powders, even when the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are pressed multiple times in the stacking direction, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are also formed into a thin film. At the same time, the cracking of the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 in the stacking direction can be suppressed, thereby improving the battery capacity and battery performance relative to the total volume of the battery.

[0171] Therefore, the battery capacity and battery performance of the all-solid-state rechargeable battery 1000 are improved, and the cracking of the metal layer can be suppressed when the first electrode powder layer 100 and the second electrode powder layer 300 are pressed into a thin film.

[0172] refer to Figure 5 This section will describe an all-solid-state rechargeable battery based on yet another example. The differences from the example described above will be described below. Figure 5 This is a cross-sectional view of an all-solid-state rechargeable battery according to yet another example.

[0173] refer to Figure 5 According to another example, the all-solid-state rechargeable battery 1000 includes a first electrode powder layer 100, a solid electrolyte powder layer 200, and a second electrode powder layer 300.

[0174] The first electrode powder layer 100 may include a first metal powder layer 110, a functional powder layer 120 disposed on the first metal powder layer 110, and a third metal powder layer 130 disposed between the functional powder layer 120 and the solid electrolyte powder layer 200.

[0175] The third metal powder layer 130 can be formed into a layer by pressing metal powder or various known metal materials, including those contained in the negative electrode current collector layer. The third metal powder layer 130 is in contact with the functional powder layer 120 and the solid electrolyte powder layer 200. The interfaces between the third metal powder layer 130 and the functional powder layer 120, and between the third metal powder layer 130 and the solid electrolyte powder layer 200, may include protrusions and depressions. Because the third metal powder layer 130 and the functional powder layer 120 are each formed into a layer by pressing their respective powders, the interfaces between the third metal powder layer 130 and the functional powder layer 120 may include protrusions and depressions. Because the third metal powder layer 130 can be formed into a thin film by pressing the powder, the third metal powder layer 130 will not crack in the pressing direction even when pressed multiple times. The thickness of the third metal powder layer 130 can be 1 μm to 8 μm. More specifically, the thickness of the third metal powder layer 130 can be less than 2 μm.

[0176] The second electrode powder layer 300 may include a second metal powder layer 310 disposed on the solid electrolyte powder layer 200, a cathode active material powder layer 320 disposed between the second metal powder layer 310 and the solid electrolyte powder layer 200, and a fourth metal powder layer 330 disposed between the cathode active material powder layer 320 and the solid electrolyte powder layer 200.

[0177] The fourth metal powder layer 330 can be formed by pressing metal powder, including the material contained in the positive electrode current collector layer, or various known metal materials. The fourth metal powder layer 330 is in contact with the cathode active material powder layer 320 and the solid electrolyte powder layer 200. The interfaces between the fourth metal powder layer 330 and the cathode active material powder layer 320, and between the fourth metal powder layer 330 and the solid electrolyte powder layer 200, may include protrusions and depressions. Because the fourth metal powder layer 330 and the cathode active material powder layer 320 are each formed into a layer by pressing their respective powders, the interfaces between the fourth metal powder layer 330 and the cathode active material powder layer 320 may include protrusions and depressions. Because the fourth metal powder layer 330 is formed into a layer by pressing powder, even when the fourth metal powder layer 330 is pressed multiple times, it can be formed into a thin film without cracking in the pressing direction. The thickness of the fourth metal powder layer 330 can be 1 μm to 8 μm. More specifically, the thickness of the fourth metal powder layer 330 can be less than 2 μm.

[0178] In an all-solid-state rechargeable battery 1000 according to other examples, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are each formed into a layer by pressing the powder of their respective layers. Therefore, the interface between the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 may include protrusions and depressions, thereby improving the battery capacity and battery performance of the all-solid-state rechargeable battery 1000. Because the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are each formed into a layer by pressing the powder of their respective layers, even when the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are pressed multiple times in the stacking direction, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 will not rupture when formed into a thin film, thereby improving the battery capacity and battery performance of the all-solid-state rechargeable battery 1000 relative to the overall battery volume.

[0179] Accordingly, an all-solid-state rechargeable battery 1000 with improved battery capacity and performance while remaining crack-free in the metal layer can be provided.

[0180] In the following text, refer to Figures 6-8 This document describes a method for manufacturing an all-solid-state rechargeable battery according to some examples. This method can be used to manufacture all-solid-state rechargeable batteries according to the examples described above, but this disclosure is not limited thereto.

[0181] Figure 6 This is a flowchart illustrating a method for manufacturing an all-solid-state rechargeable battery according to an example. Figure 7 A method for manufacturing an all-solid-state rechargeable battery according to yet another example is shown.

[0182] refer to Figure 6 and Figure 7 First, a first electrode powder layer 100 is stacked (S100). The first metal powder layer 110 can be formed, for example, by stacking metal powder including the material contained in the aforementioned negative electrode current collector layer in the recessed portion 11 of the tray 10. A functional powder layer 120 can be formed by stacking active material powder included in the aforementioned negative electrode active material layer or coating powder including the material contained in the negative electrode coating layer on the first metal powder layer 110 in the recessed portion 11 of the tray 10. By stacking the functional powder layer 120 on the first metal powder layer 110 stacked in the recessed portion 11, a first electrode powder layer 100 including the first metal powder layer 110 and the functional powder layer 120 can be stacked in the recessed portion 11 of the tray 10.

[0183] Next, the solid electrolyte powder layer 200 is stacked on the first electrode powder layer 100 (S200). For example, the solid electrolyte powder layer 200 can be stacked on the first electrode powder layer 100 by stacking solid electrolyte powder including the material of the solid electrolyte layer stacked on the first electrode powder layer 100 in the recessed portion 11 of the tray 10.

[0184] Next, the second electrode powder layer 300 is stacked on the solid electrolyte powder layer 200 (S300). For example, the cathode active material powder layer 320 can be formed by stacking active material powder comprising the material contained in the positive electrode active material layer, which is sequentially stacked on the first electrode powder layer 100 and the solid electrolyte powder layer 200 in the recessed portion 11 of the tray 10. The second metal powder layer 310 can be formed by stacking metal powder comprising the material contained in the positive electrode current collector layer, which is on the cathode active material powder layer 320. The second electrode powder layer 300, comprising the second metal powder layer 310 and the cathode active material powder layer 320, can be stacked on the first electrode powder layer 100 and the solid electrolyte powder layer 200, which are sequentially stacked in the recessed portion 11 of the tray 10. The laminate SO comprising the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 can be stacked in the recessed portion 11 of the tray 10.

[0185] Next, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are pressed along the stacking direction (S400). For example, in an inert atmosphere such as argon (Ar) gas or nitrogen (N2) gas, a stack SO including the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 can be pressed using a pressing plate 20 corresponding to the recessed portion 11 of the tray 10.

[0186] Figure 8 A pressing device is shown that can be used in a manufacturing method of an all-solid-state rechargeable battery according to another example.

[0187] refer to Figure 8 A pressing apparatus for pressing a laminate SO comprising a first electrode powder layer 100, a solid electrolyte powder layer 200, and a second electrode powder layer 300 may include a pressing plate 20 corresponding to a recessed portion 11 of a tray 10. As another example, a pressing apparatus for pressing a laminate SO comprising a first electrode powder layer 100, a solid electrolyte powder layer 200, and a second electrode powder layer 300 may include a pressing roller 30 corresponding to a recessed portion 11 of a tray 10.

[0188] Refer again Figure 6 and Figure 7The pressed first electrode powder layer 100, solid electrolyte powder layer 200, and second electrode powder layer 300 are cut into multiple cutting units CO, and the multiple cutting units CO are stacked along the stacking direction (S500). For example, the laminate SO including the first electrode powder layer 100, solid electrolyte powder layer 200, and second electrode powder layer 300 pressed by the pressing device is cut along the cutting line CL to form multiple cutting units. The multiple cutting units CO can be stacked in the recessed portion 11 of the tray 10 along the stacking direction.

[0189] Next, multiple cutting units CO are pressed in the stacking direction (S600). For example, multiple cutting units CO can be pressed using a pressing device (such as a pressing plate 20).

[0190] The above process can be performed multiple times. However, this disclosure is not limited thereto.

[0191] In another example, a method for manufacturing an all-solid-state rechargeable battery includes stacking a first electrode powder layer 100, a solid electrolyte powder layer 200, and a second electrode powder layer 300 in powder form and pressing them to form layers. Therefore, the interfaces between the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 may include protrusions and depressions, thereby improving the battery capacity and battery performance of the all-solid-state rechargeable battery 1000. In the all-solid-state rechargeable battery 1000 manufactured by the method described herein, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are each formed into layers by pressing the powder of their respective layers. Therefore, even when the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 are pressed multiple times in the stacking direction, the first electrode powder layer 100, the solid electrolyte powder layer 200, and the second electrode powder layer 300 may not break, thereby improving the battery capacity and battery performance relative to the overall battery volume.

[0192] A method for manufacturing an all-solid-state rechargeable battery with improved battery capacity and battery performance is provided, wherein metal layers of electrodes (i.e., a first electrode powder layer 100 and a second electrode powder layer 300) are pressed into a thin film without causing the metal layers to crack.

[0193] Although this disclosure has been described in conjunction with examples now considered to be practices, it should be understood that this disclosure is not limited to the disclosed examples. Rather, this disclosure covers various modifications and equivalent arrangements.

Claims

1. An all-solid-state rechargeable battery, comprising: First electrode powder layer; A solid electrolyte powder layer is disposed on the first electrode powder layer; and The second electrode powder layer is disposed on the solid electrolyte powder layer.

2. The all-solid-state rechargeable battery of claim 1, wherein the first electrode powder layer comprises: Metal powder layer; and A functional powder layer is disposed on the metal powder layer.

3. The all-solid-state rechargeable battery of claim 2, wherein the metal powder layer is in contact with the functional powder layer, and An interface is formed between the metal powder layer and the functional powder layer, the interface including protrusions and depressions.

4. The all-solid-state rechargeable battery as described in claim 2, wherein the thickness of the metal powder layer is 1 μm to 8 μm.

5. The all-solid-state rechargeable battery of claim 2, wherein the functional powder layer comprises an anode active material powder layer.

6. The all-solid-state rechargeable battery of claim 2, wherein the functional powder layer comprises an anode-coated powder layer.

7. The all-solid-state rechargeable battery of claim 2, wherein the metal powder layer is a first metal powder layer, and the first electrode powder layer further includes a second metal powder layer disposed between the functional powder layer and the solid electrolyte powder layer.

8. The all-solid-state rechargeable battery of claim 1, wherein the second electrode powder layer comprises: A metal powder layer is disposed on the solid electrolyte powder layer; and A cathode active material powder layer is disposed between the metal powder layer and the solid electrolyte powder layer.

9. The all-solid-state rechargeable battery of claim 8, wherein the metal powder layer is in contact with the cathode active material powder layer, and An interface is formed between the metal powder layer and the cathode active material powder layer, and the interface includes protrusions and depressions.

10. The all-solid-state rechargeable battery of claim 8, wherein the metal powder layer is a first metal powder layer, and the second electrode powder layer further comprises a second metal powder layer disposed between the cathode active material powder layer and the solid electrolyte powder layer.

11. A method for manufacturing an all-solid-state rechargeable battery, the method comprising: The first electrode powder layer is stacked; A solid electrolyte powder layer is stacked on the first electrode powder layer; The second electrode powder layer is stacked on the solid electrolyte powder layer; and The first electrode powder layer, the solid electrolyte powder layer, and the second electrode powder layer are pressed together in the stacking direction.

12. The method of manufacturing an all-solid-state rechargeable battery as claimed in claim 11, wherein the first electrode powder layer, the solid electrolyte powder layer and the second electrode powder layer are stacked in a recessed portion of a tray.

13. The method of manufacturing an all-solid-state rechargeable battery as claimed in claim 12, wherein pressing the first electrode powder layer, the solid electrolyte powder layer and the second electrode powder layer in the stacking direction is performed by a pressing device corresponding to the recessed portion of the tray.

14. The method for manufacturing an all-solid-state rechargeable battery as claimed in claim 13, wherein the pressing device includes a pressing plate corresponding to the recessed portion.

15. The method of manufacturing an all-solid-state rechargeable battery as claimed in claim 13, wherein the pressing device includes a pressing roller corresponding to the recessed portion.

16. The method for manufacturing an all-solid-state rechargeable battery as claimed in claim 11, further comprising cutting the pressed first electrode powder layer, solid electrolyte powder layer and second electrode powder layer into a plurality of cutting units, and stacking the plurality of cutting units in the stacking direction.

17. The method of manufacturing an all-solid-state rechargeable battery as claimed in claim 16, further comprising pressing the plurality of cutting units in the stacking direction.

18. The method for manufacturing an all-solid-state rechargeable battery as claimed in claim 11, wherein the pressing of the first electrode powder layer, the solid electrolyte powder layer, and the second electrode powder layer is performed in an inert atmosphere.

19. The method for manufacturing an all-solid-state rechargeable battery as claimed in claim 11, wherein stacking the first electrode powder layer comprises: Layered metal powder layers; as well as The functional powder layer is stacked on the metal powder layer.

20. The method for manufacturing an all-solid-state rechargeable battery as claimed in claim 11, wherein stacking the second electrode powder layer comprises: The cathode active material powder layer is stacked on the solid electrolyte powder layer; as well as The metal powder layer is stacked on the cathode active material powder layer.

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