All-solid-state rechargeable battery

Abstract

This all-solid-state rechargeable battery includes: an all-solid-state cell stack including a plurality of all-solid-state cell stacked in a first direction; a housing for internally accommodating the all-solid-state cell stack; a first end plate located between the housing and a first end of the all-solid-state cell stack in the first direction; and a plurality of first metal wave springs located between the first end plate and the housing.

Description

Technical Field

[0001] This disclosure relates to all-solid-state rechargeable batteries. Background Technology

[0002] Recently, due to reports of the risk of explosions in batteries using liquid electrolytes, the development of all-solid-state rechargeable batteries is underway. All-solid-state rechargeable batteries are those in which all materials are made of solids and use solid electrolytes.

[0003] These all-solid-state rechargeable batteries are safe because there is no risk of explosion due to electrolyte solution leakage, and they have the advantage of being easy to manufacture as thin batteries.

[0004] Traditional all-solid-state rechargeable batteries include: an all-solid-state cell stack, which consists of multiple all-solid-state unit cells stacked in one direction; a housing for storing the all-solid-state cell stack inside; and a pressurization device for pressurizing the all-solid-state cell stack and the housing. Summary of the Invention

[0005] Technical issues

[0006] One embodiment is to provide an all-solid-state rechargeable battery in which, in response to the all-solid-state cell stack whose thickness may change during charging and discharging, the all-solid-state cell stack is uniformly pressed over a wide temperature range, resulting in improved shock resistance, reduced overall thickness, and improved energy density relative to thickness.

[0007] Technical solution

[0008] A solid-state rechargeable battery is provided, comprising: a solid-state cell stack including a plurality of solid-state cell stacked in a first direction; a housing storing the solid-state cell stack inside; a first end plate located between a first end of the solid-state cell stack in the first direction and the housing; and a plurality of first metal wave springs located between the first end plate and the housing.

[0009] Multiple first metal wave springs can contact the first end plate.

[0010] The first end plate may include a plurality of first recessed portions arranged spaced apart from each other in a second direction intersecting the first direction, and a plurality of first metal wave springs may each be inserted into a plurality of first recessed portions.

[0011] It may further include a second end plate located between and in contact with the plurality of first metal wave springs and the housing.

[0012] The second end plate may include a plurality of second recessed portions, which are arranged spaced apart from each other in a second direction, corresponding to a plurality of first recessed portions of the first end plate, and a plurality of first metal wave springs may be inserted into the plurality of second recessed portions respectively.

[0013] The second end plate can contact the housing.

[0014] Multiple first metal wave springs can contact the housing.

[0015] Multiple first metal wave springs may each include a ring-shaped wave spring.

[0016] A ring-shaped wave spring may include wave springs in which the waveforms having symmetrical shapes are stacked and extended in the direction that generates elastic restoring force.

[0017] A ring-shaped wave spring may include a wave spring in which a single layer of waveform extends in a ring shape.

[0018] A ring-shaped wave spring may include a wave spring in which waveforms of the same shape are stacked and extended in the direction that generates elastic restoring force.

[0019] It may further include a third end plate and a plurality of second metal wave springs, the third end plate being located between the second end of the all-solid-state cell stack in the first direction and the housing, and the plurality of second metal wave springs being located between the third end plate and the housing.

[0020] Multiple second metal wave springs can contact the third end plate.

[0021] The third end plate may include a plurality of third recessed portions arranged spaced apart from each other in a second direction intersecting the first direction, and a plurality of second metal wave springs may each be inserted into a plurality of third recessed portions.

[0022] It may further include a fourth end plate located between and in contact with the plurality of second metal wave springs and the housing.

[0023] The fourth end plate may include a plurality of fourth recessed portions arranged to be spaced apart from each other in a second direction, corresponding to a plurality of third recessed portions of the third end plate, and a plurality of second metal wave springs may each be inserted into a plurality of fourth recessed portions.

[0024] The fourth end plate can contact the housing.

[0025] Multiple second metal wave springs can contact the housing.

[0026] All-solid-state cell stacks can further include multiple buffer pads located between multiple all-solid-state cell units.

[0027] Each of the all-solid-state cell cells may include: a negative electrode; a positive electrode located on the negative electrode; and a solid electrolyte layer located between the negative electrode and the positive electrode.

[0028] Beneficial effects

[0029] According to an embodiment, an all-solid-state rechargeable battery is provided, wherein, in response to the all-solid-state cell stack whose thickness may change during charging and discharging, the all-solid-state cell stack is uniformly pressed over a wide temperature range, resulting in improved shock resistance, reduced overall thickness, and improved energy density relative to thickness. Attached Figure Description

[0030] Figure 1 This is a cross-sectional view of an all-solid-state battery.

[0031] Figure 2 It is a cross-sectional view of an all-solid-state battery including a precipitated negative electrode.

[0032] Figure 3 This is a cross-sectional view showing an all-solid-state rechargeable battery according to an embodiment.

[0033] Figure 4 yes Figure 3 An enlarged cross-sectional view of part A in the diagram.

[0034] Figure 5 This is a view showing an example of a first metal wave spring of an all-solid-state rechargeable battery according to an embodiment.

[0035] Figure 6 This is a view showing another example of the first metal wave spring of an all-solid-state rechargeable battery according to an embodiment.

[0036] Figure 7 This is a view showing another example of the first metal wave spring of an all-solid-state rechargeable battery according to an embodiment.

[0037] Figure 8 yes Figure 3 An enlarged cross-sectional view of part B in the diagram.

[0038] Figure 9 This is a cross-sectional view showing an all-solid-state rechargeable battery according to another embodiment. Detailed Implementation

[0039] This disclosure will be described more fully below with reference to the accompanying drawings, in which embodiments of the disclosure are illustrated. As those skilled in the art will recognize, the described embodiments can be modified in various ways without departing from the scope of this disclosure.

[0040] Furthermore, unless explicitly stated otherwise, the word “including” and variations such as “comprising” or “containing…” shall be understood to imply inclusion of the stated element but not exclusion of any other element.

[0041] In the accompanying drawings, thicknesses are shown enlarged to clearly illustrate multiple layers and regions. 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 "on" another element, the element may be directly on that other element, or there may be intermediate elements present. Conversely, when an element is referred to as "directly on" another element, there are no intermediate elements present.

[0042] Furthermore, the term "layer" in this article includes not only shapes formed across the entire surface when viewed from a plan view, but also shapes formed on a portion of the surface. In this article, "or" should not be interpreted as having an exclusive meaning; for example, "A or B" is interpreted as including A, B, A+B, etc.

[0043] Positive electrode for all-solid-state rechargeable batteries

[0044] In one embodiment, as a positive electrode for an all-solid-state rechargeable battery comprising a current collector layer and a positive electrode active material layer located on the current collector layer, a positive electrode having a positive electrode active material layer for an all-solid-state rechargeable battery is provided. This positive electrode includes at least one positive electrode active material, a sulfide-based solid electrolyte, a binder, and a conductive material. However, it is not limited thereto; the positive electrode for an all-solid-state rechargeable battery may include more or fewer components than those described above.

[0045] In one embodiment, a positive electrode for an all-solid-state rechargeable battery is manufactured by coating a positive electrode composition comprising at least one of a positive electrode active material, a sulfide-based solid electrolyte, a binder, and a conductive material onto a current collector, followed by drying and rolling.

[0046] Positive electrode active material

[0047] Positive electrode active materials can be used without restriction, as long as they are typically used in all-solid-state rechargeable batteries. For example, positive electrode active materials can be compounds capable of reversibly inserting and de-intercalating lithium, and can include compounds represented by any of the following chemical formulas.

[0048] Li a A 1-b X b D2 (0.90≤a≤1.8, 0≤b≤0.5);

[0049] Li a A1-b X b O 2-c D c (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05);

[0050] 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);

[0051] 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);

[0052] 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);

[0053] 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);

[0054] 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);

[0055] 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);

[0056] Li a Ni 1-b-c Mr b X c O 2-α Tα (0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α<2);

[0057] The a Nor 1-b-c Mn b X c O 2-α T2(0.90≤a≤1.8,0≤b≤0.5,0≤c≤0.05,0<α<2);

[0058] 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);

[0059] 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);

[0060] The a NiG b O2(0.90≤a≤1.8,0.001≤b≤0.1);

[0061] The a CoG b O2(0.90≤a≤1.8,0.001≤b≤0.1);

[0062] The a Mn 1-b G b O2(0.90≤a≤1.8,0.001≤b≤0.1);

[0063] The a Mn2G b O4 (0.90≤a≤1.8,0.001≤b≤0.1);

[0064] The a Mn 1-g G g PO4 (0.90≤a≤1.8,0≤g≤0.5);

[0065] QO2;QS2;LiQS2;

[0066] V2O5;LiV2O5;

[0067] LiZO2;

[0068] LiNiVO4;

[0069] Li (3-f) J2(PO4)3 (0≤f≤2);

[0070] Li (3-f) Fe2(PO4)3 (0≤f≤2);

[0071] Li a FePO4 (0.90≤a≤1.8).

[0072] In the above chemical formulas, A is selected from the group consisting of Ni, Co, Mn and their combinations; X is selected from the group consisting of Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and their combinations; D is selected from the group consisting of O, F, S, P and their combinations; E is selected from the group consisting of Co, Mn and their combinations; T is selected from the group consisting of F, S, P and their combinations; G is selected from the group consisting of Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V and their combinations; Q is selected from the group consisting of Ti, Mo, Mn and their combinations; Z is selected from the group consisting of Cr, V, Fe, Sc, Y and their combinations; and J is selected from the group consisting of V, Cr, Mn, Co, Ni, Cu and their combinations.

[0073] Positive electrode active materials can be, for example, lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel cobalt oxide (NC), lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium nickel manganese oxide (NM), lithium manganese oxide (LMO), or lithium iron phosphate oxide (LFP), etc.

[0074] The positive electrode active material may include lithium nickel-based oxides represented by the following chemical formula 1, lithium cobalt-based oxides represented by the following chemical formula 2, lithium iron phosphate-based compounds represented by the following chemical formula 3, or combinations thereof.

[0075] [Chemical Formula 1]

[0076] Li a1 Ni x1 M 1 y1 M 2 1-x1-y1 O2

[0077] In chemical formula 1, 0.9 ≤ a1 ≤ 1.8, 0.3 ≤ x1 ≤ 1, 0 ≤ y1 ≤ 0.7, and M 1 and M 2Each is independently selected from one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W and Zr.

[0078] [Chemical Formula 2]

[0079] Li a2 Co x2 M 3 1-x2 O2

[0080] In chemical formula 2, 0.9 ≤ a² ≤ 1.8, 0.6 ≤ x² ≤ 1, M 3 It is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W and Zr.

[0081] [Chemical Formula 3]

[0082] Li a3 Fe x3 M 4 1-x3 PO4

[0083] In chemical formula 3, 0.9 ≤ a³ ≤ 1.8, 0.6 ≤ x³ ≤ 1, and M 4 It is one or more elements selected from the group consisting of Al, B, Ba, Ca, Ce, Co, Cr, Cu, F, Fe, Mg, Mn, Mo, Nb, P, S, Si, Sr, Ti, V, W and Zr.

[0084] The average particle size D50 of the positive electrode active material can be from 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 these particle size ranges can be uniformly mixed with other components within the positive electrode active material layer, and high capacity and high energy density can be achieved.

[0085] The positive electrode active material can be in the form of secondary particles made by coagulating multiple primary particles, or it can be in the form of a single particle. In addition, the positive electrode active material can be spherical or nearly spherical, or it can be polyhedral or irregular in shape.

[0086] Sulfide-based solid electrolytes

[0087] Sulfide-based solid electrolytes can be, for example, Li₂S-P₂S₅, Li₂S-P₂S₅-Lix (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, Li2S-P2S5-ZmSn (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, etc.)

[0088] Sulfide-based solid electrolytes can be obtained, for example, by mixing Li₂S and P₂S₅ in a molar ratio of about 50:50 to about 90:10 or about 50:50 to about 80:20 and selectively heat-treating them. Within the above mixing ratio range, sulfide-based solid electrolytes with excellent ionic conductivity can be prepared. The ionic conductivity can be further improved by adding SiS₂, GeS₂, B₂S₃, etc., as other components.

[0089] Mechanical grinding or solution processing can be used as mixing methods for sulfur-containing raw materials to prepare sulfide-based solid electrolytes. Mechanical grinding involves placing the starting material, grinding balls, etc., into a reactor and vigorously stirring them to form particles. Solution processing involves mixing the starting material in a solvent to obtain a solid electrolyte as a precipitate. Furthermore, if heat treatment is performed after mixing, the solid electrolyte crystals can become stronger and the ionic conductivity can be improved. For example, sulfide-based solid electrolytes can be manufactured by mixing sulfur-containing raw materials and subjecting them to heat treatment more than twice, resulting in sulfide-based solid electrolytes with high ionic conductivity and robustness.

[0090] As an example, sulfide-based solid electrolyte particles can be argyrodite-type sulfides. Argyrodite-type sulfides can be represented, for example, by the chemical formula Li. a M b P c S d A e(a, b, c, d, and e are all 0 or greater and 12 or less, M is a metal other than Li or a combination of multiple 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 (x is 0.2 or greater and 1.8 or less, and A is F, Cl, Br, or I). Specifically, silver-germanium sulfides can be Li3PS4, Li7P3S... 11 , Li7PS6, Li6PS5Cl, Li6PS5Br, Li 5.8 PS 4.8 Cl 1.2 Li 6.2 PS 5.2 Br 0.8 wait.

[0091] This sulfide-based solid electrolyte, which includes sulfide-germanium sulfides, has a temperature close to approximately 10 at room temperature. -4 S / cm to approximately 10 -2 The high ionic conductivity of S / cm (which is the ionic conductivity of ordinary liquid electrolytes) allows for a tight bond to be formed between the positive electrode active material and the solid electrolyte without degrading the ionic conductivity. Furthermore, a tight interface is formed between the electrode layer and the solid electrolyte layer. All-solid-state batteries incorporating this technology exhibit improved battery performance, such as rate performance, coulombic efficiency, and cycle life characteristics.

[0092] Sulfide-based solid electrolytes of the sulfide type can be manufactured, for example, by mixing lithium sulfide, phosphorus sulfide, and selective lithium halides. After mixing, they can be heat-treated. The heat treatment may include, for example, two or more heat treatment steps.

[0093] According to one embodiment, the average particle size D50 of the sulfide-based solid electrolyte particles 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, the sulfide-based solid electrolyte particles can be small particles with an average particle size D50 of 0.1 μm to 1.0 μm, or large particles with an average particle size D50 of 1.5 μm to 5.0 μm, depending on the location or purpose of use. Sulfide-based solid electrolyte particles within this particle size range can effectively pass between solid particles within the battery and exhibit excellent contact with electrode active materials and connectivity between solid electrolyte particles. The average particle size of the 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 D50 can be calculated from this.

[0094] The content of solid electrolyte in the positive electrode of an all-solid-state battery can be from 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%. This content is based on the total weight of the components within the positive electrode, and more specifically, on the total weight of the positive electrode active material layer.

[0095] In one embodiment, for a 100 wt% positive electrode active material layer, the positive electrode active material layer may include 50 wt% to 99.35 wt% of positive electrode active material, 0.5 wt% to 35 wt% of sulfide-based solid electrolyte, 0.1 wt% to 10 wt% of fluorinated resin binder, and 0.05 wt% to 5 wt% of vanadium oxide. If this content range is met, the positive electrode for an all-solid-state rechargeable battery maintains high adhesion while achieving high capacity and high ionic conductivity, and the viscosity of the positive electrode composition remains at an appropriate level, thereby improving processability.

[0096] adhesive

[0097] The binder improves the adhesion properties between the positive electrode active material particles and between the positive electrode active material particles and the current collector. Examples of binders include 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., but are not limited to these.

[0098] conductive materials

[0099] The positive electrode active material layer may further include a conductive material. The conductive material is included to provide electrode conductivity, and examples of conductive materials may include: carbon-based materials such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fibers, carbon nanotubes, etc.; metal-based materials including metal powders or metal fibers of copper, nickel, aluminum, silver, etc.; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0100] The positive electrode of the all-solid-state battery may include 0.1 wt% to 5 wt%, or 0.1 wt% to 3 wt% of conductive material, relative to the total weight of all components of the positive electrode or relative to the total weight of the positive electrode active material layer. Within this content range, the conductive material can improve conductivity without degrading battery performance.

[0101] When the positive electrode active material layer further includes a conductive material, for a 100 wt% positive electrode active material layer, the positive electrode active material layer may include 45 wt% to 99.25 wt% of positive electrode active material, 0.5 wt% to 35 wt% of sulfide-based solid electrolyte, 0.1 wt% to 10 wt% of fluorinated resin binder, 0.05 wt% to 5 wt% of vanadium oxide and 0.1 wt% to 5 wt% of conductive material.

[0102] In addition to the aforementioned solid electrolytes, the positive electrode for lithium secondary batteries may further include an oxide-based inorganic solid electrolyte. For example, the oxide-based inorganic solid electrolyte may include 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 (Mg3NB 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 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 x La y TiO3, 0 < x < 2, 0 < y < 3), Li2O, LiAlO2, Li2O - Al2O3 - SiO2 - P2O5 - TiO2 - GeO2 - based ceramics, garnet - based ceramics Li 3+x La3M2O 12 (M = Te, Nb or Zr; x is an integer from 1 to 10) or a combination thereof.

[0103] All - solid - state rechargeable battery

[0104] One embodiment provides an all - solid - state rechargeable battery including the above - mentioned positive electrode, negative electrode, and a solid electrolyte layer located between the positive electrode and the negative electrode. The all - solid - state rechargeable battery can also be expressed as an all - solid - state battery or an all - solid - state lithium rechargeable battery.

[0105] Figure 1 is a cross - sectional view of an all - solid - state battery.

[0106] Referring to Figure 1 , the all - solid - state battery 1000 can be a structure in which the electrode assembly is housed in a housing such as a pouch or a can. In this electrode assembly, 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 are stacked. The all - solid - state battery 1000 can further include an elastic layer 50 outside at least one of the positive electrode 20 and the negative electrode 40. Figure 1 Shows an electrode assembly including a negative electrode 40, a solid electrolyte layer 30, and a positive electrode 20, but an all - solid - state battery can be manufactured by stacking two or more electrode assemblies.

[0107] Negative electrode

[0108] The negative electrode for an all - solid - state battery can include, for example, a current collector layer and a negative electrode active material layer located on the current collector layer. The negative electrode active material layer includes a negative electrode active material and can further include a binder, a conductive material, and / or a solid electrolyte.

[0109] The negative electrode active material includes a material capable of reversible insertion and extraction of lithium ions, lithium metal, an alloy of lithium metal, a material doped or undoped with lithium, or a transition metal oxide.

[0110] Materials that can reversibly embed / extract lithium ions may include, for example, crystalline carbon, amorphous carbon, or a combination thereof as the carbon-based negative electrode active material. The crystalline carbon may be amorphous, or natural graphite or artificial graphite in the form of plates, flakes, spheres, or fibers. The amorphous carbon may be soft carbon, hard carbon, mesophase pitch carbonized product, calcined coke, etc.

[0111] The lithium metal alloy includes an alloy of lithium and a metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn.

[0112] Materials that can be doped / undoped with lithium may be Si-based negative electrode active materials or Sn-based negative electrode active materials. The Si-based negative electrode active materials may include silicon, silicon-carbon composites, SiO x (0 < x < 2), Si-Q alloys (where Q is an alkali metal, alkaline earth metal, Group 13 element, Group 14 element, Group 15 element, Group 16 element, transition metal, rare earth element, and combinations thereof, but not including Si), and the Sn-based negative electrode active materials may include Sn, SnO2, Sn-R alloys (where R is an alkali metal, alkaline earth metal, Group 13 element, Group 14 element, Group 15 element, Group 16 element, transition metal, rare earth element, and combinations thereof, but not including Sn). At least one of these materials may be mixed with SiO2. The elements Q and R may be selected from 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, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.

[0113] The silicon-carbon composite may be a silicon-carbon composite including a core containing crystalline carbon and silicon particles and an amorphous carbon coating provided on the surface of the core. The crystalline carbon may be artificial graphite, natural graphite, or a combination thereof. The amorphous carbon precursor may be coal-based pitch, mesophase pitch, petroleum-based pitch, coal-based oil, petroleum-based heavy oil, or a polymer resin such as phenolic resin, furan resin, or polyimide resin. In this case, based on the total weight of the silicon-carbon composite, the content of silicon may be about 10 wt% to about 50 wt%. In addition, based on the total weight of the silicon-carbon composite, the content of crystalline carbon may be about 10 wt% to about 70 wt%, and based on the total weight of the silicon-carbon composite, the content of amorphous carbon may be about 20 wt% to about 40 wt%. Additionally, the thickness of the amorphous carbon coating may be about 5 nm to about 100 nm.

[0114] The average particle size (D50) of the silicon particles can be from about 10 nm to about 20 μm, for example, from 10 nm to 500 nm. The silicon particles can exist in an oxidized form, and in this case, the atomic ratio of Si:O in the silicon particles, indicating the degree of oxidation, can be a weight ratio of about 99:1 to about 33:67. The silicon particles can be SiO₂. x Particles, and in this case, SiO x The range of x in the equation can be greater than approximately 0 and less than approximately 2. Here, the average particle size D50 is measured using a particle size analyzer with laser diffraction and represents particles that accumulate to approximately 50% of the total volume in the particle distribution.

[0115] Si-based or Sn-based anode active materials can be mixed with carbon-based anode active materials. When Si-based or Sn-based anode active materials are mixed with carbon-based anode active materials, the mixing ratio can be from about 1:99 to about 10:90 by weight.

[0116] In the negative electrode active material layer, the negative electrode active material may be included in an amount of about 95 wt% to about 99 wt% based on the total weight of the negative electrode active material layer.

[0117] In one embodiment, the negative electrode active material layer includes a binder and may optionally further include a conductive material. Based on the total weight of the negative electrode active material layer, the binder content in the negative electrode active material layer may be from about 1 wt% to about 5 wt%. Alternatively, when further including a conductive material, the negative electrode active material layer may include about 90 wt% to about 98 wt% of the negative electrode active material, about 1 wt% to about 5 wt% of the binder, and about 1 wt% to about 5 wt% of the conductive material.

[0118] The binder is used to ensure good adhesion between particles of the negative electrode active material, and also to adhere the negative electrode active material to the current collector. The binder can be a non-water-soluble binder, a water-soluble binder, or a combination thereof.

[0119] Examples of non-water-soluble adhesives include polyvinyl chloride, carboxylated polyvinyl chloride, polyvinyl fluoride, ethylene oxide-containing polymers, ethylene propylene copolymers, polystyrene, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, polyamide-imide, polyimide, or combinations thereof.

[0120] Water-soluble adhesives may include rubber adhesives or polymer resin adhesives. Rubber adhesives may be selected from styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, butyl rubber, fluororubber, and combinations thereof. Polymer resin adhesives may be selected from polyethylene oxide, polyvinylpyrrolidone, polyepoxychloropropane, polyphosphazene, polyacrylonitrile, ethylene propylene diene copolymer, polyvinylpyridine, chlorosulfonated polyethylene, latex, polyester resin, acrylic resin, phenolic resin, epoxy resin, polyvinyl alcohol, and combinations thereof.

[0121] When a water-soluble binder is used as the negative electrode binder, it may further include a cellulose-based compound capable of imparting viscosity. As a cellulose-based compound, one or more of carboxymethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, or their alkali metal salts may be mixed and used. As an alkali metal, Na, K, or Li may be used. Based on 100 parts by weight of the negative electrode active material, the amount of thickener used may be from about 0.1 parts by weight to about 3 parts by weight.

[0122] Conductive materials are included to provide electrode conductivity. Any electrically conductive material can be used as a conductive material unless it causes a chemical change. Examples of conductive materials include carbon-based materials such as natural graphite, synthetic graphite, carbon black, acetylene black, Ketjen black, carbon fiber, etc.; metal-based materials including powders or fibers of copper, nickel, aluminum, silver, etc.; conductive polymers such as polyphenylene derivatives; or mixtures thereof.

[0123] The current collector may include one of the following: copper foil, nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, polymer substrate coated with conductive metal, and combinations thereof.

[0124] On the other hand, the negative electrode used in all-solid-state batteries can be, for example, a precipitation-type negative electrode. A precipitation-type negative electrode can be a negative electrode that does not have a negative electrode active material during the assembly of the electrochemical battery, but lithium metal or the like is deposited during the charging process of the electrochemical battery and used as a negative electrode active material.

[0125] Figure 2 This is a cross-sectional view of an all-solid-state battery including a deposited negative electrode.

[0126] Reference Figure 2The deposition-type negative electrode 40' may include a current collector layer 41 and a negative electrode coating 45 disposed on the current collector layer 41. A rechargeable lithium battery having this deposition-type negative electrode 40' begins initial charging without a negative electrode active material, and during charging, high-density lithium metal or the like is deposited between the current collector layer 41 and the negative electrode coating 45 to form a lithium metal layer 44, which can be used as a negative electrode active material. Therefore, in an all-solid-state battery that is charged more than once, the deposition-type negative electrode 40' may include a current collector layer 41, a lithium metal layer 44 on the current collector layer 41, and a negative electrode coating 45 disposed on the metal layer. The lithium metal layer 44 refers to a layer of lithium metal or the like deposited during the charging of the electrochemical battery, and may be referred to as a metal layer, a negative electrode active material layer, etc., and serves as the negative electrode active material.

[0127] The negative electrode coating 45 includes a metal or carbon material that acts as a catalyst.

[0128] The metal may include gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or combinations thereof, and may be composed of an alloy selected from one or more of these. The metal included in the negative electrode catalyst layer may have an average particle size (D50) of less than or equal to about 4 μm (e.g., about 10 nm to about 4 μm).

[0129] The carbon material can be, for example, crystalline carbon, amorphous carbon, or a combination thereof. Crystalline carbon can be, for example, selected from at least one of the following: natural graphite, artificial graphite, mesophase carbon microspheres, and combinations thereof. Amorphous carbon can be selected from at least one of the following: carbon black, activated carbon, acetylene black, superconducting acetylene black, Ketjen black, and combinations thereof.

[0130] When the negative electrode coating 45 comprises metal and carbon materials, the metal and carbon materials can be mixed, for example, in a weight ratio of about 1:10 to about 2:1. This can effectively promote the deposition of lithium metal and improve the characteristics of the all-solid-state battery. The negative electrode coating 45 may comprise, for example, carbon materials on which a catalyst metal is loaded, or a mixture of metal particles and carbon material particles.

[0131] The negative electrode coating 45 may include, for example, metals and amorphous carbon, and in this case, it can effectively promote the deposition of lithium metal.

[0132] The negative electrode coating 45 may further include a binder, and the binder may be a conductive binder. Furthermore, the negative electrode coating 45 may further include general additives such as fillers, dispersants, ionic conductive agents, etc.

[0133] The thickness of the negative electrode coating 45 can be, for example, 100 nm to 20 μm, or 500 nm to 10 μm, or 1 μm to 5 μm.

[0134] For example, the deposited negative electrode 40' may further include a thin film on the surface of the current collector 41 (i.e., between the current collector 41 and the negative electrode coating 45). The thin film may include elements capable of forming alloys with lithium. Elements capable of forming alloys with lithium may be, for example, gold, silver, zinc, tin, indium, silicon, aluminum, bismuth, etc., which may be used alone or as an alloy of more than one. The thin film may further planarize the deposited pattern of the lithium metal layer 44 and further improve the characteristics of the all-solid-state battery. The thin film may be formed, for example, by methods such as vacuum deposition, sputtering, or electroplating. The thickness of the thin film may be, for example, from 1 nm to 500 nm.

[0135] solid electrolyte layer

[0136] The solid electrolyte layer 30 may include sulfide-based solid electrolytes, oxide-based solid electrolytes, etc. Specific details of sulfide-based solid electrolytes and oxide-based solid electrolytes are as described above.

[0137] In one example, the solid electrolyte included in the positive electrode 20 and the solid electrolyte included in the solid electrolyte layer 30 may comprise the same compound or different compounds. For example, if both the positive electrode 20 and the solid electrolyte layer 30 comprise a sulfide-based solid electrolyte of the argyrodite type, the overall performance of the all-solid-state rechargeable battery can be improved. Furthermore, as another example, if both the positive electrode 20 and the solid electrolyte layer 30 comprise the aforementioned coated solid electrolyte, the all-solid-state rechargeable battery can achieve high capacity, high energy density, and excellent initial efficiency and lifetime characteristics.

[0138] Meanwhile, the average particle size D50 of the solid electrolyte included in the positive electrode 20 can be smaller than the average particle size D50 of the solid electrolyte included in the solid electrolyte layer 30. In this case, the overall performance can be improved by maximizing the energy density of the all-solid-state battery and increasing the mobility of lithium ions. For example, the average particle size D50 of the solid electrolyte included in the positive electrode 20 can be 0.1 μm to 1.0 μm, or 0.1 μm to 0.8 μm, and the average particle size D50 of the solid electrolyte included in the solid electrolyte layer 30 can be 1.5 μm to 5.0 μm, or 2.0 μm to 4.0 μm, or 2.5 μm to 3.5 μm. If these particle size ranges are met, the energy density of the all-solid-state rechargeable battery can be maximized, and lithium ion transfer is easy, which can then suppress resistance, thereby improving the overall performance of the all-solid-state rechargeable battery. Here, the average particle size D50 of the solid electrolyte can be measured using a particle size analyzer using laser diffraction. Alternatively, about 20 particles can be selected from microscopic images such as those from a scanning electron microscope to measure the particle size and obtain the particle size distribution, and then the D50 value can be calculated.

[0139] In addition to the solid electrolyte, the solid electrolyte layer may also include a binder. Here, the binder may include, but is not limited to, styrene-butadiene rubber, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, acrylate polymers, or combinations thereof. Acrylate polymers may be, for example, butyl acrylate, polyacrylate, polymethacrylate, or combinations thereof.

[0140] A solid electrolyte layer can be formed by adding a solid electrolyte to a binder solution, coating it onto a base film, and drying the result. The solvent for the binder solution can be isobutyryl isobutyrate, xylene, toluene, benzene, hexane, or a combination thereof. Since the process for forming the solid electrolyte layer is well known in the art, its detailed description will be omitted.

[0141] The thickness of the solid electrolyte layer can be, for example, from about 10 μm to about 150 μm.

[0142] The solid electrolyte layer may further comprise alkali metal salts and / or ionic liquids and / or conductive polymers.

[0143] Alkali metal salts can be, for example, lithium salts. The lithium salt content in the solid electrolyte layer can be 1 M or greater, for example, 1 M to 4 M.

[0144] In this case, lithium salts can improve ionic conductivity by increasing the lithium ion mobility in the solid electrolyte layer.

[0145] 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(oxaloate)borate (LiBOB), lithium oxalyldifluoroborate (LIODFB), lithium difluoro(oxaloate)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.

[0146] Furthermore, lithium salts can be imide salts, such as 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.

[0147] Ionic liquids have melting points below room temperature, so they are salts that are liquid at room temperature and consist only of ions, or molten salts at room temperature.

[0148] Ionic liquids can be compounds including: a) one or more positive ions selected from: ammonium compounds, pyrrolidine-onions, pyridinium compounds, pyrimidine-onions, imidazolium compounds, piperidinium compounds, pyrazolium compounds, oxazolium compounds, pyridazine-onions, phosphonium compounds, sulfonium compounds, triazolium compounds, and mixtures thereof; and b) one or more negative ions selected from: BF4-, PF6-, AsF6-, SbF6-, AlCl4-, HSO4-, ClO4-, CH3SO3-, CF3CO2-, Cl-, Br-, I-, BF4-, SO4-, CF3SO3-, (FSO2)2N-, (C2F5SO2)2N-, (C2F5SO2,CF3SO2)N- and (CF3SO2)2N-.

[0149] Ionic liquids may be, for example, one or more selected from the group consisting of: N-methyl-N-propylpyrroledium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrroledium bis(3-trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolelium bis(trifluoromethylsulfonyl)amide, and 1-ethyl-3-methylimidazolelium bis(trifluoromethylsulfonyl)amide.

[0150] The weight ratio of solid electrolyte to ionic liquid in the solid electrolyte layer can be from about 0.1:99.9 to about 90:10, for example, from about 10:90 to about 90:10, from about 20:80 to about 90:10, from about 30:70 to about 90:10, from about 40:60 to about 90:10, or from about 50:50 to about 90:10. Solid electrolyte layers meeting these ranges can maintain or improve ionic conductivity by increasing the electrochemical contact area with the electrode. Therefore, the energy density, discharge capacity, rate performance, etc., of all-solid-state batteries can be improved.

[0151] All-solid-state rechargeable batteries can be single cells with a structure of positive electrode / solid electrolyte layer / negative electrode, dual cells with a structure of positive electrode / solid electrolyte layer / negative electrode / solid electrolyte layer / positive electrode, or stacked batteries with a structure of repeated single cells.

[0152] Solid-state batteries have no particular shape limitations; they can be coin-shaped, button-shaped, sheet-shaped, stacked, cylindrical, flat, etc. Furthermore, solid-state batteries can be used in large-size batteries used in electric vehicles, etc. For example, they can also be used in hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). In addition, they can be used in fields requiring large amounts of energy storage, and can be used in, for example, electric bicycles or power tools.

[0153] Below, refer to Figures 3 to 7 This describes an all-solid-state rechargeable battery according to an embodiment. The all-solid-state rechargeable battery according to the embodiment is a rechargeable battery that can be repeatedly charged and discharged. In the following, the positive electrode includes a cathode, and the negative electrode includes an anode.

[0154] For example, an all-solid-state rechargeable battery according to an embodiment includes an all-solid-state cell stack comprising a plurality of all-solid-state cell cells stacked in one direction. (Refer to...) Figure 2 Each of the multiple all-solid-state cell units in the all-solid-state cell stack includes an all-solid-state battery containing the aforementioned deposited negative electrode, and therefore the thickness may vary due to the lithium metal layer formed during charging, but is not limited thereto.

[0155] As another example, each of a plurality of all-solid-state cell stacks in an all-solid-state rechargeable battery according to an embodiment may include an all-solid-state battery, which includes the above-referenced... Figure 1 The negative electrode described.

[0156] Figure 3 This is a cross-sectional view showing an all-solid-state rechargeable battery according to an embodiment.

[0157] Reference Figure 3According to the embodiment, the all-solid-state rechargeable battery 1000 includes an all-solid-state cell stack 100, a housing 200, a first end plate 300, a plurality of first metal wave springs 400, a second end plate 500, a third end plate 600, a plurality of second metal wave springs 700, and a fourth end plate 800.

[0158] The all-solid-state cell stack 100 is located inside the housing 200. The all-solid-state cell stack 100 includes multiple all-solid-state cell units 110 and multiple buffer pads 120.

[0159] Multiple all-solid-state cell cells 110 are stacked in a first direction X. Each of the multiple all-solid-state cell cells 110 includes a negative electrode, a positive electrode, and a solid electrolyte layer. Here, the first direction (X) may include... Figure 3 The vertical direction, but not limited to this.

[0160] The negative electrode may include, but is not limited to, at least one of the negative electrodes included in the all-solid-state rechargeable battery described above and deposited negative electrodes. The negative electrode may have a plate shape or a foil shape, but is not limited to these.

[0161] The positive electrode is located on top of the negative electrode, with a solid electrolyte layer in between. The positive electrode may include, but is not limited to, the positive electrode included in the all-solid-state rechargeable battery described above. The positive electrode may have a plate shape or a foil shape, but is not limited to these.

[0162] A solid electrolyte layer is located between the negative electrode and the positive electrode. The solid electrolyte layer may include, but is not limited to, the solid electrolyte layer included in the all-solid-state rechargeable battery described above. The solid electrolyte layer may have the form of a layer between the negative electrode and the positive electrode, but is not limited to this.

[0163] Each of the multiple all-solid-state cell 110 can have various known stacking structures. For example, the all-solid-state cell 110 can have: a cell with a structure of positive electrode / solid electrolyte layer / negative electrode, a dual cell with a structure of positive electrode / solid electrolyte layer / negative electrode / solid electrolyte layer / positive electrode, or a stacked battery structure with a repeating structure of cell, but is not limited thereto.

[0164] Multiple buffer pads 120 are located between multiple all-solid-state cell 110 stacked along a first direction X. Each of the multiple buffer pads 120 is located between adjacent all-solid-state cell 110s among the multiple all-solid-state cell 110s. Among the multiple buffer pads 120, the uppermost buffer pad 120 in the first direction is located between the first end plate 300 and the uppermost all-solid-state cell 110 among the multiple all-solid-state cell 110s. Among the multiple buffer pads 120, the buffer pad 120 at the bottom in the first direction is located between the third end plate 600 and the lowest level all-solid-state cell 110 among the multiple all-solid-state cell 110s. The multiple buffer pads 120 may include various known elastic layers used in various known all-solid-state rechargeable batteries 1000.

[0165] The housing 200 stores a stack of all-solid-state battery cells 100 within its internal space. The housing 200 has a can shape, but is not limited to it, and may also have a bag shape. The housing 200 may have a square prism shape, but is not limited to it, and may also have a polygonal prism shape, such as a triangular prism, pentagonal prism, hexagonal prism, heptagonal prism, octagonal prism, circular prism, elliptical prism, or ring-shaped prism. Various known coatings may be applied to the inner and outer surfaces of the housing 200.

[0166] Figure 4 yes Figure 3 Enlarged cross-sectional view of part A.

[0167] Reference Figure 3 and Figure 4 A first end plate 300 is positioned between a first end 101 and a housing 200 in a first direction X of the all-solid-state cell stack 100. The first end plate 300 is located between a buffer pad 120 and a plurality of first metal wave springs 400, the buffer pad 120 being located on the top layer of the all-solid-state cell stack 100 in the first direction X. The first end plate 300 is in contact with the buffer pad 120 and the plurality of first metal wave springs 400. The first end plate 300 presses the all-solid-state cell stack 100 in the first direction by the elasticity of the plurality of first metal wave springs 400. The first end plate 300 includes a plurality of first recessed portions 310.

[0168] A plurality of first recessed portions 310 are arranged to be spaced apart from each other in a second direction Y intersecting the first direction X. Here, the second direction Y may include Figure 3The horizontal direction is included, but not limited to, the plurality of first recessed portions 310 having a shape recessed from the surface of the first end plate 300. A plurality of first metal wave springs 400 are respectively inserted into the plurality of first recessed portions 310. By inserting and supporting the plurality of first metal wave springs 400 in the plurality of first recessed portions 310, deviation of the plurality of first metal wave springs 400 from the plurality of first recessed portions 310 is suppressed.

[0169] The first end plate 300 has a plate shape including, but is not limited to, at least one of aluminum and stainless steel. For example, the first end plate 300 may include various known materials, such as polymers, amorphous materials, and ceramics.

[0170] A plurality of first metal wave springs 400 are located between the first end plate 300 and the housing 200. A plurality of first metal wave springs 400 are located between the first end plate 300 and the second end plate 500. A plurality of first metal wave springs 400 are in contact with the first end plate 300 and the second end plate 500. A plurality of first metal wave springs 400 are arranged spaced apart from each other in a second direction Y between the first end plate 300 and the second end plate 500. A plurality of first metal wave springs 400 are respectively inserted into a plurality of first recesses 310 of the first end plate 300 and a plurality of second recesses 510 of the second end plate 500, and are supported by the first recesses 310 and the second recesses 510. Since multiple first metal wave springs 400 are inserted between the first end plate 300 and the second end plate 500 and supported on multiple first recesses 310 and multiple second recesses 510, the deviation of the multiple first metal wave springs 400 from the multiple first recesses 310 of the first end plate 300 and the multiple second recesses 510 of the second end plate 500 is suppressed.

[0171] Each of the plurality of first metal wave springs 400 includes a metal wave spring. Because each of the plurality of first metal wave springs 400 includes a metal wave spring, it has greater elastic recovery than known helical springs, even though it has a thinner thickness in the first direction, thus the all-solid-state rechargeable battery 1000 is thinner in the first direction X.

[0172] In addition, since each of the plurality of first metal wave springs 400 includes a metal wave spring, even if the thickness of the all-solid cell stack 100 in the first direction X changes during charging and discharging, the first end plate 300 also presses the all-solid cell stack 100 uniformly in the first direction X through the elastic recovery of the plurality of first metal wave springs 400.

[0173] In addition, since each of the plurality of first metal wave springs 400 includes a metal wave spring, and since the physical properties of the metal do not change within the wide temperature range (e.g. -20°C to 80°C) inherent to the polymer elastic layer as a known pressure device, the first end plate 300 presses the all-solid-state cell stack 100 uniformly in the first direction through the elastic recovery of the plurality of first metal wave springs 400 over the wide temperature range.

[0174] In addition, since each of the multiple first metal wave springs 400 includes a metal wave spring, and since the all-solid-state cell stack 100 is elastic in the first direction X and is supported by the multiple first metal wave springs 400 and the first end plate 300, the impact resistance of the all-solid-state rechargeable battery 1000 is improved.

[0175] In addition, since each of the plurality of first metal wave springs 400 includes a metal wave spring, the inherent thermal conductivity of the metal is improved compared to the polymer elastic layer, which is a known pressurization device, and the heat from the all-solid-state cell stack 100 is conducted and radiated through the first end plate 300 and the plurality of first metal wave springs 400, so the heat dissipation effect of the all-solid-state cell stack 100 is improved.

[0176] For example, by including a plurality of first metal wave springs 400 and a first end plate 300 corresponding to the all-solid cell stack 100 whose thickness can be changed during charging and discharging, such an all-solid rechargeable battery 1000 can be provided, in which the all-solid cell stack 100 is uniformly pressed over a wide temperature range, shock resistance is improved, heat dissipation of the all-solid cell stack 100 is improved, the overall thickness is thinner, and at the same time, energy density is improved compared to thickness.

[0177] For example, each of the plurality of first metal wave springs 400 includes a ring-shaped wave spring. Because each of the plurality of first metal wave springs 400 includes a ring-shaped wave spring, the lifespan is improved compared to known flat wave springs, while powder generation due to friction caused by spring elastic recovery can be suppressed. Here, the flat wave spring may include, but is not limited to, a plate-type wave spring whose longitudinal cross-section has a wave-like shape.

[0178] Figure 5 This is a view showing an example of a first metal wave spring of an all-solid-state rechargeable battery according to an embodiment.

[0179] Reference Figure 5 As an example of a first metal wave spring 400, the first metal wave spring 400 may include a wave spring in which waveforms that are symmetrical to each other in form are stacked and extend in the direction of generating elastic restoring force. The first metal wave spring 400 may include, but is not limited to, peak-to-peak wave springs.

[0180] Since the first metal wave spring 400 includes wave springs in which waveforms having symmetrical forms are stacked and extended in the direction of generating elastic restoring force, the lifespan is improved compared to a flat wave spring, while the generation of powder due to friction caused by the elastic restoring of the spring can be suppressed.

[0181] Figure 6 This is a view showing another example of the first metal wave spring of an all-solid-state rechargeable battery according to an embodiment.

[0182] Reference Figure 6 As another example of the first metal wave spring 400, the first metal wave spring 400 may include a wave spring in which a single layer of waveform extends in a ring shape. The first metal wave spring 400 may include a single-turn wave spring, but is not limited thereto. Because the first metal wave spring 400 includes a wave spring in which a single layer of waveform extends in a ring shape, its thickness can be reduced while increasing its lifespan compared to a flat wave spring.

[0183] Figure 7 This is a view showing another example of the first metal wave spring of an all-solid-state rechargeable battery according to an embodiment.

[0184] Reference Figure 7 As another example of a first metal wave spring 400, the first metal wave spring 400 may include wave springs in which waveforms of the same shape are stacked and extended in the direction of generating elastic restoring force. The first metal wave spring 400 may include, but is not limited to, nested wave springs. Compared to flat wave springs, because the first metal wave spring 400 may include wave springs in which waveforms of the same shape are stacked and extended in the direction of generating elastic restoring force, its lifespan can be increased and its thickness can be reduced, while simultaneously improving elastic restoring force.

[0185] Reference Figure 3 and Figure 4 The second end plate 500 is positioned between the plurality of first metal wave springs 400 and the housing 200. The second end plate 500 contacts the housing 200 and the plurality of first metal wave springs 400. The second end plate 500 includes a plurality of second recessed portions 510.

[0186] A plurality of second recessed portions 510 are arranged to be spaced apart from each other in a second direction Y, corresponding to a plurality of first recessed portions 310 of the first end plate 300. The plurality of second recessed portions 510 face the plurality of first recessed portions 310, and a plurality of first metal wave springs 400 are located between the plurality of second recessed portions 510 and the plurality of first recessed portions 310. The plurality of second recessed portions 510 have a shape that is recessed from the surface of the second end plate 500. The plurality of first metal wave springs 400 are respectively inserted into the plurality of second recessed portions 510. By inserting and supporting the plurality of second metal wave springs 700 in the plurality of second recessed portions 510, deviation of the plurality of second metal wave springs 700 from the plurality of second recessed portions 510 is suppressed.

[0187] The second end plate 500 has a plate shape including, but is not limited to, at least one of aluminum and stainless steel. For example, the second end plate 500 may include various known materials, such as polymers, amorphous materials, and ceramics.

[0188] Figure 8 yes Figure 3 An enlarged cross-sectional view of part B in the diagram.

[0189] Reference Figure 3 and Figure 8 A third end plate 600 is located between the second end 102 of the all-solid-state cell stack 100 in the first direction X and the housing 200. The third end plate 600 is located between a buffer pad 120 and a plurality of second metal wave springs 700, the buffer pad 120 being located at the bottom of the all-solid-state cell stack 100 in the first direction X. The third end plate 600 is in contact with the buffer pad 120 and the plurality of second metal wave springs 700. The third end plate 600 presses the all-solid-state cell stack 100 in the first direction by the elastic restoring force caused by the plurality of second metal wave springs 700. The third end plate 600 includes a plurality of third recessed portions 610.

[0190] A plurality of third recessed portions 610 are arranged to be spaced apart from each other in a second direction Y. The plurality of third recessed portions 610 have a shape that recesses from the surface of the third end plate 600. Each of a plurality of second metal wave springs 700 is inserted into each of the plurality of third recessed portions 610. By inserting and supporting the plurality of second metal wave springs 700 in the plurality of third recessed portions 610, the plurality of second metal wave springs 700 are prevented from deviating from the plurality of third recessed portions 610.

[0191] The third end plate 600 has a plate shape including, but is not limited to, at least one of aluminum and stainless steel. For example, the third end plate 600 may include various known materials such as polymers, amorphous materials, and ceramics.

[0192] A plurality of second metal wave springs 700 are located between the third end plate 600 and the housing 200. A plurality of second metal wave springs 700 are located between the third end plate 600 and the fourth end plate 800. A plurality of second metal wave springs 700 are in contact with the third end plate 600 and the fourth end plate 800. A plurality of second metal wave springs 700 are arranged spaced apart from each other in the second direction Y between the third end plate 600 and the fourth end plate 800. A plurality of second metal wave springs 700 are respectively inserted into a plurality of third recesses 610 of the third end plate 600 and a plurality of fourth recesses 810 of the fourth end plate 800, and are supported on the third recesses 610 and the fourth recesses 810. By inserting and supporting a plurality of second metal wave springs 700 between the third end plate 600 and the fourth end plate 800 on a plurality of third recesses 610 and a plurality of fourth recesses 810, deviation of the plurality of second metal wave springs 700 from the plurality of third recesses 610 of the third end plate 600 and the plurality of fourth recesses 810 of the fourth end plate 800 is suppressed.

[0193] Each of the plurality of second metal wave springs 700 includes a metal wave spring. Because each of the plurality of second metal wave springs 700 includes a metal wave spring, it has greater elastic recovery than known helical springs, even though it has a thinner thickness in the first direction, thus the all-solid-state rechargeable battery 1000 is thinner in the first direction X.

[0194] In addition, since each of the plurality of second metal wave springs 700 includes a metal wave spring, even if the thickness of the all-solid cell stack 100 in the first direction X changes during charging and discharging, the third end plate 600 also presses the all-solid cell stack 100 uniformly in the first direction X through the elastic recovery of the plurality of second metal wave springs 700.

[0195] In addition, since each of the multiple second metal wave springs 700 includes a metal wave spring, and since the physical properties of the metal do not change within the wide temperature range (e.g. -20°C to 80°C) compared to the polymer elastic layer which is a known pressure device, the third end plate 600 presses the all-solid-state cell stack 100 uniformly in the first direction through the elastic recovery of the multiple second metal wave springs 700 over the wide temperature range.

[0196] In addition, since each of the multiple second metal wave springs 700 includes a metal wave spring, and the all-solid-state cell stack 100 is elastic in the first direction X and supported by the multiple second metal wave springs 700 and the third end plate 600, the impact resistance of the all-solid-state rechargeable battery 1000 is improved.

[0197] In addition, since each of the multiple second metal wave springs 700 includes a metal wave spring, the inherent thermal conductivity of the metal is improved compared to the polymer elastic layer, which is a known pressurization device, and the heat from the all-solid-state cell stack 100 is conducted and radiated through the third end plate 600 and the multiple second metal wave springs 700, so the heat dissipation effect of the all-solid-state cell stack 100 is improved.

[0198] For example, by including multiple second metal wave springs 700 and a third end plate 600 corresponding to the all-solid cell stack 100 whose thickness can be changed during charging and discharging, such an all-solid rechargeable battery 1000 can be provided, in which the all-solid cell stack 100 is uniformly pressed over a wide temperature range, improving shock resistance, improving heat dissipation of the all-solid cell stack 100, making the overall thickness thinner, and at the same time, improving energy density compared to thickness.

[0199] For example, each of the plurality of first metal wave springs 700 includes a ring-shaped wave spring. Since each of the plurality of second metal wave springs 700 includes a ring-shaped wave spring, the lifespan is improved compared to known flat wave springs, while powder generation due to friction caused by spring elastic recovery can be suppressed. Here, the flat wave spring may include, but is not limited to, a plate-type wave spring whose longitudinal cross-section has a wave-like shape.

[0200] As an example of a second metal wave spring 700, the second metal wave spring 700 may include, but is not limited to, wave springs in which waveforms of symmetrical form are stacked and extended in the direction of generating elastic restoring force.

[0201] Since the second metal wave spring 700 includes wave springs in which waveforms of symmetrical form are stacked and extended in the direction of generating elastic restoring force, the lifespan is improved compared to a flat wave spring, while the generation of powder due to friction caused by the elastic restoring of the spring can be suppressed.

[0202] As another example of the second metal wave spring 700, the second metal wave spring 700 may include a wave spring in which a single layer of waveform extends in a ring shape.

[0203] Since the second metal wave spring 700 includes a wave spring in which a single layer of wave extends in a ring shape, it can be thinner while increasing lifespan compared to a flat wave spring.

[0204] As another example of the second metal wave spring 700, the second metal wave spring 700 may include a wave spring in which waves of the same shape are stacked and extended in the direction of generating elastic restoring force.

[0205] Since the second metal wave spring 700 may include a wave spring in which waves of the same shape are stacked and extended in the direction of generating elastic restoring force, its lifespan can be increased and its thickness can be reduced compared to a flat wave spring, while its elastic restoring force can be improved.

[0206] The fourth end plate 800 is located between the plurality of second metal wave springs 700 and the housing 200. The fourth end plate 800 contacts the housing 200 and the plurality of second metal wave springs 700. The fourth end plate 800 includes a plurality of fourth recessed portions 810.

[0207] A plurality of fourth recessed portions 810 are arranged to be spaced apart from each other in the second direction Y by means of a plurality of third recessed portions 610 corresponding to the third end plate 600. The plurality of fourth recessed portions 810 face the plurality of third recessed portions 610, and a plurality of second metal wave springs 700 are located between the plurality of fourth recessed portions 810 and the plurality of third recessed portions 610. The plurality of fourth recessed portions 810 have a shape that is recessed from the surface of the fourth end plate 800. The plurality of second metal wave springs 700 are respectively inserted into the plurality of fourth recessed portions 810. By inserting and supporting the plurality of second metal wave springs 700 in the plurality of fourth recessed portions 810, deviation of the plurality of second metal wave springs 700 from the plurality of fourth recessed portions 810 is suppressed.

[0208] The fourth end plate 800 has a plate shape including, but is not limited to, at least one of aluminum and stainless steel. For example, the fourth end plate 800 may include various known materials, such as polymers, amorphous materials, and ceramics.

[0209] For example, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 includes a metal wave spring, it has greater elastic recovery than a known helical spring, even though it has a thinner thickness in the first direction, thus the all-solid-state rechargeable battery 1000 is thinner in the first direction X.

[0210] Furthermore, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 includes a metal wave spring, even if the thickness of the all-solid-state cell stack 100 in the first direction X changes during charging and discharging, the first end plate 300 and the third end plate 600 uniformly press the all-solid-state cell stack 100 in the first direction X through the elastic recovery of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700.

[0211] Furthermore, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 comprises a metal wave spring, and since the physical properties of the metal do not change within the inherent wide temperature range (e.g. -20°C to 80°C) compared to the polymer elastic layer, which is a known pressurizing device, the first end plate 300 and the third end plate 600 uniformly press the all-solid-state cell stack 100 in the first direction through the elastic recovery of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700.

[0212] In addition, since each of the multiple first metal wave springs 400 and the multiple second metal wave springs 700 includes a metal wave spring, and since the all-solid-state cell stack 100 is elastic in the first direction X and is supported by the multiple first metal wave springs 400 and the first end plate 300, as well as the multiple second metal wave springs 700 and the third end plate 600, the impact resistance of the all-solid-state rechargeable battery 1000 is improved.

[0213] Furthermore, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 includes a metal wave spring, the inherent thermal conductivity of the metal is improved compared to the polymer elastic layer, which is a known pressurization device, and the heat from the all-solid-state cell stack 100 is conducted and radiated through the first end plate 300 and the plurality of first metal wave springs 400, the third end plate 600 and the plurality of second metal wave springs 700, and the housing 200, so the heat dissipation effect of the all-solid-state cell stack 100 is improved.

[0214] For example, by including a plurality of first metal wave springs 400 and a first end plate 300, and a plurality of second metal wave springs 700 and a third end plate 600 corresponding to the all-solid-state cell stack 100 whose thickness can be changed during charging and discharging, such an all-solid-state rechargeable battery 1000 can be provided, in which the all-solid-state cell stack 100 is uniformly pressed over a wide temperature range, improving shock resistance and heat dissipation, resulting in a thinner overall thickness, while improving energy density compared to thickness.

[0215] Now, referring to Figure 9 Describes an all-solid-state rechargeable battery according to another embodiment.

[0216] The following will describe the parts that differ from the all-solid-state secondary battery according to the above embodiments.

[0217] Figure 9 This is a cross-sectional view showing an all-solid-state rechargeable battery according to another embodiment.

[0218] Reference Figure 9According to another embodiment, the all-solid-state rechargeable battery 1000 includes an all-solid-state cell stack 100, a housing 200, a first end plate 300, a plurality of first metal wave springs 400, a third end plate 600, and a plurality of second metal wave springs 700.

[0219] A plurality of first metal wave springs 400 are positioned between a first end plate 300 and a housing 200. The plurality of first metal wave springs 400 are in contact with both the first end plate 300 and the housing 200. The plurality of first metal wave springs 400 are arranged spaced apart from each other in a second direction Y between the first end plate 300 and the housing 200. Each of the plurality of first metal wave springs 400 is inserted into each of a plurality of first recesses in the first end plate 300 and supported on the first recesses. By inserting the plurality of first metal wave springs 400 between the first end plate 300 and the housing 200 and supporting them on the plurality of first recesses, deviation of the plurality of first metal wave springs 400 from the first end plate 300 and the housing 200 is prevented.

[0220] For example, the housing 200 may include a plurality of other recessed portions into which a plurality of first metal wave springs 400 are inserted and supported, but is not limited thereto.

[0221] A plurality of second metal wave springs 700 are located between the third end plate 600 and the housing 200. The plurality of second metal wave springs 700 are in contact with the third end plate 600 and the housing 200. The plurality of second metal wave springs 700 are arranged spaced apart from each other in a second direction Y between the third end plate 600 and the housing 200. Each of the plurality of second metal wave springs 700 is inserted into and supported in each of a plurality of third recesses in the third end plate 600. By inserting and supporting the plurality of second metal wave springs 700 between the third end plate 600 and the housing 200 in the plurality of third recesses, misalignment of the plurality of second metal wave springs 700 from between the third end plate 600 and the housing 200 is prevented.

[0222] For example, the housing 200 may include a plurality of other recessed portions into which a plurality of second metal wave springs 700 are inserted and supported, but is not limited thereto.

[0223] For example, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 includes a metal wave spring, it has greater elastic recovery than a known helical spring, even though it has a thinner thickness in the first direction. Therefore, the all-solid-state rechargeable battery 1000 is thinner in the first direction X.

[0224] Furthermore, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 includes a metal wave spring, even if the thickness of the all-solid-state cell stack 100 in the first direction X changes during charging and discharging, the first end plate 300 and the third end plate 600 uniformly press the all-solid-state cell stack 100 in the first direction X through the elastic recovery of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700.

[0225] Furthermore, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 comprises a metal wave spring, and since the physical properties of the metal do not change within the inherent wide temperature range (e.g. -20°C to 80°C) compared to the polymer elastic layer, which is a known pressurizing device, the first end plate 300 and the third end plate 600 uniformly press the all-solid-state cell stack 100 in the first direction through the elastic recovery of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700.

[0226] In addition, since each of the multiple first metal wave springs 400 and the multiple second metal wave springs 700 includes a metal wave spring, and since the all-solid-state cell stack 100 is elastic in the first direction X and is supported by the multiple first metal wave springs 400 and the first end plate 300, as well as the multiple second metal wave springs 700 and the third end plate 600, the impact resistance of the all-solid-state rechargeable battery 1000 is improved.

[0227] Furthermore, since each of the plurality of first metal wave springs 400 and the plurality of second metal wave springs 700 includes a metal wave spring, the inherent thermal conductivity of the metal is improved compared to the polymer elastic layer, which is a known pressurization device, and the heat from the all-solid-state cell stack 100 is conducted and radiated through the first end plate 300 and the plurality of first metal wave springs 400, the third end plate 600 and the plurality of second metal wave springs 700, and the housing 200, so the heat dissipation effect of the all-solid-state cell stack 100 is improved.

[0228] For example, by including a plurality of first metal wave springs 400 and a first end plate 300, and a plurality of second metal wave springs 700 and a third end plate 600 corresponding to the all-solid-state cell stack 100 whose thickness can be changed during charging and discharging, such an all-solid-state rechargeable battery 1000 can be provided, in which the all-solid-state cell stack 100 is uniformly pressed over a wide temperature range, improving shock resistance, improving heat dissipation of the all-solid-state cell stack 100, making the overall thickness thinner, and at the same time, improving energy density compared to thickness.

[0229] While this disclosure has been described in conjunction with embodiments that are now considered practical, it should be understood that this disclosure is not limited to the disclosed embodiments, but rather is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.

[0230] Explanation of reference numerals in the attached figures

[0231] All-solid-state cell 110, all-solid-state cell stack 100, housing 200, first end plate 300, first metal wave spring 400

Claims

1. An all-solid-state rechargeable battery, comprising: All-solid-state cell stacking, including multiple all-solid-state cell units stacked in the first direction; A housing that contains the stack of all-solid-state cells; A first end plate is located between the first end of the all-solid-state battery cell stacked in the first direction and the housing. as well as Multiple first metal wave springs are located between the first end plate and the housing.

2. The all-solid-state rechargeable battery according to claim 1, wherein, The plurality of first metal wave springs are in contact with the first end plate.

3. The all-solid-state rechargeable battery according to claim 2, wherein: The first end plate includes a plurality of first recessed portions arranged spaced apart from each other in a second direction intersecting the first direction, and Each of the plurality of first metal wave springs is inserted into the plurality of first recessed portions.

4. The all-solid-state rechargeable battery according to claim 3, further comprising a second end plate, the second end plate being between the plurality of first metal wave springs and the housing and in contact with the plurality of first metal wave springs.

5. The all-solid-state rechargeable battery according to claim 4, wherein: The second end plate includes a plurality of second recessed portions, the plurality of second recessed portions being spaced apart from each other in the second direction and corresponding to the plurality of first recessed portions of the first end plate, and Each of the plurality of first metal wave springs is inserted into the plurality of second recessed portions.

6. The all-solid-state rechargeable battery according to claim 4, wherein, The second end plate is in contact with the housing.

7. The all-solid-state rechargeable battery according to claim 2, wherein, The plurality of first metal wave springs are in contact with the housing.

8. The all-solid-state rechargeable battery according to claim 1, wherein, Each of the plurality of first metal wave springs includes a ring-shaped wave spring.

9. The all-solid-state rechargeable battery according to claim 8, wherein, The annular wave spring comprises a wave spring in which waves with symmetrical shapes are stacked and extended in the direction that generates elastic restoring force.

10. The all-solid-state rechargeable battery according to claim 8, wherein, The annular wave spring includes a wave spring in which a single layer of waveform extends in an annular shape.

11. The all-solid-state rechargeable battery according to claim 8, wherein, The annular wave spring includes a wave spring in which waveforms of the same shape are stacked and extended in the direction that generates elastic restoring force.

12. The all-solid-state rechargeable battery according to claim 1, further comprising: The third end plate is located between the second end of the all-solid-state battery cell stacked in the first direction and the housing. as well as Multiple second metal wave springs are located between the third end plate and the housing.

13. The all-solid-state rechargeable battery according to claim 12, wherein, The plurality of second metal wave springs contact the third end plate.

14. The all-solid-state rechargeable battery according to claim 13, wherein: The third end plate includes a plurality of third recessed portions spaced apart from each other in a second direction intersecting the first direction, and Each of the plurality of second metal wave springs is inserted into the plurality of third recessed portions.

15. The all-solid-state rechargeable battery of claim 14, further comprising a fourth end plate located between the plurality of second metal wave springs and the housing and in contact with the plurality of second metal wave springs.

16. The all-solid-state rechargeable battery according to claim 15, wherein: The fourth end plate includes a plurality of fourth recessed portions, the plurality of fourth recessed portions being spaced apart from each other in the second direction and corresponding to the plurality of third recessed portions of the third end plate, and Each of the plurality of second metal wave springs is inserted into the plurality of fourth recessed portions.

17. The all-solid-state rechargeable battery according to claim 15, wherein, The fourth end plate is in contact with the housing.

18. The all-solid-state rechargeable battery according to claim 12, wherein, The plurality of second metal wave springs are in contact with the housing.

19. The all-solid-state rechargeable battery according to claim 1, wherein, The all-solid-state cell stack further includes multiple buffer pads between the plurality of all-solid-state cell units.

20. The all-solid-state rechargeable battery according to claim 1, wherein, Each of the all-solid-state cell units includes: negative electrode; Positive electrode, on the negative electrode; and A solid electrolyte layer is located between the negative electrode and the positive electrode.

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