All-solid-state battery comprising lithium alloy anode

Abstract

Disclosed is an all-solid-state battery in which an anode comprises an anode material including a product of: (i) a lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn) or a mixture thereof, the product being a prelithiated metal alloy having a chemical formula of LixMy, where, in the chemical formula, Li is lithium, M is a metal and x and y are integers greater than 0, the mass ratio of the lithium to the metal being 1:4 to 1:20, and the anode including no binder material. In some aspects, the N / P ratio is between 1.00 and 2.00.

Description

All-solid-state battery containing a lithium alloy cathode

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to U.S. patent application Ser. No. 18 / 806,199, filed August 15, 2024, the entire contents of which are incorporated herein by reference.

[0003] Technology field

[0004] The present disclosure relates to a lithium alloy negative electrode, an all-solid-state battery including the lithium alloy negative electrode, and a method for manufacturing the lithium alloy negative electrode and the battery.

[0005] The rise of electrified transportation, exemplified by the widespread adoption of electric vehicles (EVs) and the emergence of urban air mobility (UAM) vehicles, continues. Simultaneously, demand for stationary energy storage systems powered by solar and wind power is growing, particularly in the residential and industrial sectors. This shift is driven in part by the urgent need to mitigate the environmental and climate impacts associated with traditional internal combustion engines and other non-renewable power sources. Consequently, the development of battery technologies that offer high energy density while also ensuring enhanced safety has become essential.

[0006] Conventional liquid lithium-ion batteries have played a crucial role in the development of electric transportation and energy storage systems, and have had a significant positive impact on green energy and climate change mitigation efforts. While these conventional liquid lithium-ion batteries offer advantages over many other energy sources, they also have certain limitations. For example, lithium-ion batteries incorporate various safety mechanisms that limit voltage and internal pressure, but these safety features typically increase weight and, in some cases, limit performance. Furthermore, lithium-ion batteries are susceptible to aging, which can lead to capacity loss and eventual failure after several years of use.

[0007] All-solid-state batteries utilize a solid electrolyte instead of a liquid one, making the entire battery solid. In conventional solid-state batteries, the solid electrolyte replaces the liquid electrolyte system, reducing the risk of fire or explosion, thereby enhancing safety. Solid electrolytes are inherently non-flammable and can withstand a wider temperature range, allowing them to function as electrochemical energy storage devices without the need for additional safety devices. Solid-state batteries offer higher energy densities and are safer than batteries using liquid electrolyte systems, such as conventional lithium-ion batteries.

[0008] For example, a lithium-sulfur battery, which uses lithium and alkali metals as negative active materials and sulfur as positive active material, has a theoretical energy density of 2,800 Wh / kg (1,675 mAh), which is significantly higher than other battery systems. Furthermore, sulfur is abundant, making it inexpensive and environmentally friendly, attracting attention as a material for portable electronic devices. Lithium metal has the advantages of being lightweight and having a high energy density, and various positive active materials can be used in lithium batteries, including sulfur-containing positive active materials with high energy capacity sulfur-sulfur bonds.

[0009] However, modification of metallic lithium as an anode material may be necessary to address issues such as high activity, large volume deformation, and lithium dendrite formation. For example, metallic lithium has a high chemical reactivity, which can cause irreversible chemical reactions with the electrolyte, consuming both the electrolyte and the metallic lithium itself, thereby reducing the anode capacity and battery cycle life. Furthermore, the significant volume deformation of lithium metal during charge and discharge leads to increased expansion and contraction of the battery. Furthermore, lithium metal is prone to the growth of lithium dendrites.

[0010] Therefore, there is a need for improved lithium materials suitable for use as cathode materials in all-solid-state batteries.

[0011] The present disclosure relates to an all-solid-state battery, wherein the negative electrode comprises a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof, wherein the product is a prelithiated metal alloy having the chemical formula LixMy, wherein Li is lithium, M is a metal, and x and y are integers greater than 0.

[0012] According to one aspect, an all-solid-state battery is provided. The all-solid-state battery comprises a negative electrode, a positive electrode, and a solid electrolyte, wherein the solid electrolyte is interposed between the negative electrode and the positive electrode, the negative electrode comprises a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof, the product being a prelithiated metal alloy having the chemical formula LixMy, wherein Li is lithium, M is a metal, x and y are integers greater than 0, a mass ratio of the lithium and the metal is 1:6 to 1:20, and the negative electrode does not include a binder material.

[0013] In some embodiments, the product comprises Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al or Li 0.95 It may be a prelithiated metal having the chemical formula Al.

[0014] In some embodiments, the product comprises Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn or Li 2.2 It may be a prelithiated metal having the chemical formula Sn.

[0015] In some embodiments, the average particle size of the lithium powder may be from 30 μm to 60 μm.

[0016] In some embodiments, the mass ratio of lithium to metal may be from 1:4 to 1:20.6. The mass ratio of lithium to metal may be from 1:4 to 1:10. The mass ratio of lithium to metal may be from 1:4 to 1:7.5. The mass ratio of lithium to metal may be from 1:4 to 1:5.

[0017] In some embodiments, the N / P ratio may be between 1.00 and 2.00. The N / P ratio may also be between 1.2 and 1.5.

[0018] According to another aspect, there is provided an all-solid-state battery comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the solid electrolyte is interposed between the negative electrode and the positive electrode, the negative electrode comprising a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof, wherein the lithium powder has an average particle size of 0.1 μm to 200 μm, the product is a prelithiated metal alloy having a chemical formula of LixMy, wherein Li is lithium, M is a metal, x and y are integers greater than 0, a mass ratio of the lithium and the metal is 1:4 to 1:20, and an N / P ratio is 1.00 to 3.00, and the negative electrode does not include a binder material.

[0019] In some embodiments, the product comprises Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al or Li 0.95 It may be a prelithiated metal having the chemical formula Al.

[0020] In some embodiments, the product comprises Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn or Li 2.2It may be a prelithiated metal having the chemical formula Sn.

[0021] In some embodiments, the average particle size of the lithium powder may be from 30 μm to 60 μm.

[0022] In some embodiments, the mass ratio of the lithium and the metal may be from 1:4 to 1:15.

[0023] In some embodiments, the N / P ratio may be between 1.00 and 2.00.

[0024] According to another aspect, there is provided an all-solid-state battery comprising a negative electrode, a positive electrode, and a solid electrolyte, wherein the solid electrolyte is interposed between the negative electrode and the positive electrode, the negative electrode comprises a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof, the product being a prelithiated metal alloy having a chemical formula of LixMy, wherein Li is lithium, M is a metal, x and y are integers greater than 0, a mass ratio of the lithium and the metal is 1:4 to 1:20, and the negative electrode does not include a binder material.

[0025] In some embodiments, the product comprises Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al or Li 0.95 It may be a prelithiated metal having the chemical formula Al.

[0026] In some embodiments, the product comprises Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn or Li 2.2 It may be a prelithiated metal having the chemical formula Sn.

[0027] In some embodiments, the average particle size of the lithium powder may be from 30 μm to 60 μm.

[0028] In some embodiments, the mass ratio of the lithium and the metal may be 1:4 to 1:15.

[0029] In some embodiments, the N / P ratio may be between 1.00 and 2.00.

[0030] According to another aspect, a method for manufacturing an all-solid-state battery according to the above aspect is provided. The method comprises the steps of compressing LPSCl powder to form an LPSCl separator layer, applying an NCM composite powder to a first surface of the compressed LPSCl separator layer and compressing it, applying a lithium and aluminum composite powder to a second surface of the LPSCl separator layer opposite to the first surface and compressing it to form a battery cell, maintaining the battery cell under a stack pressure so that an alloying reaction between the lithium and aluminum occurs, and cycling the battery cell.

[0031] Each aspect may further have one or more additional elements in any combination.

[0032] The accompanying drawings illustrate aspects of the present disclosure and, together with the detailed description, serve to further understand the technical concepts of the present disclosure. The present disclosure should not be construed as being limited to the drawings. In the drawings, the shape, size, scale, or proportion of elements may be exaggerated for clarity of explanation.

[0033] Figure 1 shows a schematic diagram of a related art battery.

[0034] Figure 2 shows a schematic diagram of a battery according to the disclosed embodiment.

[0035] Figure 3 is an SEM image of lithium particles according to the disclosed embodiment.

[0036] Figure 4 is a schematic diagram of a method for manufacturing an all-solid-state battery according to the disclosed embodiment.

[0037] Figure 5 shows a capacity-efficiency graph of a battery cell according to an embodiment.

[0038] Figure 6 shows voltage profiles at various cycles of the embodiment of Figure 5.

[0039] Figure 7 illustrates a comparison of specific capacities between alloy electrodes according to an embodiment and CCD screening for kinetics improvement according to an embodiment and a comparative example.

[0040] Figure 8 shows the XRD pattern of the embodiment.

[0041] Figure 9 shows CCD screening for improvement in reaction speed according to examples and comparative examples, comparison of initial coulombic efficiency between alloy electrodes according to examples, and comparison of specific capacity between alloy electrodes according to examples.

[0042] Figure 10 illustrates CCD screening for improvement in reaction speed according to examples and comparative examples.

[0043] Figures 11a and 11b illustrate capacity-efficiency graphs of battery cells according to examples and comparative examples.

[0044] Figure 12 shows a capacity-efficiency graph of a battery cell according to an embodiment.

[0045] Figure 13 shows the XRD pattern of the example.

[0046] Hereinafter, the present disclosure will be described in detail. It should be understood that the terms and words used in this specification and the appended claims should not be construed as limited to their ordinary or dictionary meanings, but rather should be interpreted based on meanings and concepts consistent with the technical spirit of the present disclosure, based on the principle that the inventor can appropriately define terms for the best explanation. Therefore, it should be understood that the embodiments of the present disclosure described herein and the elements depicted in the drawings are merely embodiments of the present disclosure and do not fully represent the technical spirit of the present disclosure, and that other equivalents and modifications may exist at the time of filing. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly known to those skilled in the art. In the event that there are multiple definitions for a term herein, the definitions provided herein shall take precedence.

[0047] Unless otherwise stated, all percentages, parts and ratios in this disclosure are by weight.

[0048] Unless otherwise indicated, the numerical parameters set forth in the specification and attached claims below are approximations that may vary depending upon the desired properties sought to be obtained in accordance with aspects of the present disclosure. Whenever a numerical range having a lower and an upper limit is disclosed, any number falling within that range and any subsumed range are specifically disclosed. In particular, any range of values ​​disclosed herein (in the form "from about a to about b," or, equivalently, "from about a to b," or, equivalently, "about ab") should be understood to present all numbers and ranges subsumed within the broader range of values.

[0049] Although compositions and methods are described herein as “comprising” various components or steps, it is also possible for the compositions and methods to “consist essentially of” or “consist of” the various components and steps. The terms “comprise(s)” or “include(s)” as used herein specify the presence of stated elements, but do not exclude the presence or addition of one or more other elements, unless the context clearly dictates otherwise.

[0050] The terms "about" and "substantially" are used herein to mean at or near that value, given the inherent manufacturing and material tolerances of the circumstances described, and are used to prevent unscrupulous infringers from unfairly taking advantage of the disclosure when precise or absolute values ​​are stated to aid understanding of the disclosure. The terms "about" and "approximately" when used with a numerical variable generally mean the value of that variable, and any value of that variable within experimental error (e.g., the 95% confidence interval of the mean) or within ±10% of the specified value or within a wider range. Unless otherwise stated, all numbers expressing quantities of ingredients, properties such as molecular weights, reaction conditions, and the like used in this specification and any related claims are to be understood as being modified by the term "about."

[0051] As used herein, “A and / or B” specifies “A or B or both.”

[0052] All-solid-state battery

[0053] One aspect of the present disclosure relates to a solid-state battery comprising a solid electrolyte material as an electrolyte. Specific examples of the solid-state battery include any type of primary battery, secondary battery, fuel cell, solar cell, or capacitor, such as a supercapacitor. In particular, the battery is a lithium-ion secondary battery. Aspects of the present disclosure can be implemented as secondary batteries having various form factors or battery formats, including, for example, pouch-shaped batteries, cylindrical batteries, or prismatic batteries.

[0054] FIG. 1 illustrates a conventional all-solid-state battery (100). As illustrated in FIG. 1, the conventional all-solid-state battery (100) includes a negative electrode current collector (110), a positive electrode current collector (160), a negative electrode (120), a positive electrode (130), and a solid electrolyte (140) interposed between the negative electrode (120) and the positive electrode (130).

[0055] FIG. 2 illustrates an all-solid-state battery according to the disclosed embodiment. As illustrated in FIG. 2, the all-solid-state battery (200) according to the present disclosure includes an anode (or negative electrode), a cathode (or positive electrode), and a solid electrolyte (240) interposed between the anode and the cathode. The anode (220) may include a metal portion (221) and a prelithiated metal alloy portion (222).

[0056] The electrode of an all-solid-state battery may have a structure in which an electrode active material is formed on an electrode current collector, for example, a negative electrode current collector (210) and a positive electrode current collector (260). The electrode current collector may be omitted depending on the structure of the electrode. When the electrode is a negative electrode, the electrode current collector is a negative electrode current collector.

[0057] <Cathode>

[0058] The term anode is used interchangeably with the term negative electrode. The anode current collector (210) is not particularly limited as long as it is conductive and does not cause any chemical change in the all-solid-state battery (200), and for example, copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel whose surface is treated with carbon, nickel, titanium, silver, or the like, or an aluminum-cadmium alloy, etc. may be used. In addition, the anode current collector (210), like the cathode current collector (260), may include various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a non-woven fabric having fine irregularities formed on the surface.

[0059] The cathode (220) comprises a cathode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof; wherein the product is a prelithiated metal alloy having the chemical formula LixMy, wherein Li is lithium, M is a metal, and x and y are integers greater than 0.

[0060] In certain embodiments, the mass ratio of the lithium to the metal can be, for example, 1:1 to 1:100, 1:2 to 1:50, 1:3 to 1:30, 1:4 to 1:20, 1:5 to 1:10, or 1:7 to 1:9. The negative electrode may not include a binder material. In some embodiments, the mass ratio of the lithium to the metal is 1:4 to 1:15, and in other embodiments, the mass ratio of the lithium to the metal is 1:4 to 1:10, the mass ratio of the lithium to the metal is 1:4 to 1:7.5, or the mass ratio of the lithium to the metal is 1:4 to 1:20. The range of the disclosed alloy negative electrode ensures an effective lithium diffusion coefficient, which is closely related to battery performance. A smaller metal ratio of the alloy negative electrode results in a higher lithium diffusion coefficient.

[0061] In some embodiments, the product is a prelithiated metal further comprising an additional metal selected from Al, Cu, Zn, Ga, In, Ag, or mixtures thereof. For example, in some embodiments, the additional metal is present in an amount of, for example, 0.01 to 50%, 0.1 to 30%, 1 to 25%, 1.5 to 10%, 2.5 to 5%, 3.0 to 4%, or 3.5 to 3.75% by weight.

[0062] In some embodiments, the product is a prelithiated metal having a prelithiated Li concentration in the metal in the range of, for example, 0.01 to 99.9%, 0.1 to 99.0%, 1 to 95%, 10 to 95%, 25 to 95%, 40 to 80%, or 50 to 75%. In some embodiments, the prelithiated metal is Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al and Li 0.95 It may have a chemical formula including but not limited to Al.

[0063] In some embodiments, the product is a prelithiated metal having a prelithiated Li concentration in the metal in the range of, for example, 0.01 to 300%, 0.1 to 250%, 1 to 220%, 10 to 150%, 25 to 110%, 40 to 110%, or 50 to 99%. In some embodiments, the prelithiated metal is Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn and Li 2.2 It may have a chemical formula including but not limited to Sn.

[0064] In some embodiments, the average particle size (D50) of the lithium powder can be, for example, 0.01 μm to 500 μm, 0.05 μm to 400 μm, 0.1 μm to 200 μm, 0.5 μm to 100 μm, 1 μm to 100 μm, 10 μm to 100 μm, 25 μm to 75 μm, or 30 μm to 60 μm. In some embodiments, the average particle size (D50) of the lithium powder can be in the range of 30 μm to 60 μm, as illustrated in FIG. 3 .

[0065] In some embodiments, the all-solid-state battery (200) according to some embodiments may have an N / P ratio in the range of, for example, 0.1 to 5.0, 0.5 to 3.0, 1.0 to 2.0, 1.2 to 2.0, 1.25 to 1.75, 1.01 to 1.10, 1.05 to 1.10, 1.01 to 1.05, or 1.5 to 2.0.

[0066] The above negative active material may further include lithium metal, a lithium alloy, a lithium metal composite oxide, a lithium-containing titanium composite oxide (LTO), and combinations thereof. In this case, the lithium alloy may be an alloy of lithium and at least one metal selected from Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, Al, and Sn. In addition, the lithium metal composite oxide may be an oxide (MeO) of lithium and any one metal (Me) selected from the group consisting of Si, Sn, Zn, Mg, Cd, Ce, Ni, and Fe. x ) can be, for example, Li x Fe2O3(0≤x≤1) or Li x It can be WO2(0≤x≤1).

[0067] In addition, the negative active material is Sn x Me 1-x Me' y O z(Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, elements of groups 1, 2 and 3 of the periodic table, halogens; 0 <x=1; 1=y=3; 1=z=8)와 같은 금속 복합 산화물; SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O 4　 and oxides such as Bi2O5; and carbon-containing negative electrode active materials such as crystalline carbon, amorphous carbon, or carbon composites may be used alone or in combination of two or more.

[0068] Bipolar

[0069] The term "cathode" is used interchangeably with the term "positive electrode." The positive electrode collector (260) can be used without particular limitation as long as the positive electrode collector (260) exhibits high conductivity and does not induce any chemical change in the battery (200) to which it is applied. For example, the positive electrode collector (260) can be made of stainless steel, aluminum, nickel, titanium, or calcined carbon. Alternatively, the positive electrode collector (260) can be made of aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, or silver.

[0070] The cathode current collector (260) is not limited to a specific type, and may include any material having high conductivity that does not cause chemical changes in the battery, for example, stainless steel, copper, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, and silver.

[0071] According to the present disclosure, the cathode active material comprises surface-modified, superior cathode active material particles for a sulfide-based all-solid-state battery. Additionally, additional materials may be used depending on the intended use of the lithium secondary battery. For example, transition metal compound-based active materials or sulfide-based active materials may be used.

[0072] Some embodiments relate to the cathode (230) further comprising a cathode material, a solid electrolyte, and a conductive agent. In some embodiments, the cathode material comprises a general formula LiNi x Mn y Co 1-x-y The cathode material comprises lithium nickel manganese cobalt oxide (hereinafter referred to as NMC, Li-NMC, LNMC or NCM), which is a mixed metal oxide of lithium, nickel, manganese and cobalt in O2. In some embodiments, the cathode material comprises at least one of LiCoO2, LiMn2O4, LiMnO2 or LiNiO2. In some embodiments, the cathode material comprises sulfur.

[0073] Solid electrolyte

[0074] In the case of a solid electrolyte (240) interposed between the negative electrode (220) and the positive electrode (240) in an all-solid-state battery (210), any suitable sulfide-containing electrolyte material may be used. The "sulfide-based electrolyte" used herein refers to an electrolyte containing ions (e.g., Li +) and electrically insulate the positive and negative electrodes of the electrochemical cell. Exemplary sulfide-containing electrolytes are presented in the literature [Shaojie Chenet al., "Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application," Energy Storage Materials, Volume 14, Pages 58-74 (September 2018)], which is expressly incorporated herein by reference in its entirety.

[0075] For example, many sulfide-containing electrolyte materials have (~10 -2 S cm -1 It is particularly attractive due to its high superionic conductivity and deformability. In particular, Li3P7S 11 , Li 10 GeP2S 12 , and Na3PS4 and Li6PS5Cl have been reported to exhibit high ionic conductivities, some even exhibiting conductivities close to liquid electrolytes. According to aspects of the present disclosure, the sulfide solid electrolyte materials also provide a low Young's modulus, which is beneficial for creating favorable interfacial contact with electrode materials by simple cold pressing at room temperature.

[0076] According to an aspect of the present disclosure, the sulfide-containing solid electrolyte may contain sulfur (S) and a metal belonging to group I or II of the periodic table, for example, Li. + may have an ionic conductivity of 1×10. Additionally, in one aspect of the present disclosure, the selected solid electrolyte may have an ionic conductivity of 1×10 -5 having an ionic conductivity of S / cm, or according to some embodiments of the present disclosure, 1×10 -3 It has an ionic conductivity of more than S / cm.

[0077] Non-limiting examples of the above sulfide-containing solid electrolytes may include Li-PS-based glasses, Li-PS-based glass ceramics, and argyrodite-based sulfide-containing solid electrolytes.

[0078] Non-limiting examples of the above sulfide-containing solid electrolyte may include at least one of xLi2S-yP2S5, Li2S-LiI-P2S5, Li2S-LiI-Li2O-P2S5, Li2S-LiBr-P2S5, Li2S-Li2O-P2S5, Li2S-Li3PO4-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-SiS2, Li2S-P2S5-SnS, Li2S-P2S5-Al2S3, Li2S-GeS2, or Li2S-GeS2-ZnS, Li6PS5X (X = at least one of Cl, Br or I).

[0079] In one aspect of the present disclosure, the sulfide-containing solid electrolyte may include at least one selected from an LPS-based glass or glass ceramic such as xLi2S-yP2S5, or an argyrodite-based sulfide-containing solid electrolyte (Li6PS5X; X = Cl, Br, I).

[0080] In another aspect, the solid electrolyte (240) may include a solid electrolyte commonly used in all-solid-state batteries, and for example, an inorganic solid electrolyte or an organic solid electrolyte may be used.

[0081] For inorganic solid electrolytes, ceramic materials, crystalline materials or amorphous materials can be used. For example, thio-LISICON (Li 3.25 Ge 0.25 P 0.75 S4), Li2S—SiS2, LiI—Li2S—SiS2, LiI—Li2S—P2S5, LiI—Li2S—P2O5, LiI—Li3PO4—P2S5, Li2S—P2S5, Li3PS4, Li7P3S 11, Li2O—B2O3, Li2O—B2O3—P2O5, Li2O—V2O5—SiO2, Li2O—B2O3, Li3PO4, Li2O—Li2WO4—B2O3, LiPON, LiBON, Li2O—SiO2, LiI, Li3N, Li5La3Ta2O 12 , Li7La3Zr2O 12 , Li6BaLa2Ta2O 12 , Li3PO (4-3 / 2w) N w (where w is w<1), and Li 3.6 Si 0.6 P 0.4 Inorganic solid electrolytes such as O4 can be used.

[0082] The average size of the sulfide particles is, for example, 0.1 μm to 50 μm, or 0.5 μm to 20 μm, which is within the size range of the sulfide particles used in known all-solid-state batteries. If the average size of the sulfide particles is less than the above range, the sulfide particles may form lumps. On the other hand, if the average size of the sulfide particles exceeds the above range, the porosity of the solid electrolyte produced may be high, which may deteriorate the characteristics of the battery. For example, the capacity of the battery may be reduced.

[0083] The above sulfide particles are 1×10 -4 Particles having an ionic conductivity of 1×10 S / cm or more, or sulfide particles having an ionic conductivity of 1×10 -3 It can have an ionic conductivity of S / cm or more.

[0084] In addition to the above-mentioned sulfide-based solid electrolytes, other known solid electrolytes can also be used. For example, Li2O―B2O3, Li2O―B2O3―P2O5, Li2O―V2O5―SiO2, Li3PO4, Li2O―Li2WO4―B2O3, LiPON, LiBON, Li2O―SiO2, LiI, Li3N, Li5La3Ta2O 12 , Li7La3Zr2O 12 , Li6BaLa2Ta2O 12 , Li3PO(4-3 / 2w) N w (w<1), or Li 3.6 Si 0.6 P 0.4 Inorganic solid electrolytes such as O4 can be used.

[0085] Examples of organic solid electrolytes also include organic solid electrolytes prepared by mixing lithium salts with polymer materials such as polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, agitated lysine, polyester sulfides, polyvinyl alcohol, and polyvinylidene fluoride. In this case, these may be used alone or in combination of at least two.

[0086] The above-described coated sulfide-containing electrolyte material can be used as a solid electrolyte for an all-solid-state battery. The all-solid-state battery includes a positive electrode and a negative electrode, with a solid electrolyte interposed between them.

[0087] Manufacturing

[0088] The method for manufacturing the all-solid-state battery (200) according to the present disclosure is not particularly limited and may be any suitable method known in the art. For example, the all-solid-state battery (200) may be manufactured by a dry pressing process in which electrode powder and solid electrolyte powder are manufactured, placed into a predetermined mold, and pressed, or a slurry coating process in which a slurry composition including an active material, a solvent, and a binder is manufactured, coated on a current collector, and dried. In the present disclosure, the method for manufacturing the all-solid-state battery (200) may include, but is not limited to, in situ prelithiation of pure Al with Li powder in the cell assembly procedure, as illustrated in FIG. 4 .

[0089] As illustrated in FIG. 4, this in situ prelithiation method may include preparing a separator layer by pressing LPSCl powder (e.g., 70 mg at 312 MPa for 10 seconds), spreading a desired amount of NCM composite powder on one side of the pressed LPSCl layer, and pressing the LPSCl layer (e.g., at 380 MPa for 3 minutes). This method may include Li x A method may include preparing a powder composite of lithium and aluminum at a desired mass ratio for Al1, spreading it on the other side of the LPSCl layer, and pressing it (e.g., at 125 MPa for 10 seconds). The resulting cell may then be kept stationary at a specified stack pressure (e.g., at 75 MPa for 6 hours) to complete the alloying reaction between lithium and aluminum, after which cell cycling may be performed.

[0090] As another example, a solid electrolyte (240) may be placed between an anode (230) and a cathode (220) and then compressed to assemble the cell. The assembled cell is then mounted on an outer member, and the outer member is encapsulated by heating and compression. As the outer member, a laminate case made of aluminum or stainless steel, a cylindrical metal container, or a square metal container may be suitably used.

[0091] Each electrode slurry can be coated onto the current collector by placing the electrode slurry on the current collector and uniformly dispersing the electrode slurry using a doctor blade, die casting, comma coating, or screen printing. Alternatively, the electrode slurry and current collector can be formed on separate substrates and bonded to each other by pressing or laminating. At this time, the concentration of the slurry solution or the number of coatings can be adjusted to control the final coating thickness.

[0092] The drying process is a process of removing solvent or moisture from the slurry to dry the slurry coated on the metal current collector. The drying process may vary depending on the solvent used. For example, the drying process may be performed in a vacuum oven at a temperature of 50°C to 200°C. For example, drying may be performed using a warm air drying method, a hot air drying method, a low-humidity air drying method, a vacuum drying method, a (far) infrared drying method, or an electron beam irradiation method. The drying time is not particularly limited. Typically, drying is performed within a range of 30 seconds to 24 hours.

[0093] After the above drying process, a cooling process may be additionally performed. In the cooling process, the binder may be cooled to room temperature to sufficiently form a recrystallized structure.

[0094] Additionally, if necessary, a rolling process may be performed to compress the electrode to a desired thickness by passing it through a gap between two heated rolls after the drying process to increase the capacity density of the electrode and improve the adhesion between the current collector and the active material. In the present disclosure, the rolling process is not particularly limited. A well-known rolling process such as pressing can be performed. For example, the electrode may be passed through a gap between rotating rolls, or the electrode may be pressed using a flat press.

[0095] Example

[0096] The following examples are not intended to be limiting. The disclosure provides numerous different embodiments for implementing the features of the present disclosure, and the following examples illustrate specific embodiments. It will be appreciated that other variations and methods known to those skilled in the art may be applied to the experimental procedures described below without departing from the scope of the present disclosure.

[0097] Experiment 1

[0098] Prelithiated metal cathode (Li 0.25Al1), cathode (NCM) and electrolyte material (LiPSCl), with an N / P ratio of 1.2 and a C-rate of 1.2 (1C = 2.5 mAh cm -2 ) for the battery cell (Example 1), the capacity and coulombic efficiency were tested under the conditions of a stack pressure of 75 MPa and room temperature. Figure 5 shows the specific capacity (mAh g) versus the cycle number of Example 1. -1 ) and Coulombic efficiency (%). As shown in Fig. 5, the capacity retention was 70% up to 280 cycles. Fig. 6 shows the voltage profiles of the 10th, 100th, and 280th cycles of Example 1 from the cycle characteristics (cyclability) of Fig. 5. As shown in Fig. 6, the cell performance is maintained even at high cycles, for example, 280 cycles.

[0099] Experiment 2

[0100] A cathode (NCM), electrolyte material (LiPSCl) and anode listed in Table 1 below, with an N / P ratio of 2.0 and various C-rates: 0.1C, 0.2C, 0.4C, 0.8C, 1.2C, 1.6C, 2C, 2.4C and 2.8C (1C = 2.5mAh cm -2 ), capacity and coulombic efficiency tests were performed under conditions of a stack pressure of 75 MPa and room temperature.

[0101] Sample cathode diagram Example 2 Li & Al (Li 25%) Fig. 7 c Example 3 Li & Al (Li 40%) Fig. 7 d Example 4 Li & Al (Li 50%) Fig. 7 e Example 5 Li & Al (Li 75%) Fig. 7 f Example 6 Li & Al (Li 90%) Fig. 7 g Example 7 Li & Al (Li 95%) Fig. 7 h Example 8 Li & Sn (Li 110%) Fig. 9 b Example 9 Li & Sn (Li 220%) Fig. 9 c Comparative Example 1 Al Fig. 7 b Comparative Example 2 Sn Fig. 9 a

[0102] XRD and CCD (Charge-Coupled Device) tests were performed using a powder mixing bowl. Figure 7a shows Li at various current densities. x Comparison of specific capacities between Al1 alloy electrodes is shown. Figures 7b to h show the Li with increasing prelithiation degree at N / P ratio 2 of Examples 2 to 7 and Comparative Example 1. x CCD screening for improvement in the reaction rate of Al1 alloy electrode is shown. Figure 8 shows Example 2 (Li 0.25 Al1), Example 4 (Li 0.5 Al1) and Example 5 (Li 0.75 The XRD pattern of Al1) is shown. Figures 9a to 9c show the increase in the degree of prelithiation at the N / P ratio 2 of Examples 8 and 9 and Comparative Example 2, along with Li x CCD screening for improvement of reaction rate of Sn1 alloy electrode is shown. Figure 9d shows Li x The comparison of the initial Coulombic efficiency between Sn1 alloy electrodes is shown in Fig. 9e. Li at each current density x A comparison of the specific capacitances between Sn1 alloy electrodes is illustrated. As shown in FIGS. 7 to 9, Examples 2 to 9 exhibited superior critical current densities compared to Comparative Examples 1 and 2.

[0103] Experiment 3

[0104] The cathode (NCM), electrolyte material (LiPSCl) and the anode are included and various N / P ratios and various C-rates are listed in Table 2 below: 0.1C, 0.2C, 0.4C, 0.8C, 1.2C, 1.6C, 2C, 2.4C, 2.8C (1C = 2.5mAh cm -2 ), the capacity and coulombic efficiency were tested under the conditions of a stack pressure of 75 MPa and room temperature.

[0105] Sample Cathode N / P Ratio Drawing Example 10 Li & Al (Li 50%) 2 of Fig. 10 a Example 11 Li & Al (Li 50%) 1.5 of Fig. 10 b Example 12 Li & Al (Li 50%) 1.2 of Fig. 10 c Example 13 Li & Al (Li 25%) 2 of Fig. 10 d Example 14 Li & Al (Li 25%) 1.5 of Fig. 10 e Example 15 Li & Al (Li 25%) 1.2 of Fig. 10 f Comparative Example 3 Al 2 of Fig. 10 g Comparative Example 4 Al 1.5 of Fig. 10 h Comparative Example 5 Al 1.2 of Fig. 10 i

[0106] CCD tests were performed using a powder mixing bowl. Figures 10a to 10i show CCD screening for improvement in the reaction rate of the electrodes of Examples 10 to 15 and Comparative Examples 3 to 5. As shown in Figures 10a to 10i, Examples 10 to 15 exhibited superior critical current densities compared to Comparative Examples 3 to 5.

[0107] Experiment 4

[0108] Containing positive electrode (NCM), electrolyte material (LiPSCl) and negative electrode with various N / P ratios and C-rates listed in Table 3 below: 1.2C (1C = 2.5mAh cm -2 ), the capacity and coulombic efficiency were tested under the conditions of a stack pressure of 75 MPa and room temperature.

[0109] Sample Cathode N / P Ratio Drawing Example 16Li & Al (Li 50%)2 Fig. 11a & 11b Example 17Li & Al (Li 25%)2 Fig. 11a & 11b Comparative Example 6Al2 Fig. 11a & 11b Example 18Li & Al (Li 50%)2 Fig. 12 Example 19Li & Al (Li 25%)1.2 Fig. 12

[0110] Figures 11a and 11b show the specific capacity (mAh g) versus cycle number of Examples 16 and 17 and Comparative Example 6. -1 )(Fig. 11a) and specific capacity (mAh g -1) and Coulombic efficiency (%) (Fig. 11b). As shown in Figs. 11a and 11b, the capacity retention rate for Example 16 was 82% until 1446 cycles, whereas Example 17 was short-circuited after 280 cycles and Comparative Example 6 was short-circuited after 88 cycles. As shown in Fig. 12, the capacity retention rate for Example 18 was 79% until 1500 cycles, whereas Example 19 was short-circuited after 232 cycles. These results show that the cycle characteristics of Examples 16-19 are superior to that of Comparative Example 6, and that the cycle characteristics of Examples 16 and 18 are superior to those of Examples 17 and 19. Fig. 13 shows the XRD patterns of Example 20 (Li3Sn1), Example 21 (Li2Sn1), and Example 22 (Li1Sn1). As shown in Fig. 13, Example 20 has a crystal structure more suitable for improving the critical current density compared to Examples 21 and 22.

[0111] Those skilled in the art will appreciate that the embodiments of this disclosure can be practiced within a wide range of equivalent parameters without affecting the scope of the disclosure described herein. All publications, patent applications, and patents disclosed herein are incorporated by reference in their entirety.

Claims

1. An all-solid-state battery comprising a cathode, a cathode, and a solid electrolyte, The above solid electrolyte is interposed between the cathode and the anode, The above negative electrode comprises a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof; The above product is a prelithiated metal alloy having the chemical formula LixMy, wherein Li is lithium, M is a metal, x and y are integers greater than 0; The mass ratio of the lithium and metal is 1:4 to 1:20; The above negative electrode is an all-solid-state battery that does not contain a binder material.

2. In paragraph 1, The above product is Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al or Li 0.95 All-solid-state battery with a prelithiated metal having the chemical formula Al 3. In paragraph 1 The above product is Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn or Li 2.2 An all-solid-state battery comprising a prelithiated metal having the chemical formula Sn.

4. In paragraph 1 An all-solid-state battery wherein the average particle size of the lithium powder is 30 μm to 60 μm.

5. In paragraph 1 An all-solid-state battery in which the mass ratio of lithium and metal is 1:4 to 1:

20.

6. In paragraph 1 An all-solid-state battery having an N / P ratio of 1.00 to 2.

00.

7. In paragraph 1, All-solid-state battery with an N / P ratio of 1.2 to 1.

5.

8. An all-solid-state battery comprising a cathode, a cathode, and a solid electrolyte, The above solid electrolyte is interposed between the cathode and the anode, The above negative electrode comprises a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn), or a mixture thereof; The average particle size of the lithium powder is 0.1 μm to 200 μm; The above product is a prelithiated metal alloy having the chemical formula LixMy, wherein Li is lithium, M is a metal, and x and y are integers greater than 0; The mass ratio of the lithium and metal is 1:4 to 1:20; The N / P ratio is 1.00 to 3.00; An all-solid-state battery, the cathode of which does not contain a binder material.

9. In paragraph 8, The above product is Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al or Li 0.95 All-solid-state battery with a prelithiated metal having the chemical formula Al 10. In paragraph 8, The above product is Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn or Li 2.2 An all-solid-state battery comprising a prelithiated metal having the chemical formula Sn.

11. In paragraph 8, An all-solid-state battery wherein the average particle size of the lithium powder is 30 μm to 60 μm.

12. In paragraph 8, An all-solid-state battery in which the mass ratio of lithium and metal is 1:4 to 1:

15.

13. In paragraph 8, An all-solid-state battery having an N / P ratio of 1.00 to 2.

00.

14. An all-solid-state battery comprising a cathode, a cathode, and a solid electrolyte, The above solid electrolyte is interposed between the cathode and the anode, The above negative electrode comprises a negative electrode material comprising a product of (i) lithium (Li) powder; and (ii) a metal selected from aluminum (Al), tin (Sn) or a mixture thereof; The above product is a prelithiated metal alloy having the chemical formula LixMy, wherein Li is lithium, M is a metal, and x and y are integers greater than 0; The mass ratio of the lithium and metal is 1:4 to 1:20; The above negative electrode is an all-solid-state battery that does not contain a binder material.

15. In paragraph 14, The above product is Li 0.25 Al, Li 0.4 Al, Li 0.5 Al, Li 0.75 Al, Li 0.8 Al, Li 0.9 Al or Li 0.95 An all-solid-state battery comprising a prelithiated metal having the chemical formula Al.

16. In paragraph 14, The above product is Li 0.25 Sn, Li 0.5 Sn, Li 0.75 Sn, Li 1.1 Sn or Li 2.2 An all-solid-state battery comprising a prelithiated metal having the chemical formula Sn.

17. In paragraph 14, An all-solid-state battery wherein the average particle size of the lithium powder is 30 μm to 60 μm.

18. In paragraph 14, An all-solid-state battery in which the mass ratio of lithium and metal is 1:4 to 1:

15.

19. In paragraph 14, An all-solid-state battery having an N / P ratio of 1.00 to 2.

00.

20. A method for manufacturing an all-solid-state battery according to Article 1, A step of forming an LPSCl separation membrane layer by compressing LPSCl powder; A step of applying and pressing NCM composite powder on the first surface of the compressed LPSCl membrane layer; A step of forming a battery cell by applying a powder composite of lithium and aluminum to a second surface opposite to the first surface of the LPSCl separator layer and pressing it; A step of maintaining the battery cell under stack pressure so that an alloying reaction between the lithium and aluminum occurs; and Step of cycling the above battery cell A manufacturing method comprising:

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