Alloy electrode for all-solid-state battery and manufacturing method therefor

Abstract

A negative electrode layer is disclosed. The negative electrode layer comprises a polymer binder and LiAl-containing particles. The negative electrode layer has a first surface and a second surface facing a direction opposite to the first surface. Along the general direction from the first surface to the second surface, the Li content of the LiAl-containing particles generally increases, the size of the LiAl-containing particles generally decreases, and the shape of the LiAl-containing particles generally changes from a round shape to an irregular shape having sharp corners. Molecules of the polymer binder are generally distributed throughout the negative electrode layer and surround at least a portion of the LiAl-containing particles.

Description

Alloy electrode for all-solid-state battery and method for manufacturing the same

[0001] The present disclosure relates to an alloy electrode for an all-solid-state battery, in particular a lithium-aluminum (LiAl) alloy cathode and / or cathode layer, and a method for manufacturing the cathode and / or cathode layer.

[0002] secondary battery

[0003] Rechargeable batteries are becoming an increasingly desirable power source for a wide variety of electronic devices, such as automobiles, computers, mobile phones, tools, scooters, bicycles, electric vehicles, power storage systems, drones, and other devices. Among rechargeable batteries, lithium-based batteries are particularly in the spotlight due to their ability to provide a desirable balance of voltage and energy density. Traditionally, lithium rechargeable batteries contain a liquid electrolyte, typically consisting of lithium salts dissolved in an organic solvent. However, there is growing interest in developing all-solid-state lithium rechargeable batteries as an alternative to conventional liquid electrolyte-based systems. All-solid-state batteries offer potential advantages in terms of safety, stability, and energy density. Despite these potential benefits, the development of practical all-solid-state lithium rechargeable batteries faces several significant challenges.

[0004] Challenges of All-Solid State Secondary Batteries

[0005] One of the challenges in all-solid-state battery design is achieving and maintaining sufficient lithium ion diffusion within solid electrolyte materials. Additionally, volume changes (e.g., expansion and contraction) can occur in specific battery components, such as electrodes, during discharge and charging. These volume changes can induce mechanical stress or lead to contact loss between various components within the battery structure. Contact loss between battery components can result in a degradation of overall battery capacity as well as a deterioration in charge-discharge characteristics. Researchers and engineers in the field of energy storage are actively working to address these challenges. They are focusing on developing new materials and battery designs capable of achieving desirable lithium ion diffusion while accommodating the mechanical stress associated with battery cycling. Improving the stability of interfaces within all-solid-state batteries remains an area of ​​research. Overcoming the current limitations of all-solid-state battery systems holds the potential for significant advancements in energy storage capabilities for a wide range of applications.

[0006] alloy electrode

[0007] Alloy electrodes have emerged as a promising category of all-solid-state batteries due to their potential to provide higher energy density while offering inherent safety advantages. These electrodes operate based on reversible alloying and dealloying reactions between lithium and a host metal, a mechanism that can enable high capacity and enhanced electrochemical performance compared to traditional intercalation electrodes. Integrating alloy electrodes into all-solid-state battery systems can further improve stability and safety by eliminating flammable liquid electrolytes, thereby reducing risks associated with dendrite formation and thermal runaway.

[0008] Li-Al alloy cathode

[0009] Among various alloy systems, Li-Al alloy anodes are attracting significant attention. Li-Al systems offer an attractive balance between energy density and material availability because aluminum is both air-loaded and cost-effective. In these alloys, lithium is reversibly incorporated into the aluminum matrix, forming various intermetallic phases. Since this reversible alloying reaction can provide high theoretical capacity, Li-Al alloy anodes are strong candidates for high-performance all-solid-state batteries. Furthermore, thanks to the inherent stability provided by the solid electrolyte environment, Li-Al alloys can enable more robust cycling performance and longer battery life compared to systems using conventional liquid electrolytes.

[0010] Design of alloy electrodes

[0011] The design of alloy electrodes, particularly Li-Al alloy cathodes, involves careful consideration of material composition and structural integration to maximize lithium storage and recovery efficiency. Researchers have explored various electrode architectures, including nanostructured forms and composite configurations, to optimize both the electrochemical kinetics and mechanical integrity of the electrodes. The goal is to ensure that the alloy electrodes not only provide high capacity and high energy density but also maintain stable and uniform reaction pathways throughout repetitive cycling.

[0012] Advantages of alloy electrodes

[0013] In summary, alloy electrodes offer an innovative approach to all-solid-state battery design by leveraging the high capacity and favorable electrochemical properties of alloying reactions. Li-Al alloy cathodes, possessing high theoretical capacity and the advantages of aluminum abundance and cost-effectiveness, are emerging as particularly promising candidates for next-generation energy storage applications. Integrating these into all-solid-state battery systems can pave the way for safer, more efficient, and longer-lasting batteries that meet the increasing demands of modern electronics and electric vehicle technology.

[0014] Prohibition of recognizing prior art

[0015] The discussion in this section is intended to provide background information related to the present disclosure and is not an acknowledgment of prior art.

[0016] The object of the present invention is to provide a cathode comprising particles (LiAl-containing particles) containing a lithium-aluminum alloy (LiAl).

[0017] cathode

[0018] One embodiment of the present disclosure provides a cathode. The cathode comprises a current collector and a cathode active material layer. The cathode active material layer comprises a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (hereinafter "LiAl-containing particles"). The cathode active material layer has a first surface facing in a direction opposite to the current collector and a second surface facing the current collector. In general, the closer to the second surface along the direction from the first surface to the second surface within the cathode active material layer, the more lithium is contained in the LiAl-containing particles. In general, the closer to the second surface along the said direction within the cathode active material layer, the smaller the LiAl-containing particles become. In general, the closer to the second surface along the said direction within the cathode active material layer, the less round the LiAl-containing particles become. Additionally, molecules of the polymer binder are generally distributed throughout the entire cathode active material layer so that at least a portion of the molecules of the polymer binder are interposed between two adjacent LiAl-containing particles within the cathode active material layer.

[0019] surface

[0020] In some embodiments, the cathode layer provided herein further comprises Al particles on a first surface. In some embodiments, the cathode layer provided herein further comprises Li metal on a second surface.

[0021] Molby

[0022] In some embodiments, the LiAl-containing particles have a Li:Al molar ratio of about 0.1 to about 5. In some embodiments, the LiAl-containing particles have a Li:Al molar ratio of about 0.5 to about 1. In some embodiments, the LiAl-containing particles have a Li:Al molar ratio of about 0.5.

[0023] polymer binder

[0024] In some embodiments, the polymer binder comprises at least one polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyimide (PI), carboxymethyl cellulose (CMC), succinonitrile-based polymer, styrene-butadiene rubber (SBR), polyethylene glycol (PEG), polyvinyl acetate (PVAc), polyurethane (PU), polyacrylic acid (PAA), ionic polymer, gel polymer, hydroxypropyl methylcellulose, methyl cellulose, starch, modified starch, and acrylic emulsion polymer.

[0025] Method for manufacturing a cathode

[0026] Another aspect of the present disclosure provides a method for manufacturing a cathode. An Al-containing film comprising Al particles and a polymer binder is provided, and the Al-containing film is laminated on top of a Li foil that is laminated on top of a current collector so that the surface of the Al-containing film and the surface of the Li foil come into contact with each other. Then, the Al-containing film and the Li foil are pressed together on top of the current collector to form a cathode, so that at least a portion of the Li metal in the Li foil moves toward the Al-containing film, and at least a portion of the Al particles in the Al-containing film move toward the Li foil, and the Li metal comes into contact with the surface of the Al particles to form particles containing a lithium-aluminum alloy (LiAl) (hereinafter "LiAl-containing particles"). The cathode comprises a current collector and a cathode active material layer. The cathode active material layer comprises a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (hereinafter "LiAl-containing particles"). The cathode active material layer has a first surface facing in a direction opposite to the current collector and a second surface facing the current collector. Generally, the closer to the second surface along the direction from the first surface to the second surface within the negative active material layer, the more lithium is contained in the LiAl-containing particles. Generally, the closer to the second surface along the said direction within the negative active material layer, the smaller the LiAl-containing particles become. Generally, the closer to the second surface along the said direction within the negative active material layer, the less round the LiAl-containing particles become. In addition, the molecules of the polymer binder are generally distributed throughout the entire negative active material layer so that at least a portion of the molecules of the polymer binder are interposed between two adjacent LiAl-containing particles within the negative active material layer.

[0027] Preparation of Al-containing films

[0028] In some embodiments, the method provided herein further comprises the step of preparing an Al-containing film. First, a solution or slurry comprising Al particles, a solvent, and a polymer binder is prepared. Then, a layer of said solution or slurry is applied on top of a substrate and dried to form an Al-containing film having a substantially uniform thickness.

[0029] bookbinder

[0030] In some embodiments, the polymer binder comprises at least one polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyimide (PI), carboxymethyl cellulose (CMC), succinonitrile-based polymer, styrene-butadiene rubber (SBR), polyethylene glycol (PEG), polyvinyl acetate (PVAc), polyurethane (PU), polyacrylic acid (PAA), ionic polymer, gel polymer, hydroxypropyl methylcellulose, methyl cellulose, starch, modified starch, and acrylic emulsion polymer. In some embodiments, the polymer binder is in an amount of about 0.1 to 10 wt% based on the total weight of the Al powder.

[0031] thickness of Li foil

[0032] In some embodiments, the Li foil has a thickness of about 0.1 μm to about 10 μm.

[0033] condition

[0034] In some embodiments, the Al-containing film and Li foil are pressurized under a pressure of about 100 MPa to about 500 MPa. In some embodiments, the Al-containing film and Li foil are pressurized under a pressure of about 125 MPa to about 400 MPa. In some embodiments, the Al-containing film and Li foil are pressurized for about 5 minutes to about 1 hour. In some embodiments, the Al-containing film and Li foil are pressurized for about 10 minutes to about 30 minutes. In some embodiments, the Al-containing film and Li foil are at about 20°C Pressurized at a temperature of about 150°C. In some embodiments, the Al-containing film and the Li foil are pressurized at a temperature of about 50°C to about 100°C.

[0035] All-solid-state battery

[0036] Another aspect of the present disclosure provides an all-solid-state battery comprising a negative electrode; a positive electrode; and a solid electrolyte positioned between the positive electrode and the negative electrode and configured to enable the transport of lithium ions between the positive electrode and the negative electrode. The negative electrode comprises a current collector and a negative electrode active material layer. The negative electrode active material layer comprises a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (hereinafter "LiAl-containing particles"). The negative electrode active material layer has a first surface facing in a direction opposite to the current collector and a second surface facing the current collector. In general, the closer to the second surface along the direction from the first surface to the second surface within the negative electrode active material layer, the more lithium is contained in the LiAl-containing particles. In general, the closer to the second surface along the said direction within the negative electrode active material layer, the smaller the LiAl-containing particles become. In general, the closer to the second surface along the said direction within the negative electrode active material layer, the less round the LiAl-containing particles become. In addition, the molecules of the polymer binder are generally distributed throughout the entire negative electrode active material layer, so that at least a portion of the molecules of the polymer binder are interposed between two adjacent LiAl-containing particles within the negative electrode active material layer.

[0037] Exemplary embodiment

[0038] These and other features of the present disclosure can be understood from the following detailed description ('Specific details for carrying out the invention') and will become more fully apparent from exemplary embodiments of the present disclosure. Furthermore, it will be readily understood that the purpose and advantages of the present disclosure can be realized by the means set forth in the appended claims and combinations thereof.

[0039] Overview No restrictions

[0040] It is understood that the present disclosure is not limited to the examples set forth in this summary ('Description of the Invention'). Various other embodiments are described and illustrated herein.

[0041] The method for manufacturing a battery structure according to the present invention can provide an alloy electrode for an all-solid-state battery capable of exhibiting high capacity and energy density, and a method for manufacturing the same.

[0042] FIG. 1 illustrates an exemplary process for manufacturing an exemplary alloy cathode using an embodiment of the method provided herein.

[0043] FIG. 2 illustrates an exemplary process for manufacturing an exemplary alloy cathode using another embodiment of the method provided herein.

[0044] FIG. 3 is a scanning electron microscope (SEM) image of a portion of the cross-section of an exemplary cathode manufactured by an embodiment of the method shown in FIG. 2.

[0045] Figure 4 illustrates the morphology of a portion of the cross-section of the exemplary cathode of Figure 3.

[0046] FIG. 5 is an example of an all-solid-state battery according to one embodiment.

[0047] Figure 6 shows the XRD spectra of the Al-containing film of Example 1.1 and the LiAl cathode of Example 1.4.

[0048] Figure 7 is an SEM image of the cathode of Example 1.4.

[0049] Figure 8 is the XRD spectrum of the Al-containing film of Example 2.1 and the LiAl cathode of Example 2.4.

[0050] Figure 9 shows the CCD test results for the battery of Example 3.1.

[0051] Figure 10 shows the CCD test results for the battery of Example 4.1.

[0052] No limit on examples

[0053] The examples described herein illustrate specific, non-limiting embodiments in one form, and such examples should not be construed as limiting the appended claims in any way.

[0054] Examples and embodiments

[0055] Now, the subject matter of this disclosure will be described and discussed in more detail in terms of some specific embodiments and examples, with reference to the accompanying drawings, which depict some embodiments rather than all embodiments of the invention. Unless otherwise noted, the same numbers refer to the same element or part in whole. The subject matter of this disclosure may be embodied in many different forms and should not be interpreted as being limited to the specific embodiments presented herein. Rather, these embodiments are provided to satisfy applicable legal requirements. In fact, many variations and other embodiments of the subject matter of this disclosure will come to mind to those skilled in the art to which the subject matter of this disclosure belongs. Accordingly, it should be understood that the subject matter of this disclosure is not limited to the specific embodiments disclosed, and that variations and other embodiments are intended to be included within the scope of the appended claims.

[0056] Interpretation of the scope of claims

[0057] The present disclosure is described in detail below. It should be understood that terms or words used in this specification and the appended claims should not be interpreted as being limited to their general and dictionary meanings, but should be interpreted based on the meanings and concepts corresponding to the technical aspects of the present disclosure, in accordance with the principle that the inventor is permitted to appropriately define terms for the best description. Accordingly, it should be understood that the aspects of the disclosure described herein and the elements illustrated in the drawings are merely aspects of the present disclosure and are not intended to fully describe the technical aspects of the present disclosure, and that other equivalents and modifications may have been made at the time of filing.

[0058] Technical terms

[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as generally known to those skilled in the art. If multiple definitions exist for a term in this document, the definition provided herein shall prevail.

[0060] definition

[0061] singular

[0062] The singular form of a word used herein includes the plural form unless otherwise indicated in the context. The plural encompasses the singular, and vice versa. Accordingly, references to the singular form generally include the plural of each term. For example, although the present disclosure has been described using singular terms such as layer, substrate, cell, etc., two or more of these components and other components (including combinations) may be used.

[0063] "Approximately," "roughly," and "practically"

[0064] The term “approximately” indicates and encompasses the indicated value and the range above and below that value. As used herein, “approximately,” “approximately,” and “substantially” are understood to indicate a numerical range, for example, -10% to +10% of the referenced value, preferably -5% to +5% of the referenced value, more preferably -1% to +1% of the referenced value, and most preferably -0.1% to +0.1% of the referenced value. In certain embodiments, the term “approximately” indicates ±10%, ±5%, or ±1% of the specified value. In certain embodiments, the term “approximately” indicates the specified value ± one standard deviation of the corresponding value.

[0065] "Comprise," "Consisting Essentially Of," and "Consisting Of"

[0066] The words “comprise(s)” and “comprising” should be interpreted inclusively rather than exclusively. Likewise, the terms “include,” “including,” and “or” should all be interpreted inclusively unless the context explicitly prohibits such inclusive interpretation. However, the embodiments provided by this disclosure may or may not lack any elements not specifically disclosed herein. Accordingly, the disclosure of an embodiment defined using the term “comprising” is also the disclosure of an embodiment that is “essentially composed of” the disclosed component and an embodiment that is “essentially composed of” the disclosed component. The phrase “essentially composed of” limits the scope of the disclosed component to the specified material or step and to components that do not significantly affect the fundamental and novel features of the disclosed invention. The phrase “composed of” excludes any unspecified element, step, or component.

[0067] "and / or"

[0068] The term "and / or" used in the context of "X and / or Y" must be interpreted as "X", "Y", or "X and Y".

[0069] "On" and "Over"

[0070] As used herein, terms such as “on,” “applied to,” “applied to,” “formed on,” “formed on,” “deposited on,” “deposited on,” “laminated,” “provided on,” and “provided on” mean that they are formed, laminated, deposited, or provided on a surface, but do not necessarily have to be in contact with the surface. For example, a formed layer “applied to” a substrate layer does not exclude the presence of one or more other layers of the same or different composition located between the formed layer and the substrate layer.

[0071] Markush Group

[0072] The term “combination thereof” included in any Markush-type expression used herein means a combination or mixture of one or more elements selected from the group of elements disclosed in the Markush-type expression, and means the presence of one or more elements selected from the group. The term “combination thereof” includes all possible combinations of the elements referred to by such term.

[0073] "between"

[0074] The expression "between" as used herein includes endpoints.

[0075] numerical range

[0076] Furthermore, all numeric ranges in this disclosure should be understood to include all integers, whole numbers, or fractions within such ranges. Additionally, any numeric range cited herein is intended to include all sub-ranges contained therein, and such numeric ranges should be interpreted to support claims relating to any number or subset of numbers within such ranges. For example, the disclosure of 1 to 10 should be interpreted to support ranges such as 1 to 8, 3 to 7, 1 to 9, 3.6 to 4.6, 3.5 to 9.9, etc. Where a range is given, any endpoint of such range and / or a number within such range may be combined with the ranges of this disclosure.

[0077] numerical precision

[0078] As used herein, unless otherwise explicitly specified, any numerical value expressing a value, range, amount, or percentage may be read as if preceded by the word “approximately,” even if the term is not explicitly indicated. Terms such as “including,” “same as,” “for example,” and similar terms mean “including / same as / for example,” but are not limited thereto.

[0079] Combination of embodiments

[0080] As used herein, the term “Example” is merely illustrative and descriptive, particularly where a list of terms follows, and should not be construed as exclusive or inclusive. Any embodiment disclosed herein may be combined with any other embodiment disclosed herein unless expressly indicated otherwise.

[0081] particle size

[0082] The particle size used herein is the average particle diameter (D) measured using a microscope (e.g., optical microscope, electron microscope, scanning electron microscope (SEM), transmission electron microscope (TEM), atomic force microscope (AFM), confocal microscope, or fluorescence microscope). 50 Refers to ). The above size may be the diameter of a spherical particle or the length according to the maximum dimension of an elliptical or other irregularly shaped particle. The "D" of the particle used herein 50 It refers to a diameter where 50% of the particles have a smaller diameter.

[0083] Challenges of Li-Al alloy electrodes

[0084] Project Overview

[0085] Li-Al alloy electrodes for all-solid-state batteries face challenges such as large volume expansion, mechanical stress, poor lithium ion diffusion due to phase separation issues, and interfacial interaction problems with solid electrolytes. These challenges are further complicated by the instability of lithium powder, the difficulty of scaling lithium and aluminum powders, the high density and lithiation limitations of aluminum foil, and the precision required to fabricate uniform lithium films.

[0086] Volume expansion

[0087] The development of Li-Al alloy electrodes for all-solid-state batteries faces numerous complex technical challenges stemming from both the inherent properties of the materials and processing limitations. One of the most critical challenges is the significant volume expansion that occurs during lithium insertion and extraction. The alloying reaction between lithium and aluminum can result in a volume change of up to approximately 200%, which can generate significant mechanical stress. This expansion and contraction cycle can induce cracking and structural degradation of the electrode as the cycle is repeated, thereby degrading both mechanical integrity and long-term electrochemical performance.

[0088] Poor lithium ion diffusion

[0089] Along with these mechanical problems, there is also the issue of poor lithium ion diffusion within the aluminum matrix. Since aluminum inherently has a low lithium ion diffusion coefficient, it hinders rapid charge and discharge capabilities. This situation affects various Li-alpha, such as LiAl, Li3Al2, and Li9Al4, during cycling. x The formation of the Al phase is making the process more complex. The resulting phase separation leads to a heterogeneous lithium distribution within the electrode, which can create regions with poor electrical connectivity and increased internal resistance. This heterogeneity in lithium transport exacerbates the overall performance degradation of the electrode.

[0090] Interface with solid electrolyte

[0091] Additional complex issues arise at the interface between the Li-Al alloy electrode and the solid electrolyte. Dynamic volume changes in the electrode can hinder physical contact with the solid electrolyte, increasing interfacial resistance and reducing ion transport efficiency. Furthermore, certain solid electrolytes, particularly those based on sulfide chemistry, can react with the Li-Al alloy to form a resistive interfacial layer. These chemical interactions not only impede lithium ion movement but also cause battery performance degradation over time.

[0092] Challenges in powder precursor materials

[0093] This challenge extends beyond the alloy itself to precursor materials and fabrication processes. For example, lithium powder is inherently unstable due to its high reactivity and susceptibility to rapid oxidation even upon exposure to trace amounts of moisture or oxygen. This instability necessitates strict inert atmosphere conditions during processing, significantly complicating manufacturing operations and increasing production costs. Furthermore, both lithium and aluminum powders present significant scaling challenges. Achieving a consistent particle size distribution and controlled surface reactivity on a commercial scale is difficult, and any deviation can lead to the formation of heterogeneous alloys. Such inconsistencies can result in localized areas of poor electrical connectivity and uneven mechanical stress distribution during cycling.

[0094] Challenges in layered precursor materials

[0095] Alternative approaches, such as employing aluminum foil as a precursor, also face significant limitations. The high density and crystalline nature of aluminum foil restrict effective lithium penetration during the lithiation process, leading to incomplete alloy formation and a heterogeneous distribution of the Li-Al alloy. This incomplete lithiation impairs the uniformity and performance of the resulting electrode. Similarly, using lithium films as precursors for alloy formation or as essential components of electrodes presents its own set of challenges. Fabricating uniform lithium films requires precise control of deposition conditions. Even slight irregularities in film thickness or surface coverage can lead to non-uniform alloying with aluminum, potentially exacerbating issues related to phase heterogeneity and mechanical stress.

[0096] Powder and powder

[0097] When fabricating Al-Li alloy electrodes for all-solid-state batteries using aluminum and lithium powders, several significant challenges arise due to both the inherent reactivity of the powders and the complexity of processing. Using Al and Li powders requires strict control of the processing environment (often requiring inert atmosphere conditions) and precise optimization of mixing, pressurization, and sintering parameters.

[0098] chemical reactivity

[0099] One of the most critical issues is the inherent chemical reactivity of the powders, particularly that of Li powder. Because lithium powder is extremely sensitive to air and moisture, it can oxidize rapidly even with trace amounts of oxygen or water vapor. This oxidation not only degrades the active material but can also compromise process safety by generating heat or even triggering unwanted exothermic reactions. Similarly, although aluminum is less reactive than lithium, fine Al powder is prone to forming surface oxides, which create a passivation layer that can hinder subsequent alloying processes.

[0100] Non-uniformity

[0101] Another challenge arises from the difficulty of achieving a uniform distribution when mixing powders together. Differences in particle size, shape, and density between Al and Li powders can lead to aggregation or uneven mixing, which may result in non-homogeneous alloy composition during pressurization or sintering. This non-homogenization can adversely affect the mechanical integrity and electrochemical performance of the electrode, as regions with excess or deficiency of lithium may exhibit different reaction kinetics or conductivity.

[0102] process

[0103] The processing of powder-based electrodes presents challenges even during the consolidation and sintering stages. Unlike continuous films, powders require careful control of pressure conditions to achieve sufficient densification while avoiding the formation of voids or cracks. Poor interparticle connectivity leads to higher internal resistance, which can degrade lithium diffusion efficiency during cycling. Furthermore, controlling stoichiometry and ensuring close contact between individual powder particles is more complex in powder systems, where large surface areas exacerbate issues related to oxidation and contamination.

[0104] Film and film

[0105] Using separate aluminum (Al) and lithium (Li) films to fabricate Al-Li alloy electrodes for all-solid-state batteries presents several interrelated challenges, ranging from material handling to interfacial chemistry and mechanical integrity. These challenges include controlling the uniformity and surface quality of the aluminum film, preventing oxidation and ensuring consistent film formation with highly reactive lithium, achieving close and clean interfacial contact for effective alloying, and managing mechanical stresses generated during pressurization and subsequent battery operation.

[0106] Film formation

[0107] One of the major challenges with aluminum films is ensuring uniformity and purity during film formation. Aluminum films are prone to surface oxidation during processing, which can hinder subsequent alloying with lithium. Since aluminum is denser and relatively inert compared to lithium, it is essential to achieve a uniform, defect-free film with consistent thickness and microstructure. Non-uniformity can lead to uneven lithium penetration during the alloying process, resulting in localized areas with varying alloy compositions and ultimately inconsistent electrochemical performance. Additionally, mechanical stress during processing—for example, during lamination or pressurization—can induce microcracks or delamination in the aluminum film, potentially degrading structural integrity before or during the alloying stage.

[0108] Challenges of Lithium Film

[0109] Lithium films present a series of inherent challenges due to their inherent chemical reactivity and softness. Since lithium is highly reactive with moisture and oxygen, the processing environment (typically under inert atmosphere conditions) must be strictly controlled to prevent oxidation or contamination. Furthermore, lithium films tend to be ductile and soft, making them difficult to handle without deformation. This softness can make it difficult to achieve a uniform film of consistent thickness and complicates the pressurization process used to bring the Li film into close contact with the Al film. Under pressure, lithium may not be uniformly distributed across the interface; instead, it may form localized aggregations or develop irregular morphologies, which can result in non-uniform alloying and the formation of intermetallic phases with various properties.

[0110] Interfacial contact

[0111] For effective alloying, it is crucial to ensure robust and defect-free contact at the interface between the Al and Li films. The pressurization process must overcome surface roughness and any existing oxide layers to allow lithium atoms to diffuse into the aluminum lattice. However, if the interface is not sufficiently bonded or the surface is contaminated, the diffusion of lithium into the aluminum may be inhibited. This results in incomplete alloying and the potential formation of brittle intermetallic compounds, which can compromise the mechanical and electrochemical stability of the electrode.

[0112] Dynamic behavior

[0113] Furthermore, additional complex issues arise due to the dynamic behavior of both films under mechanical pressure. The differing mechanical properties of the two films—hard aluminum and soft lithium—can lead to uneven stress distribution and localized deformation. This not only affects the interdiffusion process but also raises concerns regarding long-term cycling stability, as repeated charge-discharge cycles can exacerbate any initial inhomogeneities formed during processing.

[0114] Foil and foil

[0115] Fabricating Al-Li alloy electrodes for all-solid-state batteries using aluminum and lithium foils presents a series of distinct challenges compared to other forms of these materials. These challenges include managing the surface oxidation of aluminum, overcoming the low specific surface area and mechanical stiffness of the foils, handling the extreme reactivity and softness of the lithium foils, and resolving the issue of mechanical mismatch between the two. Due to these factors, the formation of a uniform and defect-free alloy interface becomes complex, and careful control of processing conditions—such as handling in an inert atmosphere, precise surface treatment, and optimized pressure application—is required to secure reliable electrodes for all-solid-state battery applications.

[0116] The challenge of Al foil

[0117] One of the main problems with aluminum foil is that its high density and relatively low specific surface area can limit the degree and uniformity of lithiation. In many cases, a natural oxide layer forms on the surface of aluminum foil during storage or handling, and this oxide layer must be removed or sufficient lithium must be infiltrated during the alloying process. This oxide layer can inhibit effective interdiffusion between lithium and aluminum, leading to a non-uniform alloy composition. Furthermore, the mechanical strength of aluminum foil implies that any existing surface defects or non-uniformities may persist throughout the processing, further complicating the formation of a homogeneous Li-Al alloy layer.

[0118] The challenge of Li foil

[0119] On the other hand, lithium foil is characterized by extremely high chemical reactivity and softness. Due to its high reactivity, lithium foil is highly sensitive to air and moisture; even minimal exposure can lead to oxidation or the formation of lithium compounds, resulting in a decrease in purity. Because of this reactivity, strict processing conditions under an inert atmosphere are typically required, which increases complexity and cost. Furthermore, the soft and ductile nature of lithium foil implies that it is difficult to handle without deformation. During pressurization or lamination with aluminum foil, lithium flows unevenly, which can lead to localized areas with excessive or insufficient lithium content. These non-uniformities not only affect the stoichiometry of the resulting alloy but can also induce mechanical stress and potential delamination at the interface.

[0120] Discrepancy in mechanical properties

[0121] Furthermore, when combining hard materials like aluminum foil with much softer lithium foil, differences in mechanical properties become critical during the pressurization and alloying processes. This inconsistency in hardness leads to uneven pressure distribution, which can cause uneven alloy formation and localized stress concentration. These factors can lead to the formation of microcracks or voids, which can adversely affect the battery's electrochemical performance and long-term cycling stability. Finally, because both foils are used as continuous layers, ensuring close, defect-free contact along the entire interface is more difficult than with particle or film-based systems.

[0122] Lithium plating and dendrite structure

[0123] In addition, if lithium is deposited unevenly during cycling, lithium plating and dendrites may form on the electrode surface. These dendrites can penetrate the solid electrolyte, potentially leading to serious safety risks due to short circuits. Therefore, maintaining a stable and uniformly lithiated electrode surface is essential to ensure both safety and reliable long-term battery performance.

[0124] Solving the problem

[0125] To address these multifaceted challenges, innovative fabrication strategies and material modifications are required, such as nanostructuring to better accommodate volume changes, the use of buffer layers to enhance interfacial stability, and the optimization of the Li:Al ratio. These advancements are crucial for achieving commercially viable Li-Al alloy electrodes for next-generation all-solid-state battery technology.

[0126] Method for manufacturing a cathode

[0127] One aspect of the present disclosure provides a method for manufacturing a cathode comprising Li-Al alloy-containing particles and a polymer binder. The method comprises the steps of: providing an Al-containing film comprising Al particles and a polymer binder; laminating the Al-containing film with a Li foil laminated on top of a current collector so that the surface of the Al-containing film and the surface of the Li foil come into contact with each other; and pressing the Al-containing film and the Li foil together to form the cathode provided herein, such that at least a portion of the Li metal in the Li foil moves toward the Al-containing film, at least a portion of the Al particles in the Al-containing film move toward the Li foil, and the Li metal comes into contact with the surface of the Al particles to form LiAl-containing particles. The method provided herein improves the safety and processability of electrode manufacturing and the performance of the manufactured electrode and the battery including such electrode.

[0128] Manufacturing of Al-containing films

[0129] Al-containing film

[0130] Al-containing films can be manufactured using Al powder via wet casting. This involves preparing an aluminum powder slurry well dispersed with a suitable binder and solvent, casting the slurry onto a substrate using techniques such as doctor blade or tape casting, and then carefully drying the film to form a continuous layer. After applying post-processing steps such as sintering to improve film properties, the quality can be verified through comprehensive characterization. In this process, it is necessary to precisely control formulation, casting, and heat treatment parameters to produce high-quality aluminum films suitable for additional applications.

[0131] Powder preparation and slurry formulation

[0132] First, high-purity aluminum powder is selected to ensure that the particle size distribution is suitable for forming a dense film. Next, the aluminum powder is mixed with a suitable solvent (often water or an organic solvent) and a binder system. The binder serves to hold the powder particles together after drying. Dispersants or surfactants may also be added to improve the homogeneity of the slurry and prevent the aggregation of aluminum particles. This mixture is vigorously stirred, sometimes with the help of ultrasonic stirring or a high-shear mixer, to ensure that the aluminum powder is well dispersed throughout the solvent, thereby obtaining a stable and uniform slurry.

[0133] Adjustment of rheological properties

[0134] The viscosity of the slurry is important for the subsequent casting process. It can be adjusted by controlling the concentrations of the aluminum powder, binder, and solvent. If necessary, additional rheological modifiers can be introduced to achieve a viscosity that is low enough to spread smoothly during casting yet high enough to prevent particle settling. Optimizing these parameters ensures that the slurry can be cast into a film of uniform thickness.

[0135] Casting process

[0136] Once the slurry is prepared and its rheological properties are optimized, the wet casting process begins. A common method for producing films is the doctor blade technique. In this method, the slurry is deposited onto a substrate (often a smooth, non-stick surface or carrier foil), and a doctor blade is used to spread the slurry evenly over the substrate to a controlled thickness. The gap between the doctor blade and the substrate is carefully set to achieve the desired film thickness. Depending on the scale of the film and the desired characteristics, alternative casting methods such as slot die coating or tape casting may also be used.

[0137] dry

[0138] After casting, the wet film is dried. Drying is an important step as it must uniformly remove the solvent without causing cracks or non-uniformity in the film. The drying process can be performed under conditions where temperature and humidity are controlled. In some cases, the film may be passed through a drying oven or a controlled environment chamber to ensure that the solvent evaporates at a constant rate, leaving a solid film of aluminum powder bonded by a polymer matrix.

[0139] Post-processing

[0140] Additional post-processing steps may be required. If a more conductive or mechanically rigid film is required, the dried film may undergo sintering (a thermal process that fuses aluminum particles together). The sintering temperature is carefully selected to promote neck formation between particles without melting the binder or causing oxidation of the aluminum. In some cases, a reducing atmosphere (such as a forming gas or a mixture of hydrogen and nitrogen) may be used during sintering to minimize the formation of aluminum oxide. Alternatively, other compaction techniques, such as hot pressing, may be applied to improve film density and mechanical properties.

[0141] Al powder particle size

[0142] The particle size of Al powder directly affects the uniformity, density, and electrochemical performance of the final electrode. Selecting an appropriate particle size ensures good packing density, smooth film formation, and efficient lithium diffusion during alloying. Fine aluminum powders with particle sizes up to 5 µm, such as 0.1 to 5 µm, provide a high surface area, which improves sintering and facilitates lithium diffusion. However, these ultrafine particles are highly reactive and prone to oxidation, requiring careful handling and processing in an inert atmosphere. Medium-sized aluminum powders, typically ranging in size from 5 to 20 µm, offer a balance between packing density and processability. They can be a practical choice for electrode fabrication as they reduce the risk of excessive oxidation while maintaining film uniformity. Coarser aluminum powders, in the range of 20 to 50 µm, which is larger than 20 µm, improve the mechanical strength of the film but result in a lower surface area available for lithiation, which can potentially affect alloying efficiency.

[0143] Controlled particle size distribution

[0144] Achieving optimal balance often involves the use of a controlled particle size distribution. A bimodal or multimodal size distribution combining small particles in the range of 1 to 5 µm and large particles of about 10 to 20 µm can improve film compaction and uniformity while maintaining appropriate lithium diffusion pathways. Since uncontrolled size variations can lead to surface roughness and defects that affect lithium penetration and alloying kinetics, the selection of particle size also affects the smoothness of the film.

[0145] Selection of particle size

[0146] By combining careful selection of particle size with optimized processing conditions, it is ensured that the final Al-Li alloy cathode meets the performance requirements necessary for high-efficiency all-solid-state battery applications. Al powder in the range of 5 to 20 µm may be selected because it provides a good compromise between smooth film formation, efficient lithium alloying, and manufacturability. For example, the Al powder may have a particle size of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 µm, or about that µm. In an embodiment, the Al powder may have a particle size within a range formed by selecting any two figures provided herein, such as about 5 to about 10, about 10 to about 15, about 15 to about 20, about 8 to about 18 µm, etc. In other embodiments, Al powder with a particle size of less than 5 μm and / or greater than 20 μm may also be selected. For example, the Al powder may have a particle size of 0.01, 0.1, 1, 2, 3, 4, 21, 22, 23, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65 μm, etc. In an embodiment, the Al powder may have a particle size within a range formed by selecting any two values ​​provided herein, such as, for example, about 0.01 to about 1, about 2 to about 5, about 20 to about 30, about 50 to about 60 μm, etc.

[0147] bookbinder

[0148] The binder must facilitate the formation of a continuous and uniform Al film. It must promote good adhesion between aluminum particles and between the film and the casting substrate to ensure that the film as cast exhibits the mechanical integrity required for subsequent handling and processing. The binder must be chemically inert to both the aluminum powder and any other additives in the slurry. Furthermore, the binder must not introduce contaminants that could interfere with the subsequent lithiation process or the formation of a uniform Li-Al alloy. The binder and any residues must be compatible with the solid electrolyte environment and must not leave residues that are detrimental to ion conductivity or residues capable of reacting with the solid electrolyte material.

[0149] Binder material

[0150] The binder may be one or more polymers such as polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyimide (PI), carboxymethyl cellulose (CMC), succinonitrile-based polymers, styrene-butadiene rubber (SBR), polyethylene glycol (PEG), polyvinyl acetate (PVAc), polyurethane (PU), polyacrylic acid (PAA), ionic polymers, gel polymers, hydroxypropyl methylcellulose, methyl cellulose, starch, modified starch, and acrylic emulsion polymers. For example, PVA is frequently used due to its excellent film-forming properties and water solubility. CMC provides good viscosity control and dispersion of aluminum particles. Cellulose derivatives such as hydroxypropyl methylcellulose and methyl cellulose are valuable due to their film-forming ability and are generally biodegradable. Starch and modified starch are environmentally friendly. Acrylic emulsion polymers can be designed for good adhesion and film integrity. They are commonly selected for applications where robust mechanical properties are required for the film as cast. PVAc provides strong adhesion and film formation. Certain formulations of PU binders can provide flexibility and adhesion while degrading under controlled conditions.

[0151] Conventional ideas regarding binder removal

[0152] The binder must not only facilitate uniform film casting but also be capable of efficiently lithiating aluminum during alloy formation. In many cases, the binder must be decomposed or removed during post-processing (such as sintering or lithiation) to ensure that residual carbon or impurities do not adversely affect the electrochemical performance of the Li-Al alloy cathode. Conventionally, it is considered advantageous to use a binder that burns cleanly under controlled thermal conditions, as any remaining residue can affect lithium diffusion into the aluminum matrix, thereby impacting phase formation and electrode performance.

[0153] The amazing effect of binder retention

[0154] However, surprisingly, it was discovered that retaining a binder in the Al-containing film to fabricate the cathode layer in the method provided herein has unexpected advantages. The binder plays a decisive role in determining the uniformity, surface smoothness, and loading density of the Al-containing film, which is essential for fabricating high-performance Al-Li alloy cathodes for all-solid-state batteries. The selection and optimization of the binder directly affect how well the aluminum powder is dispersed within the slurry, how smoothly the film spreads during casting, and how evenly the film dries, all of which are important for securing a dense and uniform Al film suitable for subsequent lithiation.

[0155] Improvement of film uniformity and surface smoothness

[0156] One of the primary functions of a binder in wet casting is to facilitate the formation of a continuous and defect-free film. A well-formulated binder system ensures that aluminum particles are homogeneously distributed throughout the slurry, preventing aggregation or sedimentation that could lead to a rough or uneven surface. During the drying stage, the binder helps reduce the formation of surface defects such as cracks, voids, or ridges by controlling the solvent evaporation rate. Binders with appropriate rheological properties, such as PVA or CMC, act as stabilizers to prevent uneven shrinkage when the film dries. By maintaining uniform viscosity and providing consistent adhesion between particles, the binder minimizes localized density variations that could cause topographical irregularities on the film surface. Additionally, the binder contributes to the fluidity of the slurry during casting. Binders that provide shear-thinning behavior, such as methylcellulose or PAA, allow the slurry to spread smoothly under shear forces, while maintaining stability once the film is deposited. As a result, a uniform and smooth film is formed, ensuring consistent lithium diffusion and alloying in the subsequent lithiation process.

[0157] Control of Al loading density

[0158] The aluminum loading density of the Al-containing film is another important factor affecting the performance of the Al-Li alloy cathode. The solid content of the slurry can be precisely controlled by a binder system with well-adjusted viscosity and dispersion characteristics, which determines the final aluminum mass per unit area of ​​the film. If the binder concentration is too low, aluminum particles may precipitate or be unevenly redistributed, resulting in non-uniform film thickness and inconsistent lithiation behavior. Conversely, if the binder content is excessively high, excessive porosity may occur or hinder sintering, which may reduce the overall density of the aluminum film.

[0159] Optimization of formulations

[0160] By carefully selecting binders with customized molecular weights and functional groups, formulations can be optimized to achieve a balance of film flexibility, particle adhesion, and loading control. Water-soluble binders such as PVA or CMC can fine-tune viscosity, ensuring that the slurry maintains a proper balance between spreadability and structural integrity.

[0161] Effect on Al-Li alloy formation

[0162] Well-structured Al films with smooth surfaces and controlled density significantly enhance the formation of uniform Al-Li alloy cathodes. If the aluminum film is too porous or uneven, lithium infiltration during alloying becomes inconsistent, which can lead to localized phase changes and non-uniform electrochemical performance. A denser and more evenly packed aluminum film ensures that lithium diffusion occurs in a controlled and predictable manner, thereby guaranteeing the formation of a stable Li-Al alloy with minimal resistance and optimal mechanical properties.

[0163] Effects of binders

[0164] The binder ensures that the final film has a smooth surface and optimal loading density by promoting uniform dispersion, controlling drying behavior, and fine-tuning slurry viscosity. This consequently enhances lithium alloying kinetics, improves cycling stability, and contributes to the overall electrochemical performance of the all-solid-state battery. Therefore, carefully selecting and optimizing the binder system is essential for achieving high-performance Al-Li alloy anodes. Additionally, the binder system can be optimized using additives or mixed with dispersants to improve the homogeneity of the aluminum slurry. Casting process parameters (e.g., drying temperature and time) and subsequent post-casting treatments (e.g., sintering in a reducing atmosphere) must be adjusted to match the thermal decomposition characteristics of the selected binder.

[0165] menstruum

[0166] The solvent ensures the proper dispersion of Al powder, binder solubility, and smooth film formation. The solvent must be carefully selected based on evaporation rate, compatibility with the binder, and the ability to produce a uniform and defect-free film.

[0167] aqueous solvents

[0168] Aqueous solvents, such as deionized water, are environmentally friendly and non-toxic, making them a common choice when used with water-soluble binders such as polyvinyl alcohol (PVA) or carboxymethyl cellulose (CMC). Ethanol-water and isopropanol-water mixtures are sometimes used to maintain good dispersion of solid components while reducing surface tension and improving drying behavior.

[0169] Alcohol-based solvents

[0170] Alcohol-based solvents, including ethanol, isopropanol, and methanol, exhibit rapid evaporation and good dispersibility. Ethanol and isopropanol are widely used due to their relatively low toxicity and effective drying properties, whereas methanol is less common due to its high toxicity. Butanol, with its slow drying rate, can help control film formation and reduce defects caused by rapid solvent evaporation.

[0171] ketone-based solvents

[0172] Ketone-based solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone provide good solubility for many binders. Since acetone evaporates very quickly, film defects may occur if not properly controlled, whereas MEK and cyclohexanone have a slower evaporation rate, which can improve film uniformity.

[0173] ester-based solvents

[0174] Ester solvents such as ethyl acetate and butyl acetate are commonly used in coatings due to their low toxicity and good film-forming properties. While ethyl acetate evaporates quickly, butyl acetate evaporates slowly, reducing the risk of film shrinkage and cracking. Propylene glycol monomethyl ether acetate (PGMEA) is another widely used ester solvent known for producing smooth and uniform films.

[0175] Glycol ether

[0176] Glycol ethers, including ethylene glycol, propylene glycol, diethylene glycol monomethyl ether (DEGME), and triethylene glycol monomethyl ether (TEGME), have high boiling points and slow evaporation rates, which can be advantageous for maintaining a uniform film thickness and preventing premature drying. These solvents help improve dispersion and enable formulations with high solid content.

[0177] Aromatic and hydrocarbon solvents

[0178] Aromatic and hydrocarbon solvents such as toluene, xylene, n-hexane, and n-heptane are sometimes used due to their strong dissolving power. Toluene and xylene are effective in dissolving many polymer binders, but their use is limited due to their toxicity. Non-polar hexane and heptane are useful for dispersing hydrophobic components, but caution is required during handling due to their flammability.

[0179] Chlorinated solvent

[0180] Chlorinated solvents such as dichloromethane (DCM) and chloroform have strong dissolving power but are rarely used due to high toxicity and environmental concerns. However, they may be considered for special applications requiring strong solvent action.

[0181] Ionic liquid solvents and supercritical fluids

[0182] Ionic liquid solvents such as 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM-BF4) and 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) are being explored due to their non-volatility and high thermal stability. Although these solvents are expensive, they offer unique advantages in specialized formulations. Additionally, supercritical fluids such as supercritical carbon dioxide (CO2) are being studied for solvent-free deposition methods for ultrathin film applications.

[0183] Selection of the optimal solvent

[0184] For manufacturing aluminum films for use in Li-Al alloy cathodes, aqueous solvents such as deionized water or ethanol-water mixtures are often preferred due to their low toxicity and high environmental safety. However, organic solvents such as ethanol, isopropanol, acetone, or MEK (Methyl Ethyl Ketone) may also be selected when better drying control and compatibility with specific binders are required. The optimal solvent selection depends on balancing evaporation rate, film uniformity, and process safety to ensure the fabrication of high-quality electrodes.

[0185] Dispersants and / or surfactants

[0186] Dispersants and / or surfactants stabilize aluminum (Al) powder in solvent systems. These additives help prevent particle aggregation, improve dispersion uniformity, and ensure smooth film formation. The choice depends on the solvent, binder system, and desired film characteristics, including loading density and surface smoothness.

[0187] polymer dispersant

[0188] Polymeric dispersants such as polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and polyacrylic acid (PAA) are widely used due to their ability to adsorb onto particle surfaces and provide steric stabilization. PVP is particularly effective in both aqueous and organic solvents, ensuring a well-dispersed suspension. While PEG exhibits excellent solubility and compatibility with various solvent systems, PAA is commonly used in aqueous formulations to improve dispersion stability.

[0189] Anionic dispersant

[0190] Anionic dispersants, including ammonium polyacrylate, sodium dodecyl sulfate (SDS), and sodium polyphosphate, prevent aggregation by improving the electrostatic repulsion between Al particles. Ammonium polyacrylate is commonly used in aqueous systems because it provides strong charge stabilization. SDS is a well-known surfactant that improves dispersion by reducing surface tension, but it can cause unwanted foaming. Sodium polyphosphate acts as a dispersant by breaking down particle clusters and improving the homogeneity of the suspension.

[0191] cationic dispersant

[0192] Cationic dispersants such as cetyltrimethylammonium bromide (CTAB) and polyethyleneimine (PEI) function to stabilize dispersions by adsorbing onto negatively charged surfaces and altering the zeta potential. While CTAB is effective in organic systems, PEI binds strongly to metal particles to promote better film uniformity. However, their use must be carefully controlled, as excessive cationic surfactants can lead to particle aggregation instead of dispersion.

[0193] Nonionic surfactants

[0194] Nonionic surfactants, including Triton X-100, Tween 80, and Pluronic block copolymers, help reduce surface tension and stabilize suspensions without causing electrostatic interactions. Triton X-100 is widely used to improve wettability and prevent aggregation in organic and aqueous systems. The biocompatible Tween 80 is commonly chosen for environmentally friendly formulations. Pluronic surfactants, composed of polyethylene oxide (PEO) and polypropylene oxide (PPO), provide both steric stabilization and viscosity control in dispersions.

[0195] low molecular weight dispersant

[0196] Low molecular weight dispersants such as citric acid, oleic acid, and stearic acid improve particle dispersion by modifying surface interactions. Citric acid is particularly effective in aqueous systems because it binds to metal surfaces to enhance electrostatic repulsion. Long-chain fatty acids such as oleic acid and stearic acid are more suitable for non-polar solvent systems, as they prevent particle aggregation by providing particle hindrance.

[0197] Inorganic dispersant

[0198] In some cases, inorganic dispersants including phosphoric acid, silane coupling agents, and alumina coating additives are used to improve dispersion by modifying particle surfaces. Phosphoric acid enhances charge stabilization, particularly in acidic aqueous environments. Silane coupling agents promote film integrity by improving the adhesion between Al particles and polymer binders. Alumina coating additives help reduce excessive particle deposition during processing by controlling surface interactions.

[0199] Selection of optimal dispersant or surfactant

[0200] The optimal selection of dispersants or surfactants depends on the solvent system, binder compatibility, and desired film properties. In aqueous systems, polyacrylic acid, ammonium polyacrylate, and citric acid are commonly used due to their strong dispersion effects. In organic solvents, polyvinylpyrrolidone, oleic acid, and Triton X-100 provide effective dispersion while maintaining film smoothness. To obtain a denser and more homogeneous aluminum film by further improving particle distribution, polyethylene glycol (PEG) or sodium polyacrylate can be incorporated. The careful selection and optimization of these additives ensure uniform particle distribution, prevent aggregation, and contribute to the overall performance of all-solid-state battery electrodes.

[0201] Al powder content

[0202] In the slurry, a high solid content loading is typically targeted to achieve a dense and uniform film while maintaining workable rheological properties. Aluminum powder typically constitutes about 60 to about 80 wt% of the total weight of the slurry. The slurry may contain Al powder in amounts such as 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, or 80 wt%. In the embodiments, the weight percentage of Al powder in the slurry may be within a range formed by selecting any two figures provided herein, such as about 60 to about 70, about 65 to about 75, about 70 to about 80, about 66 to about 77 wt%, etc. This high percentage helps ensure that the final film has the necessary density and conductivity required for efficient alloy formation. In other embodiments, the aluminum powder may constitute less than about 60 wt% or more than about 80 wt% of the total weight of the slurry, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 85, 90, or 95 wt%, etc. In the embodiments, the weight percentage of Al powder in the slurry may be within a range formed by selecting any two figures provided herein, such as about 20 to about 30, about 45 to about 55, about 85 to about 80, about 85 to about 90, about 40 to about 70, about 75 to about 85 wt%, etc.

[0203] Binder content

[0204] A binder, which is important for providing mechanical cohesion and assisting in film formation, is typically incorporated at a level of about 0.1 to about 10 wt% of the total slurry. The slurry may contain the binder in amounts such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 wt%. In the embodiments, the weight percentage of the binder in the slurry may be within a range formed by selecting any two figures provided herein, such as about 3 to about 5, about 4 to about 8, about 5 to about 7, about 6 to about 10 wt%, etc. The slurry may also contain a binder in amounts of less than about 0.1 wt% or more than 10 wt%, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 wt%, etc. In the embodiments, the weight percentage of the binder in the slurry may be within a range formed by selecting any two figures provided herein, such as about 0.03 to about 0.05, about 0.04 to about 0.08, about 0.05 to about 0.07, about 1 to about 20, about 5 to about 15, about 12 to about 18 wt%, etc. The precise amount depends on the molecular properties of the binder and its efficiency in promoting particle adhesion; for highly effective binders, a low percentage may be sufficient, whereas for formulations requiring higher film strength, the upper limit of that range may be used.

[0205] Solvent content

[0206] The solvent, which is essential for dispersing both the aluminum powder and the binder, typically constitutes the remainder of the composition. In practice, the solvent content may range from about 10 to about 40% by weight of the total slurry, but in many processes, the total solid loading (aluminum, binder, and any other additives) is targeted to be 60 to 80%. The slurry may contain the solvent in amounts such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40 wt%. The slurry may also contain solvent in amounts of less than about 10 wt% or more than about 40 wt%, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 wt%, etc. In the embodiments, the weight percentage of the binder in the slurry may be within a range formed by selecting any two figures provided herein, such as about 10 to about 25, about 15 to about 30, about 30 to about 35, about 30 to about 40, about 5 to about 9, about 40 to about 45, about 45 to about 50 wt%, etc. This parameter is often adjusted based on desired viscosity and drying characteristics with the aim of achieving a smooth and uniform film without defects or excessive porosity.

[0207] Dispersant or surfactant content

[0208] Optional dispersants or surfactants added to improve particle dispersion and stabilize the suspension are generally used in much smaller amounts. Typically, these additives are incorporated in an amount of about 0.5 to about 2 wt% relative to the aluminum powder, for example, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2 wt% relative to the weight of the Al powder. The weight percentage of these additives relative to the total weight of Al powder may be less than 0.5 wt% or greater than 2 wt%, such as 0.01, 0.05, 0.1, 0.2, 0.3, 0.4, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 4, 5 wt%, etc. In the embodiments, the weight percentage of these additives relative to the total weight of the Al powder may be within a range formed by selecting any two values ​​provided herein, such as about 0.5 to about 1.5, about 1 to about 1.8, about 0.6 to about 1.2, about 1.5 to about 2, about 0.01 to about 0.1, about 0.2 to about 0.3, about 2.1 to about 2.4, about 2.5 to about 3, about 4 to about 5 wt%, etc. Even a small change in this percentage can have a significant effect on the homogeneity of the slurry and, consequently, affect the quality of the final film.

[0209] Low-shear mixture

[0210] When preparing the slurry, proper mixing ensures the uniform dispersion of aluminum powder, binder, and any additives such as dispersants or surfactants. One common approach is to start with a low-shear mixing process. In this initial step, the binder is dissolved in a selected solvent to create a homogeneous solution. This step can be performed using a magnetic or mechanical stirrer set to a low speed, which ensures that the binder is completely dissolved without causing significant air ingress. Once the binder solution is prepared, the aluminum powder is slowly added to the mixture. It is important to add the powder slowly while continuously stirring to prevent clumping and ensure that the binder solution evenly coats each particle.

[0211] High-shear mixture

[0212] After initial mixing, the slurry often benefits from high-shear mixing. High-shear mixers or homogenizers can be used to further disperse aluminum particles and break down any aggregates that may have formed during initial mixing. This process involves applying strong mechanical force to the slurry, which can help reduce particle size distribution and improve the overall homogeneity of the mixture. In some cases, this process is supported by ultrasonic treatment, which applies ultrasound to the slurry to promote de-aggregation and achieve much finer dispersion. Ultrasound is particularly effective at breaking down large particle clusters, ensuring that the aluminum is uniformly distributed throughout the binder solution.

[0213] Temperature control

[0214] In addition to mechanical mixing and ultrasonic treatment, maintaining appropriate temperature control during the mixing process can also be beneficial. Slightly warming the slurry lowers the viscosity of the binder solution, which can promote better mixing and dispersion of aluminum particles. However, the temperature must be carefully controlled to avoid premature evaporation of the solvent or degradation of the binder. Furthermore, this process may include a recirculation or resting period after high-shear mixing to allow any introduced bubbles to escape and secure a more stable and homogeneous slurry.

[0215] controlled mixing

[0216] Overall, a slurry with uniformly distributed components is obtained through a combination of low-shear initial mixing, high-shear homogenization, ultrasonic treatment if necessary, and controlled temperature conditions. By carefully controlling the mixing process in this way, a high-quality aluminum film with desired mechanical and electrochemical properties is produced for use in the fabrication of Li-Al alloy cathodes for all-solid-state batteries.

[0217] Thickness of Al-containing film

[0218] The Al-containing film may have a thickness of about 0.1 to about 100 μm, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 μm. The Al-containing film may have a thickness of less than 0.1 μm or more than 100 μm, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 115, 120, 125, 130, 140, 150, 160, 170, 180, 190, 200 μm, etc. In an embodiment, the thickness of the Li foil may be within a range formed by any two values ​​selected from the values ​​provided herein, such as about 0.1 to about 1, about 0.5 to about 2, about 1 to about 5, about 5 to about 10, about 20 to about 60, about 30 to about 50, about 50 to about 80, about 40 to about 90 μm, about 0.01 to about 0.05 μm, about 0.05 to about 0.09 μm, about 105 to about 110 μm, about 0.05 to about 0.5 μm, about 50 to about 150 μm, about 150 to about 200 μm, etc.

[0219] Formation of alloys

[0220] Li foil

[0221] A Li foil is provided on the top of the current collector. The Li foil may have a thickness of about 0.1 to about 100 μm, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 μm. The Li foil may have a thickness of less than 0.1 μm or more than 100 μm, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 115, 120, 125, 130, 140, 150, 160, 170, 180, 190, 200 μm, etc. In an embodiment, the thickness of the Li foil may be within a range formed by any two values ​​selected from the figures provided herein, such as about 0.1 to about 1, about 0.5 to about 2, about 1 to about 5, about 5 to about 10 μm, about 20 to about 60, about 30 to about 50, about 50 to about 80, about 40 to about 90 μm, about 0.01 to about 0.05 μm, about 0.05 to about 0.09 μm, about 105 to about 110 μm, about 0.05 to about 0.5 μm, about 50 to about 150 μm, about 150 to about 200 μm, etc. The current collector is described in detail in the “Other Aspects” section below.

[0222] Lamination of Al-containing film and Li foil

[0223] An Al-containing film is laminated onto a Li foil. As illustrated in FIG. 1, the Al-containing film (11) has a surface (12), and the Li foil (20) has a surface (21). The Li foil (20) can be placed on top of a conductive substrate, such as copper, or a current collector (30), and the Al-containing film (11) is laminated onto the Li foil (20). As a result, the surface (11) of the Al-containing film (11) comes into contact with the surface (21) of the Li foil (20).

[0224] Sandwich composition

[0225] Alternatively, as illustrated in FIG. 2, the Li foil may be laminated in a "sandwich" configuration between two Al-containing films. In this configuration, the first Al-containing film (51) is laminated with the first conductive substrate (41), and the second Al-containing film (52) is laminated with the second conductive substrate (42). The Li foil is laminated between the first Al-containing film (51) and the second Al-containing film (52).

[0226] Al loading amount

[0227] Al loading refers to the amount of aluminum incorporated into the electrode. This is typically expressed as mass per unit area (e.g., mg / cm²). 2 It is quantified as a percentage of the total electrode composition or as a metric. Al content is an important parameter affecting the electrochemical performance, mechanical properties, and compatibility with the solid electrolyte of the electrode. In some embodiments, the Al loading amount is 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, or 7.6 mg / cm² 2 Such as, about 5 to about 7.6 mg / cm² 2 It may be within the range. The Al loading amount in this range is approximately 5 to approximately 7.5 mAh / cm² 2Electrodes with an area capacitance within the range can be produced. The Al loading amount is also 1, 1.5, 2, 2.5, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, or 8.5 mg / cm² 2 Such as, about 5 mg / cm² 2 Less than or about 7.6 mg / cm² 2 It may exceed. In the embodiments, the Al loading amount is about 4.5 to about 5, about 5 to about 5.5, about 6 to about 7, about 5.5 to about 6.5, about 6.8 to about 8.5 mg / cm² 2 It may be within the range formed by selecting any two values ​​provided here, such as the back.

[0228] Lithium insertion and extraction

[0229] One of the main roles of aluminum in Li-Al alloy electrodes is to act as an active material that undergoes reversible alloying and dealloying reactions with lithium during charge-discharge cycles. LiAl and Li x The formation of lithium-aluminum alloys, such as Al, enables lithium storage and contributes to battery capacity. However, the amount of aluminum must be carefully controlled to ensure the efficient insertion and extraction of lithium without compromising electrode stability.

[0230] Electron and ion conductivity of electrodes

[0231] The electronic and ionic conductivity of the electrode also depend on the Al loading amount. While increasing the aluminum content improves lithium storage capacity, excessive Al loading reduces the electrical conductivity of the electrode, potentially slowing down charge transport. Additionally, high Al content causes significant volume expansion during lithiation, which can induce mechanical stress and lead to structural degradation over multiple cycles.

[0232] Optimization of AI loading amount

[0233] In the case of all-solid-state batteries, where the electrode-electrolyte interface plays a critical role in battery performance, optimizing the Al loading is particularly important. To ensure efficient ion transport, the electrode must maintain close contact with the solid electrolyte. If the Al loading is too high, interfacial delamination can occur due to electrode expansion, leading to increased resistance and a decrease in overall battery efficiency. Therefore, fine-tuning the Al content and electrode thickness is essential to strike a balance between capacity, conductivity, and mechanical stability.

[0234] Processing pressure

[0235] Al-containing film(s) and Li foil are 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 211, 220, 225, 230, 235, 240, 245, 250, 255, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, 340, It can be pressurized under a pressure of about 100 to about 500 MPa, such as 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 405, 410, 415, 420, 425, 430, 435, 440, 445, 450, 455, 460, 465, 470, 475, 480, 485, 490, 495, or 500 MPa. The Al-containing film(s) and Li foil may also be pressurized under a pressure of less than 100 MPa or greater than 500 MPa, such as 50, 60, 70, 80, 90, 500, 550, 600, 650, 700, 750 MPa, etc. In an embodiment, the pressure may be within a range formed by any two values ​​selected from the values ​​provided herein, such as about 100 to about 200, about 150 to about 200, about 200 to about 350, about 125 to about 400, about 300 to about 500, about 50 to about 100, about 70 to about 120, about 450 to about 550, about 500 to about 750, about 350 to about 550 MPa, etc.

[0236] pressurized temperature

[0237] Al-containing film(s) and Li foil are 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, It can be pressurized at a temperature of about 20 to about 150°C, such as 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, or 150°C. The Al-containing film(s) and Li foil may be pressurized at temperatures below about 20°C or above 150°C, such as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 165, 170, 175, 180, 185, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300°C, etc.In an embodiment, the temperature may be within a range formed by any two values ​​selected from the values ​​provided herein, such as about 20 to about 40, about 50 to about 100, about 100 to about 120, about 60 to about 140, about 70 to about 90, about 15 to about 20, about 150 to about 200, about 125 to about 175, about 100 to about 300°C, etc.

[0238] Pressurization time

[0239] Al-containing film(s) and Li foil for a time of about 5 to about 50 minutes, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, or 60 minutes The Al-containing film(s) and Li foil may be pressurized. The Al-containing film(s) and Li foil may be pressurized for a time of less than 5 minutes or more than 60 minutes, such as 1, 2, 3, 4, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150 minutes, etc. In an embodiment, the time may be within a range formed by any two values ​​selected from the values ​​provided herein, such as about 5 minutes to about 40 minutes, about 50 minutes to about 60 minutes, about 10 minutes to about 20 minutes, about 20 minutes to about 40 minutes, about 30 minutes to about 60 minutes, about 1 minute to about 10 minutes, about 40 minutes to about 60 minutes, about 30 minutes to about 60 minutes, about 60 minutes to about 120 minutes, etc.

[0240] Calendaring

[0241] As illustrated in FIG. 2, the pressurization of Al-containing film(s) and Li foils can be achieved by calendering. Calendering is a process in which a material (often in the form of a sheet or roll) is passed through a series of rollers to compress and shape it, thereby improving its overall properties. In the context of battery manufacturing, calendering is used to compress an electrode coating on a current collector, such as forming a LiAl alloy negative electrode on a Cu current collector by the method provided herein, in order to reduce porosity and improve particle contact within the electrode. This compression increases the density of the electrode, which is important for improving electrical conductivity and energy density. Calendering ensures consistent performance by achieving a uniform thickness and microstructure across the electrode through precise control of pressure and sometimes temperature.

[0242] Isostatic Pressing

[0243] In the calendering process, pressurization is an isotropic pressing that applies uniform pressure in all directions to the Al-containing film(s) and Li foil to compress them into a dense solid LiAl alloy cathode. Depending on the material and desired properties, this technique may be performed at room temperature (known as cold isotropic pressing (CIP)) or at high temperatures (known as hot isotropic pressing (HIP)). In both cases, defects are minimized and uniform density is achieved by the process, which is important for improving the mechanical strength and overall performance of the final product.

[0244] Overview of the Alloying Process

[0245] When an Al-containing film and a Li foil are pressurized together, mechanical deformation begins at the interface, creating defects that function as diffusion channels. Then, lithium atoms migrate to the aluminum lattice through interstitial regions and defect pathways, causing the intermetallic Li-Al phase to nucleate and grow. This atomic interdiffusion process transforms the interface into a homogeneous alloy layer, which is essential for achieving desired electrochemical properties in all-solid-state battery electrodes.

[0246] Initiation of alloy formation

[0247] Specifically, when an Al-containing film and a Li foil are pressurized together, a series of atomic-scale movements are initiated, ultimately leading to interdiffusion and the formation of a new intermetallic phase. Initially, both the Al-containing film and the Li foil consist of their respective pure metal crystal lattices. When pressed together, the applied mechanical force causes the surfaces to come into extremely close contact, overcoming surface roughness and inducing local deformation. This close contact is accompanied by lattice distortion, the generation of dislocations, and voids at the interface. These defects function as rapid diffusion pathways by lowering the energy barrier for atomic movement, thereby laying the groundwork for alloy formation.

[0248] Li diffusion

[0249] At the atomic level, lithium atoms are smaller than aluminum atoms and possess higher inherent mobility, so they begin to diffuse from the Li foil into the Al-containing film. This diffusion is driven by the concentration gradient present at the interface and is enhanced by the increase in chemical potential caused by the applied pressure. Under these conditions, Li atoms leave their original lattice positions within the Li foil and migrate into the aluminum lattice through interstitial regions and along defect paths created by the pressurization process. They can also displace aluminum atoms within the lattice, thereby gradually altering the local structure of the Al film.

[0250] Alloying reaction

[0251] When lithium atoms accumulate within the aluminum matrix, they interact with surrounding aluminum atoms to induce the nucleation of intermetallic compounds. This initial nucleation is thermodynamically favorable because, under high-pressure conditions, the formation of Li-Al alloys reduces the total free energy of the system compared to isolated pure metals. As diffusion continues, the intermetallic phase grows outward from the interface. The growing alloy layer gradually adopts a characteristic crystal structure (often characteristic of phases such as LiAl), forming a transition zone that changes from a sharp interface to a more uniform alloy region.

[0252] Reaching equilibrium

[0253] Due to the high mobility of lithium, lithium diffusion is dominant; however, some aluminum atoms can diffuse to a lesser extent toward the lithium-rich side of the interface because they have larger atomic sizes and lower diffusivity. Over time, as the diffusion process progresses and the concentration gradient decreases, the system approaches a relatively uniform equilibrium state in terms of the composition and structure of the newly formed Li-Al alloy. This homogeneous intermetallic layer is critical to the performance of the electrode because it promotes consistent electrochemical behavior and mechanical stability.

[0254] cathode

[0255] One embodiment of the present disclosure is a cathode as illustrated in FIGS. 1 and 2, manufactured by the method provided herein. This cathode has a current collector and a cathode active material layer. Details regarding the current collector are provided in the “Other Embodiments” section below. As shown in FIGS. 3 and 4, the cathode active material layer comprises a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (hereinafter “LiAl-containing particles”). The cathode active material layer has a first surface (A) and a second surface (B). Al particles may be present on the first surface (A), and Li metal may be present on the second surface (B). As illustrated in FIG. 4, particles near the first surface (A), such as particles (1-3), are less lithiated than particles near the second surface (B), such as particles (4-7), and generally have a round shape. Conversely, particles close to the second surface (B), such as particles (4-7), are more lithiated than particles close to the first surface (A), such as particles (1-3), have a less rounded shape, and are generally smaller than particles with less lithiation. Additionally, molecules of the polymer binder are generally distributed throughout the cathode. It is understood that binder molecules such as 8-11 shown in FIG. 4 are merely exemplary binder molecules, and that there may be more binder molecules not shown in FIG. 4. At least a portion of the polymer molecules are interposed between two adjacent LiAl-containing particles within the cathode active material layer to create a mechanically rigid and electrochemically active composite suitable for high-performance all-solid-state battery applications. FIG. 3 is an SEM image of a cross-section of an exemplary LiAl alloy formed using the method provided herein, showing a gradient from a light gray low-lithiated region to a dark gray high-lithiated region and black non-lithiated Li metal residue.

[0256] Areas with low lithiation

[0257] LiAl-containing particles around or near the first surface (A) of the cathode layer are characterized by having a low lithium content, a large size, and a generally round shape. This region suggests that the lithiation process is less advanced or intentionally relaxed, allowing the particles to maintain a more isotropic spherical morphology.

[0258] Li content gradient

[0259] As one moves from the first surface (A) toward the second surface (B), a distinct gradient is observed in the morphology within the cathode active material layer. Along the direction (D) from the first surface (A) toward the second surface (B) within the cathode active material layer, there is a general tendency for the amount of lithium in these particles to increase. LiAl-containing particles located near the first surface (A), such as particles (1-3), have a low amount of lithium, whereas particles located closer to the second surface (B), such as particles (4-7), tend to contain more lithium. This suggests that as the LiAl-containing particles are located closer to the second surface (B), lithium accumulates more significantly within the LiAl-containing particles. The gradual increase in the lithium content within the LiAl-containing particles indicates that lithiation has occurred more extensively. The extent to which lithium increases along this direction may be influenced by factors such as lithium diffusion kinetics, electrochemical reactions, and material properties within the cathode. The overall trend shows that the lithium content increases as it moves toward the second surface (B), but there may be local variations in the lithium distribution due to factors such as differences in particle structure, reaction kinetics, or potential non-uniformity of lithium diffusion. However, despite these potential variations, the overall pattern remains unchanged. That is, LiAl-containing particles tend to store gradually more lithium as they are located deeper within the cathode active material layer and closer to the second surface (B).

[0260] Particle size gradient

[0261] At the same time, as the location of the LiAl-containing particles moves deeper into the negative electrode active material layer, the particle size tends to decrease. The average diameter or volume of individual LiAl-containing particles decreases as they are located closer to the second surface (B). That is, LiAl-containing particles near the first surface (A), such as particles (1-3), are relatively large, whereas particles found near the second surface (B), which is deeper in the negative electrode active material layer, such as particles (4-7), tend to be smaller in size. This suggests that the LiAl-containing particles gradually decompose as they move toward the second surface. The decrease in particle size may be due to processes such as particle fragmentation or dissolution-reprecipitation accompanying the enhanced incorporation of lithium. While the overall trend shows a decrease in particle size toward the second surface (B), there may be local variations due to material heterogeneity or processing conditions. However, despite these potential variations, a general pattern is maintained. That is, the LiAl-containing particles tend to become larger near the first surface (A) and gradually decrease in size as they approach the second surface (B) along the direction (D) within the cathode active material layer.

[0262] Particle shape gradient

[0263] As the size decreases, the particle shape changes from an initial shape that is generally rounded elliptical or similar to a less rounded and much more irregular geometry with sharp edges. Along the direction (D) toward the second surface (B), the LiAl-containing particles generally become less rounded in shape. This means that particles closer to the first surface (A), such as particles (1-3), are typically more spherical, rounded, or elliptical, whereas particles located closer to the second surface (B) tend to have more irregular, elongated, or angular shapes. The phrase "less rounded" refers to a deviation from an ideal spherical, elliptical, or smooth shape, indicating that LiAl-containing particles closer to the second surface (B) are more distorted, rough, or uneven compared to particles closer to the first surface (A). Some particles closer to the second surface (B), such as particles (4-7), may have irregular shapes and some may have sharp edges. This trend suggests that as the lithium concentration increases, anisotropic structural changes in the particles are induced, which may be caused by differences in growth rates due to specific crystallographic orientation or mechanical stress induced during lithiation. While the overall trend implies a decrease in roundness, there may be localized variations where some particles maintain a more rounded shape depending on their specific location or exposure to lithium or lithiation. However, despite these potential changes, a broader pattern is maintained. That is, as the LiAl-containing particles move deeper into the cathode active material layer and closer to the second surface (B), they gradually become less rounded.

[0264] "Generally"

[0265] In this context, the term "generally" is used to refer to an overall trend or pattern that applies to most materials, although local variations or exceptions may exist. For example, if it is stated that the amount of lithium in LiAl-containing particles generally increases from one surface to the other, this implies that while most particles follow this trend, there may be a few that do not exactly match it. Similarly, if it is stated that particle size generally decreases or particle shape generally changes from round or elliptical to less round, this implies that these are the dominant behaviors observed across most of the layer. Therefore, the use of "generally" conveys that the described trend does not represent an absolute and uniform variation for each individual particle, but rather a typical and characteristic trend for the entire system.

[0266] Binder distribution

[0267] A polymer binder forms a continuous network across the entire cathode layer to envelop the particles, ensuring strong adhesion and electrical contact throughout the layer. The molecules of the polymer binder are generally uniformly intermingled, with at least a portion of the molecules interposed between two adjacent LiAl-containing particles. The LiAl-containing particles can come into at least partial contact with the binder. This close association helps maintain a cohesive composite structure, facilitates electron and ion transport between particles, and minimizes the formation of isolated or poorly connected regions. The binder not only provides mechanical support but also contributes to improving overall electrode performance by distributing the active material more uniformly.

[0268] Binder Network

[0269] The polymer binder in the cathode layer is not merely an inert filler but an essential component that defines the structural and functional integrity of the composite. By controlling the distribution of the polymer binder throughout the layer so that it is present at almost or all interfaces between at least some of the LiAl-containing particles, continuous electrical connectivity and mechanical cohesion can be ensured. Once the slurry is cast and the alloy / composite is formed, binder molecules can penetrate into the inter-particle spaces. This creates a network that maintains the overall structure, minimizes microcracks, and supports efficient ion transport across the electrode.

[0270] Encapsulation

[0271] In the region near the first surface (A) of the negative electrode active material layer, the LiAl-containing particles are larger, have lower lithium content, and exhibit a more rounded shape, allowing the binder to form a relatively thicker layer around each particle. This robust encapsulation helps stabilize the large particles, ensuring that the particles maintain good contact with each other regardless of particle size. As a result, the binder absorbs mechanical stress and provides a buffering effect that mitigates the risk of delamination during electrode handling and operation.

[0272] Interwoven Network

[0273] As the binder moves toward the second surface (B), which is smaller, has a higher lithium content, and has a less rounded shape, the binder can be distributed as a finer and more closely intertwined network penetrating the complex contours of the irregularly shaped particles. This fine distribution is essential to fill the gap volume increased by the small particles and sharp edges and to ensure that there are no isolated regions within the electrode. The presence of the binder at these interfaces not only fixes the particles together but also promotes a more uniform electrochemical reaction by maintaining consistent ion and electron pathways.

[0274] continuity

[0275] Overall continuity of binder distribution can be achieved through the manufacturing process. Slurry formulations, mixing, and / or casting conditions can be optimized to promote continuous dispersion of the binder along with LiAl-containing particles. Even as particle characteristics change along a gradient from larger, more rounded or elliptical particles to smaller, less rounded particles, the binder adapts to these changes and maintains a state of proximity to or contact with the particle surfaces. This continuous and adaptive distribution of the binder is fundamental to maintaining the mechanical resilience of the cathode layer, ensuring efficient lithiation / delithiation cycles, and ultimately improving the performance and lifespan of the all-solid-state battery.

[0276] Binder mechanics

[0277] During the pressurization and alloying process, the binder exhibits dynamic behavior to accommodate the changing morphology of the LiAl-containing particles. Initially, when the cathode is formed, the binder is uniformly dispersed throughout the composite, surrounding larger and rounder LiAl-containing particles or interposed between two adjacent LiAl-containing particles near the first surface. When pressure is applied, due to the viscoelastic properties of the binder, it flows and conforms along the surface of the particles, filling the gap spaces and establishing strong mechanical and electrical connections.

[0278] Binder redistribution

[0279] As the alloying process progresses and lithium diffuses into the aluminum, the morphology of the LiAl-containing particles begins to change. In regions closer to the second surface, where lithiation is more extensive, the particle size decreases, and the particle shape changes from a generally smooth, round or elliptical geometry to a less rounded geometry. Under the influence of applied pressure and associated mechanical stress, the binder continuously redistributes itself to maintain proximity or contact with the newly formed particle surface. The molecular chains of the binder are stretched, reoriented, and / or reflowed into smaller and more complex voids that form as the particle shape changes, thereby minimizing potential discontinuities in the negative electrode active material layer.

[0280] Dynamic adjustment

[0281] This dynamic adjustment is achieved through a combination of capillary forces, stress-induced flow, and the binder's inherent tendency to minimize surface energy. The binder adapts to increasing particle irregularities by maintaining a continuous phase that penetrates fine gaps and envelops even the smallest, sharp-edged particles. This not only ensures mechanical cohesion across the gradient but also preserves the electrical and ionic pathways essential for effective cell operation.

[0282] Securing Morphology

[0283] Furthermore, the reconfigured distribution of the binder can be further stabilized by any thermal or chemical effects, such as slight hardening or crosslinking, during the pressurization and alloying processes. This "locking in" of the binder arrangement helps secure a gradient morphology, ensuring that the cathode active material layer remains robust even under subsequent cycling and operating stresses.

[0284] Effects of binders

[0285] In summary, the binder dynamically adapts to the gradient of the cathode active material layer by flowing, redistributing, and conforming according to changing particle size and shape, thereby ensuring a continuous, connected, mechanically resilient, and electrochemically efficient Li-Al alloy cathode electrode for all-solid-state batteries.

[0286] Li:Al molar ratio

[0287] LiAl-containing particles include 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or 5, etc. The same may have a Li:Al molar ratio of about 0.1 to about 5. The Li:Al molar ratio may also be less than about 0.1 or greater than about 5, such as 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 7, 8, 9, 10, etc. In an embodiment, the molar ratio may be within a range formed by selecting any two values ​​provided herein, such as about 0.5 to about 1, about 0.5 to about 1.5, about 0.1 to about 2, about 1 to about 5, about 0.01 to about 0.05, about 2.5 to about 7, about 5 to about 10, about 0.7 to about 1.2, etc.

[0288] All-solid-state battery and method of manufacturing and use thereof

[0289] All-solid-state battery

[0290] One embodiment of the present disclosure is an all-solid-state battery comprising a cathode, an anode provided in the present disclosure, and a solid electrolyte positioned between the anode and the cathode and configured to enable the transport of lithium ions between the anode and the cathode. More details regarding the all-solid-state battery are provided in the “Other Aspects” section below.

[0291] Method for manufacturing a battery

[0292] Another aspect of the present disclosure is a method for manufacturing an all-solid-state battery provided herein. A positive electrode, a solid electrolyte, and a negative electrode can be pressed to form a compressed cell, and the compressed cell can be sealed in a pouch material to form a pouch.

[0293] Battery manufacturing process

[0294] Specifically, the anode, solid electrolyte, and the cathode provided herein are carefully stacked in the desired order to ensure proper alignment. This stacking is typically performed in an inert atmosphere to prevent contamination or oxidation, particularly of sensitive materials such as lithium metal. Once the layers of components are assembled, the entire stack can be placed in a die or mold designed to accommodate the material and maintain alignment during compression. A plunger, typically part of a uniaxial hydraulic or mechanical press, can be used to apply uniform and controlled pressure across the stack. The plunger moves steadily downward until the assembly reaches a predetermined pressure level. This pressurizing action brings the layers into close contact, reducing gaps, voids, or interfacial defects that could increase resistance and hinder ion transport. The applied pressure not only improves physical contact at the interface but also helps the layers align by slightly deforming the surfaces or causing them to interlock. By maintaining this pressure for a set residence time, the material can settle into a stable configuration with minimized interfacial resistance. In some manufacturing processes, following this pressurization step, additional treatments such as thermal annealing further strengthen the bonding between layers and optimize the microstructure of the electrolyte or electrode material.

[0295] In Situ Process

[0296] Alternatively, an in-situ process may be adopted, in which the alloy cathode layer is manufactured simultaneously with the battery. In this in-situ process, a sandwich assembly of a Cu substrate-Al-containing film-Li foil-Al-containing film-Cu substrate, as provided herein and illustrated in FIG. 2b, replaces the cathode already formed in the process described above. When a plunger applies uniform and controlled pressure to the stack, close contact between the layers is enhanced. This pressurization step performs several key functions. First, it minimizes gaps or voids between the lithium foil and the Al-containing film, which is critical for securing effective ion and electron pathways across the interface. Second, the applied pressure induces the diffusion of lithium atoms from the lithium foil into the aluminum film. Under these conditions, lithium gradually interdiflates with aluminum to form a Li-Al alloy directly at the interface. This in-situ alloy formation not only produces a more uniform cathode layer but also improves the mechanical and electrochemical integration between the electrode and the solid electrolyte.

[0297] Optimization

[0298] The process can be further optimized by carefully controlling the residence time and pressure during pressurization, and subsequent heat treatment may be applied in some cases. This heat treatment step enhances the kinetics of lithium diffusion into aluminum, which can lead to the formation of a more complete and uniform Li-Al alloy. By creating the cathode in situ, this method avoids potential problems associated with handling pre-alloyed electrodes, such as interfacial mismatch or inhomogeneity, and ultimately contributes to the development of all-solid-state batteries with reduced internal resistance and improved cycling stability.

[0299] enter

[0300] The applied pressure is 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 305, 310, 315, 320, 325, 330, 335, It may be about 100 to about 500 MPa, such as 340, 345, 350, 355, 360, 365, 370, 375, 380, 385, 390, 395, 400, 405, 410, 415, 420, 425, 430, 435, 440, 445, 450, 455, 460, 465, 470, 475, 480, 485, 490, 495, or 500 MPa. The applied pressure may be less than about 100 MPa or greater than 500 MPa, such as 50, 60, 70, 80, 90, 550, 600, 650, 700, or 750 MPa. In an embodiment, the pressure may be within a range formed by selecting any two values ​​provided herein, such as about 100 to about 200, about 125 to about 400, about 200 to about 300, about 250 to about 450, about 50 to about 100, about 80 to about 250, about 450 to about 650, about 500 to about 750 MPa, etc.

[0301] Manufacturing of pouch cells

[0302] A pouch cell can be manufactured. A stack of a positive electrode layer, a solid electrolyte layer, and a negative electrode layer can be placed between two flexible current collector foils that serve as the external electrical contacts of the cell. Next, the entire assembly is inserted into a pouch cell case, which is typically made of an impermeable polymer film such as aluminum-laminated polyethylene terephthalate (PET) or a similar barrier material. Mechanical lamination or pressurization steps can be performed, and a plunger or hydraulic press can be used to apply uniform pressure across the entire stack. Once the layers are fully pressurized together, the pouch cell is sealed using heat sealing or ultrasonic welding techniques. The sealing process must be performed under controlled conditions to prevent any moisture or oxygen from penetrating the cell, as moisture or oxygen can decompose sensitive materials such as lithium or solid electrolytes. Finally, the assembled pouch cell can undergo a formation process involving initial charge-discharge cycles. This step helps stabilize the interfaces and effectively mitigate any minor defects in the contact or uniformity of the layers through in-situ electrochemical reactions. After formation, a series of quality control tests, typically such as impedance spectroscopy and cycling tests, are performed on the pouch cell to verify whether the internal interface is stable and whether the cell meets performance specifications.

[0303] Further details are provided in the "Other Modes" section below.

[0304] Other modes

[0305] The following provides other aspects of the present disclosure. Additional features, embodiments, and examples discussed below may be applied to the various aspects of the invention discussed above. However, in the event of a conflict between the information in the foregoing discussion and the information in the following discussion, the information in the foregoing section shall apply.

[0306] solid-state lithium-ion battery

[0307] Solid-state batteries can be charged and discharged multiple times. An all-solid-state battery comprises a positive electrode and a negative electrode, and an electrolyte that allows lithium ions to move between the electrodes. In contrast to conventional liquid electrolyte batteries, all-solid-state batteries do not contain a fluid liquid. When a circuit is formed between the electrodes, electricity flows between them. During charging of a lithium-ion rechargeable battery, lithium ions are released from the positive electrode and absorbed into the active material of the negative electrode. During discharging of a lithium-ion rechargeable battery, lithium ions are released from the negative electrode and absorbed into the active material of the positive electrode. Lithium ions transfer energy as they move back and forth between the electrodes.

[0308] Solid-state battery composition

[0309] The present disclosure provides an all-solid-state battery (100) comprising a positive electrode (102), a negative electrode (104), and a solid electrolyte layer (106) located between the positive electrode (102) and the negative electrode (104). Although listed as examples, the all-solid-state battery (100) does not require all of these components. For example, in some configurations, such as an anodeless system, the negative electrode (104) may be omitted.

[0310] Random additional layer

[0311] The solid battery (100) may optionally include additional layers or layers such as, for example, a separator layer, a protective layer, a suppression layer, a solid electrolyte interface layer, or a combination thereof.

[0312] protective layer

[0313] For example, a protective layer may be integrated between the electrodes (102 and 104) and the solid electrolyte layer (106). The protective layer may serve to improve the overall cycle life and safety of the battery by mitigating dendrite formation, particularly on the negative electrode side.

[0314] protective layer material

[0315] This protective layer may include materials such as lithium phosphate, lithium titanate, or lithium lanthanum zirconium oxide (LLZO), which can help prevent undesirable side reactions at the electrode-electrolyte interface.

[0316] Separator layer

[0317] Some components of the solid-state battery (100) may also include a separator layer. These separator layers can provide additional mechanical support to the battery structure while still enabling efficient ion transport. The separator layer may also be designed to have a gradient structure with characteristics optimized for contact with both the positive and negative electrodes.

[0318] Separator layer material

[0319] Traditional liquid electrolyte batteries often use porous polymer separator layers, but all-solid-state batteries can employ thin ceramic or glass-ceramic layers as separators. For this purpose, materials such as LLZO, LATP (lithium aluminum titanium phosphate), or LAGP (lithium aluminum germanium phosphate) can be used.

[0320] Solid-state battery cell

[0321] FIG. 5 is a drawing illustrating a cell (101) of an all-solid-state battery (100) according to one embodiment. The cell (101) includes a positive electrode (102), a negative electrode (104), and a solid electrolyte layer (106) located between the positive electrode (102) and the negative electrode (104). The cell (101) may optionally include additional layers or layers, such as, for example, a separator layer, a protective layer, a suppression layer, a solid electrolyte interface layer, or a combination thereof.

[0322] Cell composition

[0323] As illustrated in FIG. 5, the all-solid-state battery (100) may include a single cell (101). In other examples, the all-solid-state battery (100) may include a plurality of cells, such as at least two cells, at least three cells, or at least four cells. Connecting the cells in series increases the voltage of the all-solid-state battery (100), and connecting the cells in parallel increases the ampere-hour capacity of the all-solid-state battery (100).

[0324] Cell dimensions

[0325] The cell (101) may have a width (w1), a length (l1), and a thickness (t1).

[0326] Cell thickness

[0327] The thickness (t1) of the cell (101) is approximately 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 3000, 4000, 5000 μm, or any other figure between any two exemplary figures listed herein, or any figure in the range of about 100 μm to about 5000 μm. In some embodiments, the thickness (t1) of the cell (101) may be within a range formed by selecting any two figures within the range of about 100 μm to about 5000 μm, for example, between about 100 μm and about 5,000 μm or between about 100 μm and about 1,000 μm.

[0328] Width aspect ratio

[0329] The width (w1) of the cell (101) can be substantially larger than the thickness (t1) of the cell (101). In some embodiments, the aspect ratio of width (w1) to thickness (t1) is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, at least 260, at least 270, at least 280, at least 290, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550, at least 600, at least 650, at least 700, at least 750, at least It may be 800, at least 850, at least 900, at least 950, at least 1000, at least 2000, at least 3000, at least 4000, at least 5000, at least 6000, at least 7000, at least 8000, at least 9000, or at least 10000.

[0330] Aspect ratio of length

[0331] The length (l1) of the cell (101) can be substantially larger than the thickness (t1) of the cell (101). In some embodiments, the aspect ratio of length (l1) to thickness (t1) is at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 70, at least 80, at least 90, at least 100, at least 110, at least 120, at least 130, at least 140, at least 150, at least 160, at least 170, at least 180, at least 190, at least 200, at least 210, at least 220, at least 230, at least 240, at least 250, at least 260, at least 270, at least 280, at least 290, at least 300, at least 350, at least 400, at least 450, at least 500, at least 550, at least 600, at least 650, at least 700, at least 750, at least It may be 800, at least 850, at least 900, at least 950, at least 1000, at least 2000, at least 3000, at least 4000, at least 5000, at least 6000, at least 7000, at least 8000, at least 9000, or at least 10000.

[0332] anode

[0333] The positive electrode (102) is associated with one polarity (e.g., the positive electrode) of the all-solid-state battery (100). The positive electrode (102) is configured as the positive electrode during the discharge of the all-solid-state battery (100). The positive electrode (102) is suitable for lithium ion diffusion between the current collector (108) and the solid electrolyte layer (106). The positive electrode (102) is electrically connected to the current collector (108).

[0334] Positioning of the positive electrode

[0335] In one embodiment, the positive electrode (102) is formed on the current collector (108) and is in direct contact with the current collector (108). In another embodiment, another functional layer may be interposed between the positive electrode (102) and the current collector (108).

[0336] materials for the anode

[0337] The anode (102) may be capable of reversibly absorbing and releasing lithium ions. For example, the anode (102) may include an anode active material, conductive carbon, a solid electrolyte material, a binder, etc., or a combination thereof. Optionally, the anode (102) may further include additives such as, for example, an oxidation stabilizer, a reduction stabilizer, a flame retardant, a heat stabilizer, an antifogging agent, a thickener, etc., or a combination thereof.

[0338] Examples of additives

[0339] Examples of these additives may include butylated hydroxyanisole (BHA) or butylated hydroxytoluene (BHT) as an oxidation stabilizer, ascorbic acid or sodium sulfite as a reduction stabilizer, aluminum hydroxide or magnesium hydroxide as a flame retardant, phenolic compounds or phosphites as heat stabilizers, polyethylene glycol or silica nanoparticles as antifogging agents, and carboxymethyl cellulose (CMC) or xanthan gum as a thickener.

[0340] positive electrode active material

[0341] The cathode active material is lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), Li[Ni a Co b Mn c M 1 d ]O2(here M 1 is any element selected from the group consisting of Al, Ga, In, or combinations thereof, and 0.3≤a<1.0, 0≤b≤0.5, 0≤c≤0.5, 0≤d≤0.1, and a+b+c+d=1), Li(Li e M 2 f-e-f M 3 f' )O 2-g A g (where 0≤e≤0.2, 0.6≤f≤1, 0≤f'≤0.2, 0≤g≤0.2, and M 2comprises Mn, and at least one element selected from the group consisting of Ni, Co, Fe, Cr, V, Cu, Zn, and Ti, and M 3 is at least one element selected from the group consisting of Al, Mg, and B, and A is at least one element selected from the group consisting of P, F, S, and N), or a compound substituted with one or more transition metals; Li 1+h Mn 2-h Lithium manganese oxide, such as LiMnO3, LiMn2O3, LiMnO2, etc., represented by the chemical formula O4 (where 0 ≤ h ≤ 0.33); lithium copper oxide (Li2CuO2); vanadium oxide such as LiV3O8, V2O5, or Cu2V2O7; LiNi 1-i M 4 i O2(here M 4 Ni-site type lithium nickel oxide represented by the chemical formula =Co, Mn, Al, Cu, Fe, Mg, B, or Ga, where 0.01≤y≤0.3; LiMn 2-j M 5 j O2(here M 5 =Co, Ni, Fe, Cr, Zn, or Ta, and 0.01≤y≤0.1) or Li2Mn3M 6 O8(here M 6 Lithium manganese complex oxide represented by the chemical formula (=Fe, Co, Ni, Cu or Zn); LiMn2O4 in which Li is partially substituted with alkaline earth metal ions; disulfide compounds; LiFe3O4, Fe2(MoO4)3; etc.; or a combination thereof may be included.

[0342] Phosphate-based materials

[0343] In addition to the aforementioned cathode active material, other types of materials may be included in the cathode. For example, lithium iron phosphate (LiFePO4) can be used as the cathode active material due to its excellent thermal stability and long cycle life. Lithium manganese iron phosphate (LiMnx Fe 1-x Other phosphate-based materials such as PO4 or lithium cobalt phosphate (LiCoPO4) may also be suitable.

[0344] Layered oxide materials

[0345] The cathode active material is also Li(Ni 1-x-y Co x Mn y )O2(NCM) or Li(Ni 1-x-y Co x Al y It may include layered oxide materials having various compositions such as )O2 (NCA), wherein the ratios of Ni, Co, Mn, and Al can be adjusted to optimize performance characteristics. For example, to achieve higher energy density, NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 NCM materials with a high nickel content, such as O2), can be used. In some cases, the cathode active material may be LiNi, which can provide high-voltage operation. 0.5 Mn 1.5 It may include a spinel structure such as O4. Alternatively, materials with a taborite structure such as LiFeSO4F or LiVPO4F may be adopted for the possibility of high energy density and good thermal stability.

[0346] Composite or blended cathode materials

[0347] Composite or blended cathode materials combining more than one type of active material may also be used. For example, a blend of layered oxide and spinel material may be adopted to balance energy density and power performance. As another example, lithium iron phosphate may be blended with one or more of the above-mentioned cathode active materials. In some embodiments, the cathode active material may include a surface-modified version of the aforementioned compound, wherein the surface modification is aimed at improving stability, conductivity, or other performance indicators.

[0348] Emerging Classes of Materials

[0349] The cathode active material may also include novel materials such as disordered rock salt structures (e.g., Li3NbO4-based materials) or high-entropy oxides, which can provide a desirable combination of high capacity and structural stability. In some cases, the electrochemical properties of the cathode active material can be further tuned by incorporating dopants or substituent elements.

[0350] Particulate Nature of Positive Electrode Active Material

[0351] The positive active material can be in the form of particles. The cathode active material is about 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 5 ㎛, 10 ㎛, 15 ㎛, 20 ㎛, 25 ㎛, 30 ㎛, 35 ㎛, 40 ㎛, 45 ㎛, 50 ㎛, 55 ㎛, 60 ㎛, 65 ㎛, 70 ㎛, 75 ㎛, 80 ㎛, 85 ㎛, 90 ㎛, 95 ㎛, 100 ㎛, 110 ㎛, 120 ㎛, 130 µm, 140 µm, 150 µm, 160 µm, 170 µm, 180 µm, 190 µm, 200 µm, 210 µm, 220 µm, 230 µm, 240 µm, 250 µm, 260 µm, 270 µm, 280 µm, 290 µm, 300 µm, 310 µm, 320 µm, 330 µm, 340 µm, 350 µm, 360 µm, 370 µm, 380 µm, 390 µm, 400 µm, 410 µm, 420 µm, 430 µm, 440 µm, 450 µm, 460 µm, 470 µm, 480 µm, 490 µm, 500 µm, 550 µm, 600 µm, 650 µm, 700 µm, 750 µm, 800 µm, 850 µm, 900 µm, 950 µm, 1,000 µm,Alternatively, it may have a particle size in the range of about 1 nm to about 1,000 µm, such as any other figure between the two exemplary figures listed herein. In an embodiment, the particle size of the positive active material may be within the range formed by selecting any two figures in the range of about 1 nm to about 1,000 µm, for example, between about 10 nm and about 1,000 µm. The gaps between the positive active material particles in the positive electrode (102) may be filled with a solid electrolyte material.

[0352] Amount of positive active material of the positive electrode

[0353] The amount of positive active material of the solid-state battery (100) affects the charge / discharge capacity of the all-solid-state battery (100). To manufacture a high-capacity positive electrode (102), a high level of positive active material may be included in the positive electrode (102). For example, the positive electrode (102) may include 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 98, or 99 wt%, about that wt%, or more than that wt% of positive active material based on the total weight of the positive electrode (102), or may include any other wt% of positive active material between any two values ​​(wt%) listed herein. In an embodiment, the positive active material of the positive electrode (102) may be within a range formed by selecting any two values ​​within the range of greater than 0 to about 100 wt%, for example, between about 40 wt% and about 98 wt%.

[0354] Positive electrode conductive material

[0355] The conductive material of the positive electrode (102) is not particularly limited as long as it is conductive without causing chemical changes in the all-solid-state battery (100). For example, the conductive material may include graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black or thermal black; conductive fibers such as carbon fibers or metal fibers; carbon nanotubes (CNT) including both single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT); metal powders such as fluorocarbon, aluminum or nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide; conductive polymers such as polyphenylene derivatives; or a combination thereof.

[0356] Amount of positive electrode conductive material

[0357] The anode (102) comprises a conductive material such as 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt% based on the total weight of the anode (102). In an embodiment, the conductive material of the anode (102) may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, between about 1 wt% and about 30 wt%.

[0358] Binder material

[0359] The binder may include various types of binder polymers, such as, for example, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, polymers thereof in which hydrogen atoms are substituted with Li, Na, or Ca, various copolymers thereof, or combinations thereof.

[0360] Other binder materials

[0361] In addition to the binder materials described above, other types of binder materials may be used in the anode to improve the performance and stability of the anode. For example, water-soluble binders such as sodium alginate, gelatin, or polyacrylamide may be used to improve the environmental friendliness of the electrode manufacturing process. These binders can also provide advantages in terms of the flexibility and adhesive strength of the electrode. In some cases, conductive binders such as poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) or polyaniline (PANI) may be used to simultaneously improve the mechanical integrity and electrical conductivity of the electrode.

[0362] New Binder System

[0363] Novel binder systems, such as self-healing polymers or supramolecular assemblies, can be incorporated to improve the long-term stability and cycle life of the battery. Additionally, the mechanical, thermal, and electrochemical properties of the electrode can be customized by using composite binders that combine multiple polymers or incorporate inorganic nanoparticles. In some embodiments, bio-derived or biodegradable binders, such as cellulose derivatives or chitosan, may be employed to reduce the environmental impact of battery production and disposal.

[0364] Amount of anode binder

[0365] The anode (102) may contain a binder such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 wt% based on the total weight of the anode (102). In an embodiment, the binder in the anode (102) may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, between about 1 wt% and about 30 wt%.

[0366] solid electrolyte materials

[0367] The solid electrolyte material of the anode (102) may be configured to be the same as the material for the solid electrolyte layer (106) discussed below. The solid electrolyte material of the anode (102) may be the same as or different from the material for the solid electrolyte layer (106).

[0368] Amount of solid electrolyte material of the anode

[0369] The anode (102) may comprise about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 wt% of solid electrolyte material based on the total weight of the anode (102). In an embodiment, the amount of solid electrolyte material of the anode (102) may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, between about 1 wt% and about 30 wt%.

[0370] Thickness of the anode

[0371] The thickness (t2) of the anode (102) is 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, Any number in the range greater than 0 to 1000 μm, such as 980, 990, or 1,000 μm, or about that number, or any other number between any two exemplary numbers listed herein. In an embodiment, the thickness (t2) of the anode (102) may be within a range formed by selecting any two numbers in the range greater than 0 to about 1000 μm, for example, between about 10 μm and about 1,000 μm.

[0372] Porosity of the anode

[0373] The porosity of the anode (102) may be any value in the range of 0 to 20 vol%, such as 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 vol%, or any other vol% within the range of 0 to 20 vol%, based on the total volume of the anode (102). In an embodiment, the porosity of the anode (102) may be within a range formed by selecting any two values ​​within the range of 0 to 20 vol%, for example, between 0 vol% and about 18 vol%.

[0374] Lithium ion diffusion of the anode

[0375] The positive electrode (102) is 1 x 10 -14 cm 2 / s, 1 x 10 -13 cm 2 / s, 1 x 10 -12 cm 2 / s, 1 x 10 -11 cm 2 / s, 1 x 10 -10 cm 2 / s, 1 x 10 -9 cm 2 / s, 1 x 10 -8 cm 2 / s or 1 x 10 -7 cm 2 Like / s, greater than 0 to 1 x 10 -7 cm 2 Any number in the range / s or about that number, or greater than 0 to 1 x 10 -7 cm 2 It may include any other value of lithium ion diffusivity within the range of / s. In an embodiment, the lithium ion diffusivity of the anode (102) is greater than 0 to 1 x 10 -7 cm 2 It can be within a range formed by selecting any two numbers within the / s range, for example, 1 x 10 -14 cm 2 / s and about 1 x 10 -7 cm 2 It can be between / s

[0376] Current collectors of both poles

[0377] The current collector (108) collects electrical energy generated from the positive electrode (102) and supports the positive electrode (102).

[0378] Materials for positive electrode current collectors

[0379] The material of the current collector (108) is not particularly limited as long as it enables close contact with the positive electrode (102), has suitable electrical conductivity, and does not cause significant chemical changes in the all-solid-state battery (100) within the voltage range of the all-solid-state battery (100). For example, the current collector (108) may be made of or include various materials such as metal, conductive carbon, or conductive ceramic, but is not limited thereto. The metal of the current collector (108) may include one or more selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, iron, iron alloy (e.g., steel, stainless steel), silver, silver alloy, gold, platinum, palladium, chromium, molybdenum, tungsten, tantalum, niobium, zirconium, vanadium, manganese, cobalt, indium, tin, lead, bismuth, or combinations thereof, but is not limited thereto.

[0380] Geometric structure of the entire house

[0381] The current collector (108) may also be configured with various other geometric shapes to optimize its performance and integration with the anode (102), and may be sized to fit specific form factors such as pouch, cylindrical and / or prismatic form factors.

[0382] Shape of the positive and negative current collectors

[0383] By forming fine surface irregularities on the surface of the current collector (108), the adhesion between the anode (102) and the current collector (108) can be increased. The current collector (108) may have various shapes, such as, for example, a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven web, or a combination thereof.

[0384] Examples of the shape and size of the entire house

[0385] For example, the current collector (108) may be structured as a mesh or grid that can provide enhanced mechanical support while maintaining a high surface area for electrode contact. In some embodiments, the current collector (108) may be designed in a corrugated or wavy pattern that potentially increases the contact area with the anode material and improves overall conductivity. Additionally, the current collector (108) may be fabricated as a perforated sheet that enables better electrolyte penetration and ion transport. In certain cases, the current collector (108) may be formed as a three-dimensional structure such as an interconnected fiber network or a honeycomb configuration, which can improve the structural integrity of the electrode assembly while facilitating efficient current collection.

[0386] Thickness of the positive current collector

[0387] The thickness (t3) of the entire house (108) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, Any number in the range greater than 0 to 500 μm, such as 440, 450, 460, 470, 480, 490, or 500 μm, or about that number, or any other number between any two exemplary numbers listed herein. In an embodiment, the thickness (t3) of the current collector (108) may be within the range formed by selecting any two numbers in the range greater than 0 to 500 μm, for example, between about 5 μm and about 500 μm.

[0388] Method for manufacturing an anode

[0389] The positive electrode (102) can be obtained in various ways.

[0390] Dry powder coating process

[0391] For example, a dry powder coating process may be employed in which a negative electrode active material, a conductive additive, and a binder are mixed in a dry state and then applied directly to a current collector (108) using electrostatic deposition or mechanical compression. This method can reduce environmental impact by reducing the use of solvents.

[0392] 3D printing

[0393] In some cases, the anode (102) can be fabricated using additive manufacturing technology such as 3D printing. This approach allows for precise control of the electrode structure and porosity, which can potentially improve the performance and energy density of the electrode. Depending on the specific material and desired electrode properties, various 3D printing methods may be used, including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW).

[0394] Electrospinning

[0395] Another method for manufacturing the anode (102) may involve electrospinning. In this process, a solution containing a cathode active material, a conductive additive, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be collected directly onto a current collector (108) to form a highly porous electrode structure with an increased surface area.

[0396] Tape casting

[0397] In some embodiments, the anode (102) may be prepared using a tape casting method. This technique involves spreading a slurry of electrode material onto a carrier film using a doctor blade, followed by drying and calendering. The resulting electrode tape can then be laminated onto a current collector (108).

[0398] Spray coating

[0399] Alternatively, the anode (102) can be manufactured using spray coating technology. In this method, a fine mist of electrode slurry is sprayed onto the current collector (108) using compressed air or ultrasonic spraying. This approach can produce a thin and uniform electrode layer and can be particularly useful for large-scale production.

[0400] Freeze-casting

[0401] In certain cases, the anode (102) can be prepared using a freeze casting method. This process involves freezing a slurry of electrode material and then sublimating the ice to create a porous structure. Then, the obtained porous electrode can be sintered and attached to a current collector (108).

[0402] Sol-gel process

[0403] For some applications, the anode (102) may be prepared using a sol-gel process. This method involves forming a colloidal suspension (sol) and then converting it into a gel-like network containing the anode active material and other components. This gel can be applied to a current collector (108) and then heat-treated to form a final electrode structure.

[0404] Slurry-based process

[0405] For example, a positive active material can be mixed and stirred with a solvent, and optionally a binder, a conductive material, and a dispersant to form a slurry. Then, the slurry can be applied (e.g., coated) to a current collector (108), and then pressed and dried to obtain a positive electrode (102).

[0406] Method for applying anode slurry

[0407] The application of the slurry for the anode (102) may include using a technology selected from the group consisting of slot die coating, gravure coating, spin coating, spray coating, roll coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, Toppan printing, intaglio printing, offset printing, etc., and combinations thereof.

[0408] Double layer slot die coating

[0409] In some embodiments, the anode (102) may be fabricated using double-layer slot die coating (DLD) technology. This method involves applying two distinct layers of electrode material to the current collector (108) simultaneously in a single pass. The DLD process creates a gradient structure within the electrode, which can potentially optimize both the electrochemical performance and mechanical properties of the anode. Additionally, this technology may incorporate a functional intermediate layer or protective coating as part of the electrode manufacturing process, which can potentially improve overall battery performance and lifespan.

[0410] Solvent for anode slurry

[0411] The solvent for forming the anode (102) may include water and / or organic solvents such as, for example, N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, dimethylacetamide, dimethyl sulfoxide (DMSO), isopropyl alcohol, etc., or a combination thereof. The solvent may be used in an amount sufficient to dissolve and disperse electrode components such as the anode active material, binder, and conductive material, taking into account the slurry coating thickness, production yield, etc., or a combination thereof. Additional solvents that may be used include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0412] Solvent-free method

[0413] In some embodiments of the present disclosure, the anode (102) may be prepared using a solvent-free method, such as dry powder processing or melt extrusion, which can reduce the use of liquid solvents and provide environmental and cost advantages.

[0414] Dispersant for anode slurry

[0415] The dispersant forming the anode (102) may include an aqueous dispersant and / or an organic dispersant such as, for example, N-methyl-2-pyrrolidone. Other possible dispersants may include various surfactants such as polyvinylpyrrolidone (PVP), carboxymethyl cellulose (CMC), sodium dodecyl sulfate (SDS), Triton X-100, polyethylene glycol (PEG), polyacrylic acid (PAA), and polysorbate or poloxamer.

[0416] Drying technology for anode slurry

[0417] The slurry for the anode (102) can be dried by irradiating it with heat, an electron beam (E-beam), gamma rays, or ultraviolet rays (G, H, I-rays), or a combination thereof, to vaporize the solvent. For example, the slurry can be vacuum dried at room temperature. In the drying step, the solvent is removed through evaporation, but other components remain intact without evaporating to form the anode (102).

[0418] Additional drying technology

[0419] In addition to the drying technique described above, the anode (102) can be dried using other methods such as infrared (IR) drying, microwave drying, or freeze drying.

[0420] Combination of drying technologies

[0421] In some embodiments, a combination of drying techniques, such as using vacuum drying after convection heating, may be employed to optimize the drying process and ensure complete solvent removal while maintaining the integrity of the electrode structure.

[0422] Cathode general

[0423] The negative electrode (104) is associated with one polarity (e.g., negative electrode) of the all-solid-state battery (100) that is different from the polarity of the positive electrode (102). The negative electrode (104) is configured as a negative electrode during the discharge of the all-solid-state battery (100). The negative electrode (104) is suitable for lithium ion diffusion between the current collector (110) and the solid electrolyte layer (106).

[0424] Positioning of the cathode

[0425] The negative electrode (104) is electrically connected to the current collector (110). In an embodiment, the negative electrode (104) is formed on the current collector (110) and is in direct contact with the current collector (110). In another embodiment, another functional layer may be interposed between the negative electrode (104) and the current collector (110).

[0426] Cathode-free system

[0427] As described above, in some embodiments, the all-solid-state battery (100) may utilize a cathode-free system. In this configuration, the cathode (104) may be omitted, and lithium metal may be deposited directly onto the current collector (110) during charging. This approach may potentially increase the energy density of the battery and eliminate the need for a separate cathode material, while potentially reducing the overall thickness of the battery structure.

[0428] cathode materials

[0429] The negative electrode (104) may be capable of reversibly absorbing and releasing lithium ions. For example, the negative electrode (104) may include a negative electrode active material, a binder, etc., or a combination thereof.

[0430] Cathode additive

[0431] Optionally, the cathode (104) may further include additives such as, for example, an oxidation stabilizer (e.g., butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate, tert-butylhydroquinone), a reduction stabilizer (e.g., ascorbic acid, sodium sulfite, erythorbic acid, sodium metabisulfite), a flame retardant (e.g., aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine cyanurate), a heat or light stabilizer (e.g., a UV absorber such as a phenol compound, a phosphite, a hindered amine light stabilizer, benzophenone or benzotriazole), an anti-fogging agent (e.g., polyethylene glycol, silica nanoparticles, glycerol, sorbitol), a thickener (e.g., carboxymethyl cellulose, xanthan gum), or a combination thereof.

[0432] Other additives for cathodes

[0433] Additionally, conductive additives such as carbon black, graphene, or carbon nanotubes may be incorporated to improve electrical conductivity, and binder modifiers such as styrene-butadiene rubber or polyacrylic acid may be used to improve adhesion and mechanical stability. Functional additives such as fluoroethylene carbonate or vinylene carbonate may also be included to promote the formation of a stable solid electrolyte interface layer on the cathode surface.

[0434] materials for cathode active materials

[0435] The negative electrode active material is made of or includes various materials such as, for example, alkali metals, alkaline earth metals, Group 3B metals, transition metals, metalloids, alloys thereof, conductive carbon, etc., but is not limited thereto. In an embodiment, the negative electrode active material may include silicon, silicon alloy, lithium, lithium alloy, conductive carbon, or a combination thereof, but is not limited thereto. In an embodiment, the lithium alloy is made of or includes a lithium alloy comprising silicon, chlorine, or a combination thereof. A lithium metal thin film may also be used as the negative electrode active material.

[0436] Other materials for cathode active materials

[0437] The negative electrode active material is a carbon-based material such as artificial graphite, natural graphite, graphitized carbon fiber, amorphous carbon, etc.; a metal compound capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys, Al alloys, etc.; SiO x (0 <x<2), SnO2, 바나듐 산화물 또는 리튬 바나듐 산화물과 같은 리튬 이온을 도핑 및 탈도핑할 수 있는 금속 산화물; 및 Si―C 복합체 또는 Sn―C 복합체와 같은 금속 화합물과 탄소계 재료를 포함하는 복합체를 포함할 수 있다.

[0438] carbon-based materials

[0439] Carbon-based materials may include low-crystallinity carbon, high-crystallinity carbon, etc., or combinations thereof. Representative examples of low-crystallinity carbon are soft carbon or hard carbon, and representative examples of high-crystallinity carbon are high-temperature calcined carbon such as amorphous, plate-like, flake-like, spherical, or fibrous natural or artificial graphite, Kish graphite, pyrolytic carbon, mesophase pitch-based carbon fibers, mesocarbon microbeads, mesophase pitch, coke derived from petroleum or coal tar pitch, etc., or combinations thereof.

[0440] Metal-carbon composite materials

[0441] Alternatively, according to an embodiment of the present disclosure, the cathode (104) may comprise a cathode material having a metal-carbon composite, such as a silver-carbon compound or composite in which silver particles are composited between amorphous and / or crystalline carbon particles. While silver is used exemplarily, other metals including, for example, tin, silicon, zinc, or combinations thereof may be used.

[0442] Additional materials for cathode active materials

[0443] In addition to the aforementioned materials, the negative electrode active material is lithium titanate (Li4Ti5O2) capable of providing excellent cycling stability and high-rate performance. 12 Titanium-based compounds such as ) or titanium dioxide (TiO2) may also be included. Other potential materials include molybdenum oxide (MoO2), which can provide high theoretical capacity. x ), iron oxide (FeO x ) or nickel oxide (NiO x It may include transition metal oxides such as ). In some cases, composite materials combining different active materials, such as silicon-graphite composites or tin-carbon composites, can be used to mitigate individual limitations while utilizing the advantages of multiple materials.

[0444] Dentite formation

[0445] If the negative electrode (104) is made of lithium or a lithium alloy or includes the same, dendrites may be formed on the negative electrode (104). Dendrites are metallic lithium structures formed when excess lithium ions accumulate on the surface of the negative electrode (104). The formed dendrites can damage the solid electrolyte layer (106) and / or reduce the battery capacity of the all-solid-state battery (100) and / or cause undesirable performance of the all-solid-state battery (100). Since these structures can grow through the electrolyte and potentially cause short circuits and safety hazards, dendrite formation is a critical issue in lithium-based batteries. The growth rate and morphology of dendrites can be influenced by factors such as current density, temperature, and the properties of the electrolyte-electrode interface.

[0446] Benefits of Solid Electrolytes in Mitigating Dentite Formation

[0447] Solid electrolytes offer several advantages over liquid electrolytes in mitigating dendrite formation. The mechanical strength of solid electrolytes can help inhibit dendrite growth by providing a physical barrier to lithium metal penetration. Additionally, the uniform ion distribution of solid electrolytes can promote lithium deposition more evenly, thereby reducing the likelihood of localized dendrite nucleation. Some solid electrolytes may further inhibit dendrite formation by forming a stable interface with the lithium metal anode. However, while solid electrolytes can significantly reduce the risk of dendrite growth, they cannot completely eliminate it, and research is underway aimed at developing advanced solid electrolyte materials with enhanced dendrite inhibition capabilities.

[0448] Shape of the negative electrode active material

[0449] The cathode active material may be in the form of particles or in a continuous unitary form (e.g., a thin film or a sheet).

[0450] particle size

[0451] 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 110 nm nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm, 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm, 600 nm, 610 nm, 620 nm, 630 nm, 640 nm, 660 nm, 640 nm, 650 nm, 660 nm, 670 nm, 680 nm, 690 nm, 700 nm, 710 nm, 720 nm, 730 nm, 740 nm, 750 nm, 760 nm, 770 nm, 780 nm, 790 nm, 800 nm, 810 nm, 820 nm, 830 nm, 840 nm, 850 nm, 860 nm, 870 nm, 880 nm, 890 nm, 900 nm, 910 nm, 920 nm, 930 nm, 940 nm, 950 nm, 960 nm, 970 nm, 980 nm, 890 nm, 980 nm, 990 nm, 1000 nm, 2 ㎛, 3 ㎛, 4 ㎛, 5 ㎛, 6 ㎛, 7 ㎛, 8 ㎛, 9 ㎛, 10 ㎛, 15 ㎛, 20 ㎛, 25㎛, 30㎛, 35㎛, 40㎛, 45㎛, 50㎛,55 µm, 60 µm, 65 µm, 70 µm, 75 µm, 80 µm, 85 µm, 90 µm, 95 µm, 100 µm, 110 µm, 120 µm, 130 µm, 140 µm, 150 µm, 160 µm, 170 µm, 180 µm, 190 µm, 200 µm, 210 µm, 220 µm, 230 µm, 240 µm, 250 µm, 260 µm, 270 µm, 280 µm, 290 µm, 300 µm, 310 µm, 320 µm, 330 µm, 340 µm, 350 µm, 360 µm, 370 µm, 380 µm, 390 µm, 400 µm, 410 µm, 420 µm, 430 µm, 440 µm, 450 µm, 460 µm, 470 µm, 480 µm, 490 µm, 500 µm, 510 µm, 520 µm, 530 µm, 540 µm, 550 µm, 560 µm, 570 µm, 580 µm, 590 µm, 600 µm, 610 µm, 620 µm, 630 µm, 640 µm, 650 µm, 660 µm, 670 µm, 680 µm, 690 µm, 700 µm, 710 µm, Any numerical value in the range of 10 nm to 1000 µm or about 10 nm to about 1000 µm, such as 720 µm, 730 µm, 740 µm, 750 µm, 760 µm, 770 µm, 780 µm, 790 µm, 800 µm, 810 µm, 820 µm, 830 µm, 840 µm, 850 µm, 860 µm, 870 µm, 880 µm, 890 µm, 900 µm, 910 µm, 920 µm, 930 µm, 940 µm, 950 µm, 960 µm, 970 µm, 980 µm, 990 µm, or 1,000 µm, or about 10 nm to about It may include particle sizes of any other numerical value within the range of 1000 μm. In an embodiment, the particle size of the negative electrode active material may be within a range formed by selecting any two numerical values ​​in the range of 10 nm to 1000 μm or about 10 nm to about 1000 μm, and may be, for example, between about 10 nm and about 1,000 μm.

[0452] Amount of negative electrode active material of the negative electrode

[0453] The amount of negative active material in the solid-state battery (100) affects the charge / discharge capacity of the all-solid-state battery (100). To manufacture a high-capacity negative electrode (104), a high level of negative active material may be included in the negative electrode (104). For example, the negative electrode (104) includes 70, 80, 90, 95, 98, 99, or 100 wt%, about that wt%, or more than that wt% of negative active material based on the total weight of the negative electrode (104). In an embodiment, the negative active material of the negative electrode (104) may be within a range formed by selecting any two values ​​listed in the preceding sentence, for example, between about 70 wt% and about 100 wt%.

[0454] Material for cathode binder

[0455] The binder may include various types of binder polymers, such as, for example, polyvinylidene fluoride-co-hexafluoropropylene (PVdF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylate, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene butadiene rubber (SBR), fluororubber, polyacrylic acid, polymers thereof in which hydrogen atoms are substituted with Li, Na, or Ca, various copolymers thereof, or combinations thereof.

[0456] Examples of materials for cathode binders

[0457] In addition to the binders mentioned above, other binders suitable for use in the anode may include polyimide, polyamide-imide, polyurethane, polyethylene oxide (PEO), poly(ethylene-covinyl acetate) (PEVA), poly(vinyl acetate) (PVA), alginate, chitosan, guar gum, xanthan gum, carrageenan, pectin, gelatin, lignin, and various water-soluble polymers or derivatives thereof. In some cases, conductive polymers such as polypyrrole, polyaniline, or poly(3,4-ethylenedioxythiophene) (PEDOT) may also be used as binders to simultaneously improve adhesion and electrical conductivity within the cathode.

[0458] Amount of negative electrode binder

[0459] The cathode (104) may contain a binder in an amount of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 wt%, based on the total weight of the cathode (104), or any other wt% in the range between 0 and 30 wt%. In an embodiment, the binder of the cathode (104) may be within a range formed by selecting any two values ​​in the range between 0 and 30 wt%, for example, between about 0 wt% and about 30 wt%.

[0460] thickness of the cathode

[0461] The cathode (104) may have a thickness of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 μm, or any other thickness between about 10 μm and about 100 μm. In an embodiment, the thickness (t4) of the cathode (104) may be within a range formed by selecting any two values ​​in the range of 10 μm to about 100 μm, for example, between about 10 μm and about 100 μm or between about 10 μm and about 20 μm.

[0462] Porosity of the cathode

[0463] The porosity of the cathode (104) may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 vol% based on the total volume of the cathode (104), or any other vol% in the range of 0 to 18 vol%. In an embodiment, the porosity of the cathode (104) may be within a range formed by selecting any two values ​​in the range between 0 vol% and about 18 vol%.

[0464] Lithium ion diffusion of the cathode.

[0465] The negative electrode (104) is 1 x 10 -14 cm 2 / s, 1 x 10 -13 cm 2 / s, 1 x 10 -12 cm 2 / s, 1 x 10 -11 cm 2 / s, 1 x 10 -10 cm 2 / s, 1 x 10 -9 cm 2 / s, 1 x 10 -8 cm 2 / s or 1 x 10 -7 cm 2 Includes lithium ion diffusivity such as / s, or 1 x 10 -14 cm2 / s and 1 x 10 -7 cm 2 Between / s or about 1 x 10 -14 cm 2 / s and about 1 x 10 -7 cm 2 It may include lithium ion diffusivity of any other value between / s. In an embodiment, the lithium ion diffusivity of the cathode (104) is 1 x 10 -14 cm 2 / s to 1 x 10 -7 cm 2 / s or about 1 x 10 -14 cm 2 / s to about 1 x 10 -7 cm 2 It can be within the range formed by selecting any two values ​​in the / s range.

[0466] cathode current collector

[0467] The current collector (110) collects electrical energy generated from the negative electrode (104) and supports the negative electrode (104).

[0468] materials for cathode current collectors

[0469] The material of the current collector (110) is not particularly limited as long as it enables close contact with the negative electrode (104), has suitable electrical conductivity, and does not cause significant chemical changes in the all-solid-state battery (100) within the voltage range of the all-solid-state battery (100). For example, the current collector (110) may be made of or contain metal or conductive carbon, but is not limited thereto.

[0470] Metal for current collectors

[0471] The metal of the current collector (110) may include one or more selected from the group consisting of aluminum, aluminum alloy, copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, iron, iron alloy (e.g., steel, stainless steel), silver, silver alloy, or a combination thereof, but is not limited thereto.

[0472] shape of the cathode current collector

[0473] By forming fine surface irregularities on the surface of the current collector (110), the adhesion of the cathode (104) to the current collector (110) can be increased. The current collector (110) may have various shapes, such as, for example, a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven web, or a combination thereof. In addition to the aforementioned shapes, the current collector (110) may be composed of a honeycomb structure, a perforated sheet, a woven or nonwoven mesh, a sintered porous body, or a three-dimensional interconnected network. These various shapes can be tailored to optimize the surface area, mechanical strength, and current collection efficiency of the current collector (110).

[0474] Design of the cathode current collector

[0475] Additionally, the current collector (110) can be designed to accommodate all-solid-state batteries of different form factors, such as pouch cells, cylindrical cells, or prismatic cells, each of which can provide advantages in terms of packaging efficiency, thermal management, and overall battery performance.

[0476] Thickness of the cathode current collector

[0477] The thickness (t5) of the entire house (110) is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, It may be 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or 500 μm, etc., or any other numeric value in the range of 1 μm to 500 μm or about 1 μm to about 500 μm. In an embodiment, the thickness (t5) of the current collector (110) may be within a range formed by selecting any two values ​​in the range of 1 μm to 500 μm or about 1 μm to about 500 μm, for example, between about 5 μm and about 500 μm.

[0478] Method for manufacturing a cathode

[0479] The cathode (104) can be obtained by various methods, such as atomic deposition, extrusion, rolling, slurry methods, or combinations thereof. In addition to the methods described above, the cathode (104) can be manufactured using various other techniques, including dry electrode processes. These alternative methods may offer advantages in terms of environmental impact, cost efficiency, and scalability.

[0480] Dry powder coating

[0481] Dry powder coating can be employed as an alternative to the slurry method. In this process, a negative active material, a conductive additive, and a binder are mixed in a dry state and then applied directly to a current collector (110) using electrostatic deposition or mechanical compression. This method can potentially reduce environmental impact and processing time by reducing the use of solvents.

[0482] 3D printing

[0483] Additive manufacturing technologies such as 3D printing can be used to fabricate the cathode (104). Depending on the specific material and desired electrode properties, various 3D printing methods including fused deposition modeling (FDM), selective laser sintering (SLS), or direct ink writing (DIW) can be used. By this approach, the electrode structure and porosity can be precisely controlled.

[0484] electrospinning

[0485] Electrospinning is another potential method for manufacturing the cathode (104). In this process, a solution containing a positive active material, a conductive additive, and a polymer binder is extruded through a nozzle under an electric field to form nanofibers. These fibers can be collected directly onto a current collector (110) to form a porous electrode structure with an increased surface area.

[0486] Tape casting

[0487] Tape casting can be employed to prepare the cathode (104). This technique involves spreading a slurry of electrode material onto a carrier film using a doctor blade, followed by drying and calendering. Then, the obtained electrode tape can be laminated onto a current collector (110).

[0488] Spray coating

[0489] Spray coating technology can be used to fabricate the cathode (104). A fine mist of electrode slurry is sprayed onto the current collector (110) using compressed air or ultrasonic spraying. This approach can produce a thin and uniform electrode layer and can be particularly useful for large-scale production.

[0490] Freeze casting

[0491] Freeze casting is another potential method for manufacturing a cathode (104). This process involves freezing a slurry of electrode material and then sublimating the ice to create a porous structure. Then, the obtained porous electrode can be sintered and attached to a current collector (110).

[0492] Sol-gel process

[0493] In some cases, a sol-gel process may be used to prepare the cathode (104). This method involves forming a colloidal suspension (sol) and then converting it into a gel-like network containing the cathode active material and other components. This gel may be applied to a current collector (110) and then heat-treated to form a final electrode structure.

[0494] vapor deposition

[0495] For specific applications, physical vapor deposition (PVD) or chemical vapor deposition (CVD) techniques may be employed to create a thin film cathode directly on the current collector (110). These methods can produce a very uniform and dense electrode layer, which can be particularly advantageous for certain types of all-solid-state batteries.

[0496] Alloying and ball milling

[0497] A composite cathode material can be prepared using mechanical alloying and high-energy ball milling, and then pressed onto an electrode or applied to a current collector (110) using one of the aforementioned methods. This technique may be particularly useful for making nanostructured or amorphous cathode materials with improved electrochemical properties.

[0498] Slurry method

[0499] For example, the cathode active material can be mixed and stirred with a solvent, and optionally a binder and a dispersant to form a slurry. Then, the slurry can be applied (e.g., coated) to a current collector (110), and then pressed and dried to obtain a cathode (104).

[0500] Method for applying cathode slurry

[0501] The application of the slurry for the cathode (104) may include using a technique selected from the group consisting of slot die coating, gravure coating, spin coating, spray coating, roll coating, curtain coating, extrusion, casting, screen printing, inkjet printing, spray printing, gravure printing, thermal transfer printing, top plate printing, intaglio printing, offset printing, etc., and combinations thereof. In addition to the aforementioned techniques, other methods of applying the cathode slurry to the current collector may include doctor blade coating, dip coating, and meniscus coating.

[0502] Double slot die layer coating

[0503] Double slot die layer coating may also be employed, which allows two separate electrode material layers to be applied simultaneously to the current collector in a single pass. This method can potentially create a gradient structure within the electrode to optimize both electrochemical performance and mechanical properties.

[0504] Solvent for cathode slurry

[0505] The solvent for forming the cathode (104) may include water and / or organic solvents such as, for example, N-methylpyrrolidone (NMP), dimethylformamide (DMF), acetone, dimethylacetamide, dimethyl sulfoxide (DMSO), isopropyl alcohol, or a combination thereof. The solvent may be used in an amount sufficient to dissolve and disperse electrode components, such as the cathode active material and binder, taking into account the slurry coating thickness, production yield, etc., or a combination thereof. Additional organic solvents that may be used include ethanol, methanol, propanol, butanol, ethyl acetate, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and toluene.

[0506] Solvent-free method

[0507] In some embodiments, the cathode (104) can be prepared using a solvent-free method such as dry powder processing or melt extrusion, which eliminates the need for a liquid solvent and can provide environmental and cost advantages.

[0508] Dispersant for cathode slurry

[0509] The dispersant forming the cathode (104) may include an aqueous dispersant and / or an organic dispersant such as, for example, N-methyl-2-pyrrolidone. Other examples of aqueous dispersants may include sodium dodecyl sulfate (SDS), polyvinylpyrrolidone (PVP), and carboxymethyl cellulose (CMC), and additional organic dispersants may include various surfactants such as Triton X-100, polyethylene glycol (PEG), and polysorbate or poloxamer.

[0510] Dispersant-free method

[0511] In some embodiments, the cathode (104) can be prepared using a method that does not require a dispersant, such as dry powder processing or a specific additive manufacturing technique.

[0512] Drying technology for cathode slurry

[0513] The slurry for the cathode (104) can be dried by irradiating it with heat, an electron beam (E-beam), gamma rays, or ultraviolet rays (G, H, I-rays), or a combination thereof, to vaporize the solvent. For example, the slurry can be vacuum dried at room temperature. In the drying step, the solvent is removed through evaporation, but other components remain intact without evaporating to form the cathode (104).

[0514] Other drying technologies

[0515] In addition to the drying techniques described above, various other methods can be employed to dry the cathode slurry. These additional techniques can provide various advantages depending on the specific material, production requirements, and desired electrode characteristics.

[0516] Infrared (IR) drying

[0517] Infrared (IR) drying can be used to rapidly heat the electrode surface to promote efficient solvent evaporation. This method is particularly effective for thin electrode coatings and allows for precise control of the drying process.

[0518] Microwave drying

[0519] Microwave drying is another option that provides volumetric heating of the electrode material, potentially leading to more uniform drying across the entire electrode thickness. In some cases, a combination of convection drying and microwave drying can be employed to optimize both drying speed and uniformity.

[0520] Freeze-drying

[0521] Freeze-drying (also known as lyophilization) can be used for certain electrode formulations. This process involves freezing a slurry and then sublimating the solvent under vacuum conditions. Freeze-drying can help maintain the porous structure of the electrode, which can be advantageous for electrolyte penetration and ion transport.

[0522] Supercritical CO2 drying

[0523] Supercritical CO2 drying is an advanced technology applicable to specialty electrode materials. This method involves replacing the solvent with liquid CO2 and then purging it to a supercritical state for discharge. This approach can help preserve delicate nanostructures within electrodes and may be particularly useful for aerogel-based electrodes.

[0524] 2-stage drying

[0525] In some cases, a two-stage drying process may be employed. For example, initial drying may be performed at a low temperature to remove the bulk solvent, and then at a high temperature stage, the residual solvent may be removed and any desired chemical reaction within the electrode material may be potentially initiated.

[0526] Ultrasonic drying

[0527] Ultrasonic drying may also be considered for certain electrode formulations. By using high-frequency sound waves to agitate solvent molecules, this technique can potentially accelerate the drying process and improve the removal of solvent from the porous structure within the electrode.

[0528] General solid electrolyte layer

[0529] The solid electrolyte layer (106) is suitable for lithium ion diffusion between the positive electrode (102) and the negative electrode (104). The solid electrolyte layer (106) provides an electrically conductive path for the movement of charge carriers between the positive electrode (102) and the negative electrode (104). The solid electrolyte layer (106) is electrically connected to the positive electrode (102) and the negative electrode (104).

[0530] Location of solid electrolytes

[0531] In an embodiment, a solid electrolyte layer (106) is formed on an anode (102) or a cathode (104) and is in direct contact with the anode (102) or the cathode (104). In an embodiment, the solid electrolyte layer (106) is in direct contact with the anode (102) and the cathode (104). In another embodiment, another functional layer may be interposed between the solid electrolyte layer (106) and the anode (102) and / or the cathode (104).

[0532] Materials for solid electrolyte layers

[0533] The solid electrolyte layer (106) can transport lithium ions. The material of the solid electrolyte layer (106) is not particularly limited, provided that it enables close contact with adjacent layers, has suitable electrical conductivity, and does not cause significant chemical changes in the solid-state battery (100) over the voltage range of the solid-state battery (100). For example, the solid electrolyte layer (106) may include various inorganic solid electrolytes, polymeric solid electrolytes, and / or polymeric gel electrolytes, but is not limited thereto. Additionally or alternatively, the solid electrolyte layer (106) may include ceramic electrolytes, glass electrolytes, hybrid organic-inorganic electrolytes, and nanostructured electrolytes, but is not limited to these categories.

[0534] Inorganic solid electrolyte

[0535] Inorganic solid electrolytes may include, but are not limited to, crystalline solid electrolytes, amorphous solid electrolytes, glass-ceramic solid electrolytes, etc. Inorganic solid electrolytes may be sulfide-based, oxide-based, etc., or combinations thereof. In addition to sulfide-based and oxide-based inorganic solid electrolytes, other types of inorganic solid electrolytes may include halide-based electrolytes, nitride-based electrolytes, and borate-based electrolytes. For example, antiperovskites (LiRAP) such as lithium-rich Li3OCl and Li3OBr, lithium nitride (Li3N), and lithium borohydride (LiBH4) have been studied as potential solid electrolyte materials for lithium-ion batteries.

[0536] Sulfide-based solid electrolytes

[0537] Sulfide-based solid electrolytes contain sulfur (S) and have the ionic conductivity of a metal belonging to Group I or Group II of the periodic table, and may include Li-P-S glass or Li-P-S glass ceramics.

[0538] Examples of sulfide-based solid electrolytes

[0539] For example, sulfide-based solid electrolytes may include lithium sulfide, silicon sulfide, germanium sulfide, and boron sulfide. Specific examples of inorganic solid electrolytes are Li 3.833 Sn 0.833 As 0.166 S4, Li4SnS4, Li 3.25 Ge 0.25 P 0.75 S4, Li2S―P2S0, B2S 3― Li2S, XLi2S-(100-x)P2S5(x=70-80), Li2S―SiS 2― Li3N, Li2S―P2S 5― LiI, Li2S―SiS 2― LiI, Li2S—B2S3-LiI, Li3N, LISICON, LIPON (Li 3+y PO 4-x N x ), thio-LISICON(Li3.25 Ge 0.25 P 0.75 S4), Li2O―Al2O 3― TiO 2― P2O5(LATP), Li2S—P2S5, Li2S—LiI—P2S5, Li2S—LiI—Li2O—P2S5, Li2S—LiBr—P2S5, Li2S—Li2O—P2S5, Li2S—Li3PO 4― P2S5, Li2S―P2S 5― P2O5, Li2S―P2S 5― SiS2, Li2S―P2S 5― SnS, Li2S―P2S 5― Al2S3, Li2S—GeS2, Li2S—GeS 2― ZnS, Li 10 GeP2S 12 (LGPS), Li7P3S 11 , Li6PS5Cl, Li6PS5Br, Li6PS5I, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , Li 11 Si2PS 12 It may include, etc., or a combination thereof.

[0540] Doped Variant

[0541] In some cases, doped variants of these materials, e.g., Al-doped Li, are used to further improve ionic conductivity or stability. 10 GeP2S 12 Alternatively, Sb-doped Li6PS5Cl may be used.

[0542] oxide-based solid electrolytes

[0543] Oxide-based solid electrolyte materials contain oxygen (O) and have the ionic conductivity of metals belonging to Group I or Group II of the periodic table.

[0544] Examples of oxide-based solid electrolyte materials

[0545] Oxide-based solid electrolyte materials include LLTO-based compounds and Li6La2CaTa2O 12 , Li6La2ANb2O 12 (A is Ca or Sr), Li2Nd3TeSbO 12 , Li3BO 2.5 N 0.5 , Li9SiA1O8, LAGP-based compounds, LATP-based compounds, Li 1+x Ti 2-x Al x Si y (PO4) 3-y (0≤x≤1, 0≤y≤1), LiAl x Zr 2-x (PO4)3(0≤x≤1, 0≤y≤1), LiTi x Zr 2-x (PO4)3 (0≤x≤1, 0≤y≤1), lisicon compounds, lipon compounds, perovskite compounds, NASICON compounds, and LLZO-based or LLZO-derived compounds (e.g., Al-doped Li7La3Zr2O 12 and Ta doping Li7La3Zr2O 12 It may include at least one selected from the group consisting of ). Lithium-rich antiperovskites such as Li3OCl and Li3OBr have also been studied as potential oxide-based solid electrolytes.

[0546] Complex oxide electrolyte

[0547] In some cases, a composite oxide electrolyte combining multiple oxide materials, such as an LLZO-LATP composite, can be adopted to utilize the advantages of different oxide systems.

[0548] Polymer solid electrolyte

[0549] Polymer solid electrolytes are composites of electrolyte salts and polymer resins and have lithium ion conductivity. Polymer solid electrolytes may include polyether polymers, polycarbonate polymers, acrylate polymers, polysiloxane polymers, phosphazene polymers, polyethylene derivatives, alkylene oxide derivatives, phosphate polymers, polyagitation lysine, polyester sulfides, polyvinyl alcohol, polyvinylidene fluoride, polymers containing ion-dissociable groups, biopolymers such as poly(ethyleneimine) (PEI), poly(methyl methacrylate) (PMMA), poly(acrylonitrile) (PAN), poly(ethylene succinate) (PES), chitosan, and cellulose derivatives, or combinations thereof.

[0550] Polymer resin for solid polymer electrolytes

[0551] The solid polymer electrolyte may include polymer resins such as branched copolymers comprising a polyethylene oxide (PEO) backbone copolymerized with a comonomer comprising amorphous polymers such as, for example, PMMA, polycarbonate, polydiloxane (PDMS) and / or phosphazene, comb polymers, cross-linked polymer resins, polyethylene glycol (PEG), polypropylene oxide (PPO), polyacrylonitrile (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(ethylene oxide-co-propylene oxide) (PEO-PPO), poly(ethyleneimine) (PEI), poly(vinylpyrrolidone) (PVP), poly(vinyl alcohol) (PVA), various block copolymers or graft copolymers incorporating these materials, or combinations thereof.

[0552] polymer gel electrolyte

[0553] Polymer gel electrolytes can be formed by incorporating an organic electrolyte containing an organic solvent, an electrolyte salt, an ionic liquid, a monomer, or an oligomer into a polymer resin, or by combining the same. Polymer resins for polymer gels may include polyether polymers, PVC polymers, PMMA polymers, polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene: PVDF-co-HFP), etc., or combinations thereof.

[0554] Examples of polymer gel electrolytes

[0555] Examples of polymer gel electrolytes suitable for solid-state batteries that optimize the electrochemical and physical properties of solid electrolytes include poly(ethylene oxide) (PEO), poly(methyl methacrylate-co-ethyl acrylate) (PMMA-EA), poly(acrylonitrile-co-methyl methacrylate) (PAN-MMA), poly(vinyl acetate) (PVAc), poly(ethylene glycol diacrylate) (PEGDA), poly(vinyl pyrrolidone) (PVP), poly(ethylene glycol methyl ether acrylate) (PEGMEA), poly(ethylene glycol methyl ether methacrylate) (PEGMEMA), poly(ionic liquid) (PIL), poly(ethylene glycol-co-propylene glycol) (PEG-PPG), poly(vinyl alcohol-co-ethylene) (PVA-PE), poly(acrylamide) (PAM), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(ethylene glycol-co-polyethylene). It includes oxide (PEG-PEO) and poly(methacrylic acid) (PMAA)-based gel electrolytes.

[0556] electrolytes

[0557] The electrolyte is an ionizable lithium salt, and Li + X - It can be displayed as. X - is F - , Cl - , Br - , NO3 - , N(CN)2- , BF4 - , ClO4 - , AlO4 - , AlCl4 - , PF6 - , SbF6 - , AsF6 - , BF2C2O4 - , BC4O8 - , (CF3)2PF4 - , (CF3)3PF3 - , (CF3)4PF2 - , (CF3)5PF - , (CF3)6P - , CF3SO3 - , C4F9SO3 - , CF3CF2SO3 - , (CF3SO2)2N - , (F2SO2)2N - , CF3CF2(CF3)2CO - , (CF3SO2)2CH, CF3(CF2)7SO3 - , CF3CO2 - , CH3CO2 - , SCN - , (CF3CF2SO2)2N - It may include anions selected from a group consisting of the following.

[0558] Examples of lithium salts

[0559] For example, lithium salts include LiTFSI, LiCl, LiBr, LiI, LiClO4, lithium tetrafluoroborate (LiBF4), and LiB 10 Cl 10, lithium hexafluorophosphate (LiPF6), LiAsF6, LiSbF6, LiAlCl4, LiSCN, LiCF3CO2, LiCH3SO3, LiCF3SO3, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC4F9SO3, LiC(CF3SO2)3, (CF3SO2)2NLi, lithium chloroborate, lithium lower aliphatic carboxylate, lithium imide 4-phenylborate, lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 4,5-dicyano-2-(trifluoromethyl)imidazolade (LiTDI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), etc., and It may be any one selected from the group consisting of combinations thereof. The electrolyte salt may include any combination of the salts described herein.

[0560] Amount of electrolytes

[0561] The solid electrolyte layer (106) contains an electrolyte salt (if present) in an amount of 0, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, or 400 parts by weight, etc., based on the total weight of the solid electrolyte layer (106), or any amount between 0 parts by weight and 400 parts by weight. It may be included in other values. In an embodiment, the electrolyte salt in the solid electrolyte layer (106) may be within a range formed by selecting any two values ​​between about 0 parts by weight and about 400 parts by weight or about 60 and 400 parts by weight based on the total weight of the solid electrolyte layer (106).

[0562] Ionic conductivity of the solid electrolyte layer

[0563] The solid electrolyte layer (106) may have suitable reduction stability and / or ionic conductivity. Since the solid electrolyte layer (106) primarily functions to transport lithium ions between electrodes, the solid electrolyte layer (106) is, for example, 10 -7 S / cm, 10 -6 S / cm, 10 -5 S / cm or 10 -4 S / cm, about that S / cm, or a desirable ionic conductivity greater than that S / cm, or about 10 -7 It may include any other desirable ionic conductivity greater than S / cm.

[0564] Thickness of the solid electrolyte layer

[0565] The thickness (t6) of the solid electrolyte layer (106) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, or 1,000 μm, etc., or any other numeric value between 0 and 1,000 μm or between 0 and about 1,000 μm. In an embodiment, the thickness (t6) of the solid electrolyte layer (106) may be within a range formed by selecting any two numeric values ​​in the range between 0 and 1,000 μm or between 0 and about 1,000 μm, for example, between about 5 μm and about 1,000 μm, between about 30 μm and about 100 μm, or between about 30 μm and about 50 μm.

[0566] Unfinished Product

[0567] A cell (101) as illustrated in FIG. 5 may be provided as a semi-finished product. In an embodiment, the cell (101) is stored, transported, and / or delivered to a reseller, customer, etc., who will complete the manufacture of a battery assembly or battery product containing the cell (101). In another embodiment, the cell (101) is a finished battery assembly or battery product.

[0568] Battery sealing

[0569] The manufacturing of the all-solid-state battery (100) can be completed by sealing the enclosure (112) of the all-solid-state battery to operate as a battery. The sealing process may involve various techniques to reliably protect internal components from external environmental factors and maintain the integrity of the battery structure. For example, the enclosure (112) may be hermetically sealed using methods such as laser welding, ultrasonic welding, or adhesive bonding. In some cases, the sealing process may also include introducing a protective atmosphere to create a vacuum within the enclosure or removing air. This sealing step may help prevent the ingress of moisture, which could potentially degrade the performance of the sulfide-based solid electrolyte. Additionally, the sealing process may incorporate safety features, such as a pressure relief mechanism, to manage any gas accumulation that may occur during battery operation.

[0570] After sealing the battery

[0571] When properly sealed, the all-solid-state battery (100) is ready to undergo final quality control inspections, which may include electrical testing, leak detection, and visual inspection. If these inspections are passed, the all-solid-state battery (100) can be packaged and sold as a finished product ready for integration into various electronic devices, electric vehicles, energy storage systems, etc.

[0572] Battery composition

[0573] The solid-state battery (100) is provided in various configurations to suit different applications and device requirements. In some embodiments, the battery may be manufactured in a cylindrical shape, which may be advantageous for certain types of portable electronic devices or automotive applications. Alternatively, the all-solid-state battery (100) may be produced in a prismatic shape, which may enable more efficient space utilization in devices with a rectangular form factor. In other cases, a pouch shape may be adopted, which provides shape flexibility and potentially reduces the overall battery weight. The pouch shape may be particularly more suitable for the all-solid-state battery because uniform pressure can be easily applied and controlled within the battery.

[0574] Selection of configuration

[0575] The choice of configuration may depend on factors such as the intended use, space constraints, thermal management requirements, and manufacturing considerations. In some embodiments, hybrid or custom configurations combining different forms of elements may be available as desired. The diversity of battery form factors enables the integration of all-solid-state batteries into a wide range of products, from small wearable devices to large-scale energy storage systems.

[0576] voltage

[0577] The solid-state battery (100) is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 48, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, It is configured to output a voltage such as 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or 500 V, or any other voltage between 0 and 500 V DC or between 0 and about 500 V DC. In an embodiment, the output voltage of the all-solid-state battery (100) may be within a range formed by selecting any two values ​​in the range between 0 and 500 V or between 0 and about 500 V, for example, between about 1 V DC and about 500 V DC.

[0578] volume

[0579] The solid-state battery (100) may be configured to have a capacity of 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, or 300 mAh / g, about that mAh / g, or more than that mAh / g, or any other value of capacity between 0 and 300 mAh / g or between 0 and about 300 mAh / g. In an embodiment, the output voltage of the all-solid-state battery (100) may have a capacity formed by selecting any two values ​​in the range between 0 and 300 mAh / g or between 0 and about 300 mAh / g, for example, may have a capacity between about 100 mAh / g and about 300 mAh / g.

[0580] Volume expansion calculation

[0581] The solid-state battery (100) can be configured to have a desirable volume expansion rate. The volume expansion rate is the first charge / discharge compared to the initial thickness. 　 It can be calculated from the change in thickness after the cycle. The volume expansion rate may be the ratio of the change in thickness to the initial thickness. The first charge-discharge cycle is performed by CC-CV charging, which charges the battery to 0.1 C and cuts off at 0.02 C at 4.25 to 4.4 V, and CC discharge, which discharges the battery to 0.1 C and cuts off at 3 V. The volume expansion rate is calculated by Equation 1 below, where A represents the thickness before charge-discharge and B represents the thickness after charge-discharge. The thickness can be measured using a Mouser micrometer or a scanning electron microscope (SEM).

[0582] Equation 1:

[0583] Volume expansion rate = [(BA) / A] × 100

[0584] C-rate

[0585] The C-rate used herein refers to the rate at which a battery is discharged relative to its maximum capacity. For example, a 1C rate means that the entire battery is discharged within one hour. That is, for a battery with a capacity of 20 C / s, the discharge current at 1C is 20 C / s.

[0586] Other examples of volume expansion

[0587] Other exemplary methods for measuring and calculating the volume expansion rate of a solid-state battery may include volume expansion measurements (e.g., gas pycnometry), in-situ dilatometry, X-ray tomography, strain gauge measurements, optical methods (e.g., digital image correlation or laser interferometry), pressure-based methods, and electrochemical strain microscopy.

[0588] Examples

[0589] The following embodiments are described more fully to facilitate understanding of the present disclosure. However, the following embodiments are for illustrative purposes only and the scope of the present disclosure is not limited thereto.

[0590] Example 1

[0591] Example 1.1: Al-containing film

[0592] Al particles are obtained from Sigma-Aldrich. Poly(styrene-ethylene / butylene-styrene) block copolymer polymer binder is also obtained from Sigma-Aldrich. A slurry is prepared by adding 1 g of Al particles and 0.001 g of polymer binder to 0.5 ml of xylene. This slurry is spread over a Cu foil using a doctor blade. The substrate having the slurry top layer is dried at 80°C (temperature) for 2 hours (duration) to form an Al-containing film as shown in Fig. 1. The obtained Al-containing film has a thickness of 50 μm as measured by a scanning electron microscope (SEM).

[0593] Example 1.2: Li foil

[0594] The Li foil is obtained from Honjo Chemical Corporation. This Li foil has a thickness of 20 μm and is integrated with a 12 μm Cu substrate.

[0595] Example 1.3: Cathode Assembly

[0596] The Al-containing film of Example 1.1 is laminated on top of the Li foil of Example 1.2.

[0597] Example 1.4: Alloy cathode

[0598] The assembly of Example 1.3 is pressurized at 250 MPa for 1 hour.

[0599] Example 1.5: Characterization of Alloy Cathode

[0600] Example 1.5.1: Alloy phase

[0601] XRD is performed on the LiAl alloy cathode obtained in Example 1.4. Figure 6 is the XRD spectrum of this LiAl alloy cathode. Figure 8 is the XRD spectrum of LiAl alloy cathodes fabricated under three different pressurization conditions of 125, 250, and 400 MPa for 30 minutes, respectively.

[0602] Example 1.5.2: SEM

[0603] SEM is performed on the alloy cathode of Example 1.4. Figure 7 is an SEM image of the cathode.

[0604] Example 1.5.3: Thickness

[0605] The thickness of the cathode layer of Example 1.4 is measured using SEM. The result shows that the thickness of the cathode layer is 50 μm.

[0606] Example 2

[0607] Example 2.1: Al-containing film

[0608] Repeat Example 1.1.

[0609] Example 2.2: Li foil

[0610] A 50 µm free-standing Li foil is used.

[0611] Example 2.3: Cathode Assembly

[0612] As shown in Fig. 2, a cathode assembly is prepared using a 50 μm Li foil sandwiched between two Al-containing films.

[0613] Example 2.4: Alloy cathode

[0614] The cathode assembly of Example 2.3 is passed through a 200 μm gap between two rollers. Then, the Cu foil attached to both sides of the cathode assembly is peeled off.

[0615] Example 2.5: Characterization of Alloy Cathode

[0616] Example 2.5.1: SEM

[0617] Figure 3 is an SEM of the cross-section of the cathode formed in Example 2.4, showing that the Al particles were broken down into smaller particles due to lithiation.

[0618] Example 2.5.2: Thickness

[0619] From the SEM of the cathode of Example 2.5.1, the thickness of the formed cathode was measured to be 91 μm.

[0620] Example 3

[0621] Example 3.1: Battery assembly using the negative electrode of Example 1.4

[0622] Provides an anode layer of NCM811. Provides a solid electrolyte layer of LPSCl. The anode layer, the solid electrolyte layer, and the cathode of Example 1.4 are placed in a titanium jig cell, and then the assembly is pressurized at room temperature under a pressure of 3 tons for 3 minutes.

[0623] Example 3.2: Battery test of Example 3.1

[0624] A CCD test was performed on the battery prepared in Example 3.1, and the results are shown in FIG. 9.

[0625] Example 4

[0626] Example 4.1: Battery assembly using the negative electrode of Example 2.4

[0627] Provides an anode layer of NCM811. Provides a solid electrolyte layer of LPSCl. The anode layer, the solid electrolyte layer, and the cathode of Example 2.4 are placed in a titanium jig cell, and then the assembly is pressurized at room temperature under a pressure of 3 tons for 3 minutes.

[0628] Example 4.2: Battery test of Example 4.1

[0629] A charge-discharge test was performed on the battery prepared in Example 4.1, and the results are shown in FIG. 10.

[0630] Included combinations and characteristics

[0631] Various features and characteristics are described in this specification to provide an understanding of the composition, structure, production, function, and / or operation of the present disclosure, including the disclosed compositions, coatings, and methods. It is understood that the various features and characteristics of the present disclosure described in this specification may be combined in any appropriate manner, regardless of whether such features and characteristics are explicitly described in combination in this specification. The inventors and applicants explicitly intend that such combinations of features and characteristics fall within the scope of the present disclosure as described in this specification. Accordingly, the claims may be amended to cite any combination of any features and characteristics that are explicitly or essentially described in this specification or explicitly or essentially supported by this specification. Additionally, the applicant reserves the right to amend the claims to affirmatively waive features and characteristics that may exist in the prior art even if those features and characteristics are not explicitly described in this specification. Accordingly, any such amendment does not add novelty to the specification or claims and complies with the detailed description requirement, the sufficiency of description requirement, and the novelty requirement.

[0632] By reference

[0633] Any patent, publication, or other document identified in this specification is incorporated by reference in its entirety unless otherwise indicated, provided that the incorporated material does not conflict with any prior descriptions, definitions, statements, examples, or other disclosed material explicitly set forth in this specification. Accordingly, to the extent necessary, the express disclosures set forth in this specification take precedence over any conflicting material incorporated by reference. Any material or part thereof incorporated by reference in this specification but conflicting with any prior definitions, statements, or other disclosed material set forth in this specification is incorporated only to the extent that no conflict arises between such incorporated material and the prior disclosed material. The applicant reserves the right to amend this specification to explicitly incorporate any subject or part thereof incorporated by reference. Any amendment to this specification to add such incorporated subject shall comply with the detailed description requirement, the sufficiency of description requirement, and the novelty requirement.

[0634] Examples of various forms

[0635] While the present disclosure provides descriptions of various specific embodiments for the purpose of illustrating various aspects and / or potential uses of the present disclosure, it is understood by those skilled in the art that modifications and variations will occur. Accordingly, the present disclosure should be understood broadly, at least to the same extent as the claims, and should not be defined more narrowly by the specific exemplary embodiments provided herein.

[0636]

[0637] [Explanation of the symbol]

[0638] 1, 2, 3; particles near the first surface

[0639] 4, 5, 6, 7: Particles near the second surface

[0640] 8, 9, 10: Binder molecules

[0641] 11: Al-containing film

[0642] 12: Al-containing film surface

[0643] 20: Li foil

[0644] 21: Li foil surface

[0645] 30: Whole house

[0646] 41: First conductive substrate

[0647] 42: Second conductive substrate

[0648] 51: First Al-containing film

[0649] 52: Secondary Al-containing film

[0650] 100: All-solid-state battery

[0651] 101: Cell

[0652] 102: Anode

[0653] 104: Cathode

[0654] 106: Solid electrolyte layer

[0655] 108: Whole house

[0656] 110: Whole house

[0657] 112: Enclosure

[0658] A: First surface of the negative electrode active material layer

[0659] B: Second surface of the negative electrode active material layer

Claims

1. As a cathode, The whole house; and A negative electrode active material layer comprising a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (LiAl-containing particles). Includes, The above negative electrode active material layer has a first surface facing in a direction opposite to the current collector and a second surface facing the current collector; Generally, the closer to the second surface along the direction from the first surface to the second surface within the cathode active material layer, the more lithium is contained in the LiAl-containing particles, and Generally, the closer to the second surface along the direction within the cathode active material layer, the smaller the LiAl-containing particles become, and Generally, the closer to the second surface along the direction within the cathode active material layer, the less round the LiAl-containing particles become; The molecules of the polymer binder are generally distributed throughout the entire cathode active material layer, such that at least a portion of the molecules of the polymer binder are interposed between two adjacent LiAl-containing particles within the cathode active material layer. cathode.

2. In Paragraph 1, A further comprising Al particles on the first surface, cathode.

3. In Paragraph 1, further comprising Li metal on the second surface above, cathode.

4. In Paragraph 1, The above LiAl-containing particles have a Li:Al molar ratio of about 0.1 to about 5, cathode.

5. In Paragraph 1, The above LiAl-containing particles have a Li:Al molar ratio of about 0.5 to about 1, cathode.

6. In Paragraph 1, The above LiAl-containing particles have a Li:Al molar ratio of about 0.5, cathode.

7. In Paragraph 1, The polymer binder comprises at least one polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyimide (PI), carboxymethyl cellulose (CMC), succinonitrile-based polymer, styrene-butadiene rubber (SBR), polyethylene glycol (PEG), polyvinyl acetate (PVAc), polyurethane (PU), polyacrylic acid (PAA), ionic polymer, gel polymer, hydroxypropyl methylcellulose, methyl cellulose, starch, modified starch, and acrylic emulsion polymer. cathode.

8. As a method for manufacturing a cathode, A step of providing an Al-containing film comprising Al particles and a polymer binder; A step of laminating the above Al-containing film with a Li foil so that the surface of the above Al-containing film and the surface of the above Li foil come into contact with each other; and By applying pressure to the above Al-containing film and the above Li foil together to form a cathode, At least a portion of the Li metal within the above Li foil is moved toward the above Al-containing film, and At least some of the Al particles within the Al-containing film are moved toward the Li foil, and A step of causing the above Li metal to come into contact with the surface of the above Al particles to form particles containing a lithium-aluminum alloy (LiAl) (LiAl-containing particles). Includes, The above cathode is The whole house; and A negative electrode active material layer comprising a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (LiAl-containing particles). Includes, The above negative electrode active material layer has a first surface facing in a direction opposite to the current collector and a second surface facing the current collector; Generally, the closer to the second surface along the direction from the first surface to the second surface within the cathode active material layer, the more lithium is contained in the LiAl-containing particles, and Generally, the closer to the second surface along the direction within the cathode active material layer, the smaller the LiAl-containing particles become, and Generally, the closer to the second surface along the direction within the cathode active material layer, the less round the LiAl-containing particles become; The molecules of the polymer binder are generally distributed throughout the entire cathode active material layer, such that at least a portion of the molecules of the polymer binder are interposed between two adjacent LiAl-containing particles within the cathode active material layer. Method for manufacturing a cathode.

9. In Paragraph 8, The step includes preparing the above Al-containing film, and this step A step of preparing a solution or slurry comprising Al particles, a solvent, and a polymer binder; A step of providing a layer of the solution or slurry on top of a substrate; and The method includes the step of drying a layer of the solution or slurry on the substrate to form an Al-containing film, wherein the Al-containing film has a substantially homogeneous thickness. Method for manufacturing a cathode.

10. In Paragraph 8, The polymer binder comprises at least one polymer selected from the group consisting of polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polyacrylonitrile (PAN), polyimide (PI), carboxymethyl cellulose (CMC), succinonitrile-based polymer, styrene-butadiene rubber (SBR), polyethylene glycol (PEG), polyvinyl acetate (PVAc), polyurethane (PU), polyacrylic acid (PAA), ionic polymer, gel polymer, hydroxypropyl methylcellulose, methyl cellulose, starch, modified starch, and acrylic emulsion polymer. Method for manufacturing a cathode.

11. In Paragraph 8, The above polymer binder is in an amount of about 0.1 to 10 wt% based on the total weight of the Al particles, Method for manufacturing a cathode.

12. In Paragraph 8, The above Li foil has a thickness of about 0.1 μm to about 10 μm, Method for manufacturing a cathode.

13. In Paragraph 8, The above Al-containing film and the above Li foil are pressurized under a pressure of about 100 MPa to about 500 MPa, Method for manufacturing a cathode.

14. In Paragraph 8, The above Al-containing film and the above Li foil are pressurized under a pressure of about 125 MPa to about 400 MPa, Method for manufacturing a cathode.

15. In Paragraph 8, The above Al-containing film and the above Li foil are pressurized for about 5 minutes to about 1 hour, Method for manufacturing a cathode.

16. In Paragraph 8, The above Al-containing film and the above Li foil are pressurized for about 10 minutes to about 30 minutes, Method for manufacturing a cathode.

17. In Paragraph 8, The above Al-containing film and the above Li foil are pressurized at a temperature of about 20°C to about 150°C, Method for manufacturing a cathode.

18. In Paragraph 8, The above Al-containing film and the above Li foil are pressurized at a temperature of about 50°C to about 100°C, Method for manufacturing a cathode.

19. As an all-solid-state battery, cathode; Anode; and A solid electrolyte located between the anode and the cathode and configured to enable the transport of lithium ions between the anode and the cathode Includes, The above cathode is The whole house; and A negative electrode active material layer comprising a polymer binder and particles containing a lithium-aluminum alloy (LiAl) (LiAl-containing particles). Includes, The above negative electrode active material layer has a first surface facing in a direction opposite to the current collector and a second surface facing the current collector; Generally, the closer to the second surface along the direction from the first surface to the second surface within the cathode active material layer, the more lithium is contained in the LiAl-containing particles, and Generally, the closer to the second surface along the direction within the cathode active material layer, the smaller the LiAl-containing particles become, and Generally, the closer to the second surface along the direction within the cathode active material layer, the less round the LiAl-containing particles become; The molecules of the polymer binder are generally distributed throughout the entire cathode active material layer, such that at least a portion of the molecules of the polymer binder are interposed between two adjacent LiAl-containing particles within the cathode active material layer. All-solid-state battery.

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