Anode and method of manufacture and use thereof

Abstract

Amorphous glasses, anodes containing particles formed from these amorphous glasses, and electrochemical cells (e.g., batteries) containing these anodes are disclosed. The amorphous glasses can be formed from mixtures containing two or more active components and two or more amorphous-forming components.

Description

Cross-reference of related applications

[0001] This application claims the interests of U.S. Provisional Patent Application No. 62 / 713,137, filed on 1 August 2018, which is incorporated herein by reference in its entirety. [Background technology]

[0002] Lithium-ion batteries are used in applications requiring high energy density or high power density. Due to their density characteristics, lithium-ion batteries are suitable for electric vehicles (EVs) as well as portable electronic devices such as mobile phones, tablets, laptops, and digital cameras. Typically, recharging these batteries takes much longer than refueling a standard liquid-fueled vehicle. However, consumer demand is ultimately for a refueling experience of similar length to that of a liquid-fueled vehicle, i.e., less than 10 minutes. Similarly, faster charging for consumer portable electronic devices is desired.

[0003] Battery research and development over the past decade has focused on increasing the energy density of battery cells through larger capacity materials and thicker electrodes. However, this thicker electrode system struggles to function at higher charge rates. Compared to thinner coated electrodes, thicker electrodes may degrade more rapidly if charging is too fast. Lower charge rates are necessary to allow lithium ions to reach all storage sites in the active material on the electrodes. Generally, the more storage sites there are per unit area of ​​material, the longer it takes for those sites to accommodate lithium ions. If the charge rate is too high, there is a risk that the materials will be exposed to lithium ions at a rate that cannot accommodate them. This can lead to lithium plating on the anode surface, increased battery temperature, and other harmful side chemical reactions that degrade lifespan and performance characteristics.

[0004] During charging, lithium ions migrate from the cathode electrode and intercalate (i.e., are inserted) into the anode electrode, or react with the anode to form a stable structure. As the charging rate increases, lithium ions migrate from the cathode to the anode more rapidly. At high charging rates and typically high states of charge (SOC), the available storage sites are filled or nearly filled, and intercalation or anode reactions stall, preventing lithium ions from moving into the anode material. As a result, lithium ions deposit or plate onto the surface of the anode as lithium metal. Lithium plating can lead to dendrite growth, increased resistance, and potentially short circuits.

[0005] There are many anodic chemistrys with varying levels of technological maturity. Carbon-based anodes, such as graphite, are among the most abundant materials in the lithium-ion battery industry. However, if graphite is lithitated during recharging, the electrochemical potential of the electrode may become very low. Therefore, lithium plating may occur more easily, especially when the battery is charged rapidly and as it approaches a fully charged state. Lithium titanate (LTO), when fully lithitated compared to graphite, has a higher potential, lower density, and is more difficult to lithium plate. LTO may be suitable for repeated and reliable charging at high rates of as high as 10C. New anodic chemistrys are currently being studied, but none have matured to the point where they are viable candidates for extremely fast charging. For example, silicon offers the advantage of fast charging in the form of thinner anode thicknesses due to its much larger area capacity compared to graphite anodes, but silicon-containing electrodes for fast charging applications are still underdeveloped and their feasibility is uncertain.

[0006] State-of-the-art high-energy battery cell technology can deliver 200 Wh / kg with a 2C (30-minute) charge. The main limitation is that charging the graphite anode at a higher rate than this can significantly reduce battery life and safety due to increased lithium plating and battery temperature. The Department of Energy (DOE) requires next-generation fast-charging battery cells, called ultrafast chargers, to exceed 2Ah, achieve 500 6C charge / 1C discharge cycles, and have a specific energy (i.e., charge acceptivity) delivered from the fast-charging protocol fade of less than 20%, while achieving or improving upon the specific energy and cost of state-of-the-art cells. The charge rate does not need to be constant current, but the charge protocol must be completed within 10 minutes. The DOE specification is for a charge protocol that delivers at least 180 Wh / kg of stored energy to the cell in the early stages of its life (i.e., initial cell characteristics test). The energy delivered is determined by discharging a rapidly charged cell to a defined minimum voltage at a C / 3 rate. Upon completion of 500 6C charge* / 1C discharge cycles, the battery should have a fade of less than 20% of the delivered specific energy from the fast charging protocol (i.e., 144 Wh / kg or more).

[0007] Therefore, it is necessary to meet or exceed the specifications of next-generation ultrafast charging lithium-ion batteries. [Overview of the project]

[0008] Provided herein is an anode comprising particles formed from amorphous glass. The amorphous glass can be formed from a mixture comprising two or more active ingredients and two or more amorphous-forming ingredients.

[0009] The particle size and particle size distribution can vary. In some cases, the particles may have an aspect ratio of 10 or less, for example, an aspect ratio of 5 or less, or an aspect ratio of 2 or less. In some embodiments, the particles may be substantially spherical.

[0010] In one embodiment, the particles include a monodisperse collection of particles.

[0011] In some embodiments, the particles may include a collection of fine particles. For example, in some embodiments, the particles may include a collection of fine particles that have an average particle size of 1 to 15 microns (e.g., 1 to 5 microns) as measured by scanning electron microscopy (SEM). In other embodiments, the particles may include a collection of nanoparticles. For example, in some embodiments, the collection of nanoparticles may have an average particle size of 25 nm to less than 1 micron (e.g., 100 nm to 750 nm) as measured by scanning electron microscopy (SEM).

[0012] Two or more active ingredients can constitute 51 mol% to 99 mol% (e.g., 80 mol% to 95 mol%) of the amorphous glass. Two or more amorphous-forming components can constitute 1 mol% to 49 mol% (e.g., 5 mol% to 25 mol%, or 5 mol% to 20 mol%) of the amorphous glass. Two or more active ingredients and two or more amorphous-forming components can be present in the amorphous glass in molar ratios of 1.1:1 to 50:1, for example, 1.1:1 to 25:1, 2:1 to 25:1, 2:1 to 20:1, 4:1 to 20:1, 5:1 to 15:1, or 5:1 to 10:1.

[0013] The two or more active ingredients may include silicon, tin, lead, antimony, germanium, gallium, indium, bismuth, or any combination thereof. In some embodiments, the two or more active ingredients may include silicon. In some embodiments, the two or more active ingredients may include tin.

[0014] In some embodiments, the amorphous glass may include SiSn-based glass (e.g., glass containing silicon, tin, optionally one or more additional active ingredients, and two or more amorphous components). In the case of SiSn-based amorphous glass, the two or more active ingredients include silicon and tin, and silicon and tin can be present in a molar ratio of 1.1:1 to 20:1 (e.g., 2:1 to 15:1 or 3:1 to 12:1).

[0015] Two or more amorphous-forming components may include electrochemically inert components that are favorable for glass formation. Examples of suitable amorphous-forming components include iron, aluminum, titanium, copper, nickel, cobalt, manganese, zirconium, yttrium, boron, niobium, molybdenum, tungsten, or any combination thereof.

[0016] In some embodiments, the amorphous-forming components may include one or more lanthanides. For example, one or more lanthanides may constitute 1 mol% to 25 mol% (e.g., 5 mol% to 20 mol% or 10 mol% to 20 mol%) of the amorphous glass.

[0017] In some embodiments, two or more amorphous components may include one or more Group 4 elements. For example, one or more Group 4 elements may constitute 1 mol% to 15 mol% (e.g., 1 mol% to 10 mol% or 2 mol% to 8 mol%) of the amorphous glass.

[0018] In some embodiments, the amorphous-forming components include two or more amorphous elements, one or more Group 13 elements. For example, one or more Group 13 elements can constitute 1 mol% to 8 mol% (e.g., 2 mol% to 6 mol% or 3 mol% to 4 mol%) of the amorphous glass.

[0019] In some embodiments, amorphous glass includes glass defined by the following formula.

[0020] Si x Sny 1 AFM a 2 AFM b 3 AFM c 4 AFM d wherein 1 AFM, 2 AFM, 3 AFM and 4 AFM each represent different elements selected from iron, aluminum, titanium, copper, nickel, cobalt, manganese, gallium, indium, zirconium, and yttrium, x is 50 - 90, y is 1 - 40, a is 0.5 - 20, b is 0.5 - 15, c is 0 - 10, and d is 0 - 10.

[0021] In some examples, the amorphous glass can include SiSnCeFeAlTi glass (e.g., Si 60 Sn 12 Ce 18 Fe5Al3Ti2).

[0022] In some examples, the amorphous glass can include SiSnFeAlTi glass (e.g., Si 73 Sn 15 Fe6Al4Ti2).

[0023] In some examples, the amorphous glass can include SiSnAlTi glass (e.g., Si 78 Sn 16 Al4Ti2).

[0024] Particles can be formed by a wide variety of suitable methods. In some embodiments, particles can be formed by pulverizing bulk solid materials. For example, particles can be formed by ball milling or other suitable pulverization methods. In other embodiments, particles can be formed by a template process. In a suitable template process, particle size can be controlled by using a porous membrane or a self-assembled array of spherical particles as a template. For example, the template process may include absorbing a precursor solution containing a metal precursor into the template and calcining the template.

[0025] Optionally, in some embodiments, the particles may further include carbonaceous material disposed on the surface of the particles.

[0026] The particles can be dispersed in a binder. The binder may include polymeric binders such as vinylidene fluoride (PVDF), polyaniline, or a combination thereof. In some embodiments, the polymeric binder may include a conductive polymer. The binder may also include carbonaceous materials such as carbon black.

[0027] Electrochemical cells comprising the anode described herein are also provided. For example, an electrochemical cell comprising the anode, cathode and electrolyte disposed between the anode and cathode as described herein is provided. In some cases, the electrochemical cell can constitute a lithium-ion battery, and the cathode is a lithium-based cathode (e.g., lithium iron phosphate, LiNi 1-x Mn x / 2 Co x / 2O2 (where x = 0.4 or 0.2 in the formula) or LiNi 0.8 Co 0.15 Al 0.05 (Contains O2)

[0028] In some embodiments, the electrochemical cell can exhibit an energy density of at least 180 Wh / kg at room temperature.

[0029] In some embodiments, the electrochemical cell exhibits charging rates of 1 to 10 minutes up to 30% of the state of charge (SOC), 1 to 10 minutes up to 50% of the state of charge (SOC), 1 to 10 minutes up to 70% of the state of charge (SOC), and / or 1 to 10 minutes up to 90% of the state of charge (SOC).

[0030] A collection of particles formed from amorphous glass is also provided. Amorphous glass may include glass defined by the following formula.

[0031] Si x Sn y 1 AFM a 2 AFM b 3 AFM c 4 AFM d During the ceremony, 1 AFM, 2 AFM, 3 AFM and 4 AFM represents different elements selected from iron, aluminum, titanium, copper, nickel, cobalt, manganese, gallium, indium, zirconium, and yttrium, where x is between 50 and 90, y is between 1 and 40, a is between 0.5 and 20, b is between 0.5 and 15, c is between 0 and 10, and d is between 0 and 10.

[0032] The particle size and particle size distribution can vary. In some cases, the particles may have an aspect ratio of 10 or less, for example, an aspect ratio of 5 or less, or an aspect ratio of 2 or less. In some embodiments, the particles may be substantially spherical.

[0033] In one embodiment, the particles include a monodisperse collection of particles.

[0034] In some embodiments, the particles may include a collection of fine particles. For example, in some embodiments, the particles may include a collection of fine particles that have an average particle size of 1 to 15 microns (e.g., 1 to 5 microns) as measured by scanning electron microscopy (SEM). In other embodiments, the particles may include a collection of nanoparticles. For example, in some embodiments, the collection of nanoparticles may have an average particle size of 25 nm to less than 1 micron (e.g., 100 nm to 750 nm) as measured by scanning electron microscopy (SEM).

[0035] Two or more active ingredients can constitute 51 mol% to 99 mol% (e.g., 80 mol% to 95 mol%) of the amorphous glass. Two or more amorphous-forming components can constitute 1 mol% to 49 mol% (e.g., 5 mol% to 25 mol%, or 5 mol% to 20 mol%) of the amorphous glass. Two or more active ingredients and two or more amorphous-forming components can be present in the amorphous glass in molar ratios of 1.1:1 to 50:1, for example, 1.1:1 to 25:1, 2:1 to 25:1, 2:1 to 20:1, 4:1 to 20:1, 5:1 to 15:1, or 5:1 to 10:1. [Brief explanation of the drawing]

[0036] [Figure 1] Table 1 shows the X-ray diffraction patterns of the compositions shown (from top to bottom: Sn94Al4Ti2, Si94Al4Ti2, Si78Sn16Al4Ti2, Si73Sn15Fe6Al4Ti2, and Si60Sn12Ce18Fe5Al3Ti2) and the diffraction patterns of the corresponding species (Sn, SnO2, SnO, SiO2, and FeSi). [Figure 2] The images show backscatter scanning electron microscopy (SEM) images of Si78Sn16Al4Ti2 active particles before casting (panel a), a magnified view of the surface of the active particles (panel b), and EDS images of the SEM images shown in panel b, scanned for the elements Si (panel c), Al (panel d), Sn (panel e), and Ti (panel f). [Figure 3A]SEM micrographs of bulk Si73Sn15Fe6Al4Ti2 are shown. [Figure 3B] The image shows a SEM micrograph of a non-porous PHB film. [Figure 3C] This image shows a SEM micrograph of a porous PHB film fabricated using the phase inversion method. [Figure 3D] This image shows a SEM micrograph of a porous PHB film fabricated using the phase inversion method. [Figure 3E] This image shows a SEM micrograph of a porous PHB film fabricated using a phase inversion method during the template synthesis of amorphous metal particles. [Figure 3F] This image shows a SEM micrograph of a porous PHB film fabricated using a phase inversion method during the template synthesis of amorphous metal particles. [Figure 3G] This image shows a SEM micrograph of a porous PHB film fabricated using polystyrene nanospheres. [Figure 3H] This image shows a SEM micrograph of a porous PHB film fabricated using polystyrene nanospheres during the template synthesis of amorphous metal particles. [Figure 3I] This image shows a SEM micrograph of a porous PHB film fabricated using polystyrene nanospheres during the template synthesis of amorphous metal particles. [Figure 4A] Table 1 shows a plot of the rate capability test results for the compositions shown in the table, at rates ranging from C / 2 to 60C. [Figure 4B] Table 2 shows plots of rate capability tests for the compositions listed, ranging from C / 2 to 60C. [Figure 4C] Table 2 shows plots illustrating the capacity as a function of Sn percent in the compositions. The capacity was obtained from the final point at each rate for each composition. [Figure 5A] This shows long-term cycling plots of ball-milled amorphous metal and unmilled amorphous metal at a charge rate of 13C. The cells were cycled from 0.05V to 3V relative to Li / Li+. [Figure 5B]This plot shows the rate capacity test results for ball milled and unmilled materials at rates ranging from C / 2 to 60C. The cells were cycled from 0.05V to 3V relative to Li / Li+. [Figure 6] This plot shows comparative charge / discharge cycle data for Si73Sn15Al4Ti2Fe6, Si73Sn15Al4Ti2Fe6-SR1, Si73Sn15Al4Ti2Fe6-SR2, and Si73Sn15Al4Ti2Fe6-SR3, recorded at a current density of 6C in 1 mol L-1 LiPF6 in an EC / DMC 1:1 V / V solution. [Figure 7] This plot shows the capacities of Si73Sn15Al4Ti2Fe6-SR3 at a current density of 6C for electrodes with different masses of active material in 1 mol L-1 LiPF6 in an EC / DMC 1:1 V / V solution. [Figure 8] This is a plot showing the long-term cycling properties of Si73Sn15Al4Ti2Fe6. [Figure 9A] Figure 9A shows the volume of 0.32 mg of Si73Sn15Al4Ti2Fe6 in 1 mol L-1 LiPF6 in an EC:DMC 1:1 V / V solution after 1000 cycles at a current density of 6C. [Figure 9B] Figure 9B shows the volume of 0.4 mg of Si73Sn15Al4Ti2Fe6 in 1 mol L-1 LiPF6 in an EC:DMC 1:1 V / V solution after 1000 cycles at a current density of 6C. [Figure 10A] The rate of change in an electrode prepared from 0.3 mg of Si73Sn15Al4Ti2Fe6-SR3 in 1 mol L-1 LiPF6 in an EC:DMC 1:1 V / V solution is shown (Figure 10A). [Figure 10B] Figure 10B shows the rate change in an electrode prepared from 1.02 mg of Si73Sn15Al4Ti2Fe6-SR3 in 1 mol L-1 LiPF6 in an EC:DMC 1:1 V / V solution. [Figure 11]These are cyclic voltammograms of lithium and Si78Sn16Al4Ti2 half-cells cycled from 3V to 0.005V at 5mV / s, 2.5mV / s, 1mV / s, 0.5mV / s, 0.25mV / s, and 0.1mV / s. [Figure 12] These are cyclic voltammograms of sodium and Si78Sn16Al4Ti2 half-cells cycled from 3 V to 0.005 V at 35 V / s. [Figure 13] This is a rate performance plot of Si60Sn12Ce18Fe5Al3Ti2 and Si78Sn16Al4Ti2. Each composition is shown in two sets of colors. The sodium half-cells were cycled at rates of C / 24, C / 10, and C / 3. [Figure 14A] The charge / discharge profiles of all batteries, cycled at a rate of C / 6, with LiFePO4 as the working electrode and amorphous metals as the counter and reference electrodes, are shown. [Figure 14B] The charge / discharge cycle data for all batteries, cycled at a rate of 10C in a potential range of 1 to 3.5V for Li / Li+, is shown. [Figure 15A] The charge / discharge profiles of all batteries, cycled at a rate of C / 10, with LiFePO4 as the working electrode and amorphous metals as the counter and reference electrodes, are shown. [Figure 15B] The charge / discharge cycle data for all batteries, cycled at a rate of 10C within a potential range of 0.005 to 4.5V for Li / Li+, is shown. [Figure 16A] The charge / discharge cycle data for the entire battery, including the amorphous metal anode, reference electrode, and NMC working electrode, is shown (Figure 16A). [Figure 16B] The charge / discharge cycle data for the entire battery, including the amorphous metal anode and reference electrode, and the NCA as the working electrode, is shown (Figure 16B). The cells were cycled at a rate of 10C for Li / Li+ between 0.05 and 4.5V. [Modes for carrying out the invention]

[0037] Unless otherwise specified, abbreviations used herein have their conventional meanings within the field of chemistry.

[0038] As used herein and in the following claims, the terms “comprise” (and its forms, derivatives, or variations thereof, such as “comprising” and “comprises”) and “include” (and its forms, derivatives, or variations thereof, such as “including” and “includes”) are inclusive (i.e., non-limiting) and do not exclude additional elements or steps. For example, the terms “comprise” and / or “comprising,” as used herein, specify the presence of the described features, integers, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and / or groups thereof. Thus, these terms are intended not only to include the enumerated elements or steps, but may also include other elements or steps not expressly cited. Furthermore, as used herein, the use of the terms "a" or "an" in conjunction with an element may mean "one (kind)," but also coincides with the meanings of "one or more (kinds)," "at least one (kind)," and "one (kind) or more." Thus, an element preceded by "a" or "an" does not preclude the existence of additional identical elements, unless further constraints are imposed.

[0039] The use of the term "approximately" applies to all numerical values, whether explicitly stated or not. Generally, this term indicates a range of numbers that a person skilled in the art would consider to be a reasonable deviation of a given number (i.e., having equivalent function or results). For example, the term can be interpreted to include a deviation of ±10% of a given number, but only if such a deviation does not alter the final function or result of the value. Thus, a value of approximately 1% can be interpreted as a range of 0.9% to 1.1%. Furthermore, a range can be interpreted to include the beginning and end of the range. For example, unless otherwise specified herein, the range of 10% to 20% (i.e., the 10% to 20% range) may include 10%, and also include 20%, and include percentages between 10% and 20%.

[0040] Where combinations, subsets, or groups of elements (e.g., combinations of components in a composition, or combinations of steps in a method) are disclosed, specific references to each of the various individual and collective combinations and permutations of these elements may not be expressly disclosed, and each will be specifically considered and described herein. For example, where an item is described herein as comprising components of type A, type B, type C, or any combination thereof, it is understood that this phrase describes all of the various individual and collective combinations and permutations of these components. For example, in some embodiments, the item described by this phrase may include only components of type A. In some embodiments, the item described by this phrase may include only components of type B. In some embodiments, the item described by this phrase may include only components of type C. In some embodiments, the item described by this phrase may include components of type A and type B. In some embodiments, the item described by this phrase may include components of type A and type C. In some embodiments, the item described by this phrase may include components of type B and type C. In some embodiments, the item described by this phrase may include components of type A, components of type B, and components of type C. In some embodiments, the item described by this phrase may include two or more components of type A (e.g., A1 and A2). In some embodiments, the item described by this phrase may include two or more components of type B (e.g., B1 and B2). In some embodiments, the item described by this phrase may include two or more components of type C (e.g., C1 and C2).In some embodiments, the items described by this phrase may include two or more first components (e.g., two or more type A components (A1 and A2)), optionally one or more second components (e.g., optionally one or more type B components), and optionally one or more third components (e.g., optionally one or more type C components). In some embodiments, the items described by this phrase may include two or more first components (e.g., two or more type C components (C1 and C2)), optionally one or more second components (e.g., optionally one or more type A components), and optionally one or more third components (e.g., optionally one or more type B components). The phrases “the combination” and “the arbitrary combination” are used as synonyms herein.

[0041] As used herein, the terms “active ingredient” and “active material” are used synonymously and refer to a substance that reacts with a working ion (e.g., lithium) under conditions that normally occur during the charging and discharging of a battery (e.g., a lithium-ion battery). Most amorphous glasses described herein may contain two or more active ingredients.

[0042] As used herein, the terms “inactive component” and “inactive substance” are used synonymously and refer to substances that do not react with working ions (e.g., lithium) under conditions that normally occur during the charging and discharging of batteries (e.g., lithium-ion batteries). Two or more inactive components may be present as minor components of the amorphous glass described herein.

[0043] As used herein, the term “metal” refers to both metals and metalloids such as silicon and germanium. Metals are often in their elemental state.

[0044] As used herein, the term "lithiating" refers to the process of adding lithium to the amorphous glass described herein (i.e., the reduction of lithium ions). Similarly, the term "sodiumating" refers to a similar process in which sodium is added to the amorphous glass described herein.

[0045] As used herein, the term “delithiation” refers to the process of removing lithium from the amorphous glass described herein (i.e., the oxidation of lithium ions). Similarly, the term “desodiumlation” refers to a similar process in which sodium is removed from the amorphous glass described herein.

[0046] As used herein, the term "charging" refers to the process of supplying electrochemical energy to a battery.

[0047] As used herein, the term “discharge” refers to the process of removing electrochemical energy from a battery (i.e., discharge is the process of using a battery to perform a useful task).

[0048] As used herein, the term "cathode" refers to the electrode on which electrochemical reduction occurs during the discharge process. During discharge, the cathode is lithified. During charging, lithium atoms are removed from this electrode.

[0049] As used herein, the term "anode" refers to an electrode that undergoes electrochemical oxidation during the discharge process. During discharge, the anode is delithiated. During charging, lithium atoms are added to this electrode.

[0050] As used herein, "monodisperse" and "uniform particle size distribution" generally refer to a group of particles where all particles are the same or nearly the same diameter. As used herein, monodisperse distribution refers to a particle distribution where 80% of the distribution (e.g., 85%, 90%, or 95%) is within 25% of the median particle size (e.g., within 20%, 15%, 10%, or 5%).

[0051] Provided herein is an anode comprising particles formed from amorphous glass. The amorphous glass can be formed from a mixture comprising two or more active ingredients and two or more amorphous-forming ingredients.

[0052] The particle size and particle size distribution can vary. The particles can have any preferred shape or combination of shapes. For example, particles can be flattened, elongated, bladed, isotropic, or a combination thereof. In some embodiments, the particles can be non-fibrous. Elongated particles and fibers can be characterized with respect to their aspect ratio. As used herein, “aspect ratio” refers to the length divided by the diameter of the particle or fiber. In some cases, particles can have an aspect ratio of 10 or less, for example, an aspect ratio of 5 or less, or an aspect ratio of 2 or less. In some embodiments, the particles can be substantially spherical.

[0053] A population of particles may have an average particle size. "Average particle size" and "mean particle size" are used interchangeably herein and generally represent the statistically average particle size of a particle in a population. For substantially spherical particles, the particle diameter may represent, for example, the hydrodynamic diameter. As used herein, the hydrodynamic diameter of a particle may represent the maximum straight-line distance between two points on the surface of the particle. For non-spherical particles, the particle diameter may represent, for example, the minimum cross-sectional dimension of the particle (i.e., the minimum straight-line distance passing through the center of the particle and intersecting two points on the surface of the particle). The average particle size can be measured using methods known in the art, such as scanning electron microscopy (SEM), transmission electron microscopy, and / or evaluation by dynamic light scattering.

[0054] In some embodiments, the particles may include a collection of fine particles. For example, in some embodiments, the particles may include a collection of fine particles having an average particle size of at least 1 micron (e.g., at least 2 microns, at least 3 microns, at least 4 microns, at least 5 microns, at least 6 microns, at least 7 microns, at least 8 microns, at least 9 microns, at least 10 microns, at least 11 microns, at least 12 microns, at least 13 microns or at least 14 microns) as measured by SEM. In some embodiments, the particles may include a collection of fine particles having an average particle size of 15 microns or less (e.g., 14 microns or less, 13 microns or less, 12 microns or less, 11 microns or less, 10 microns or less, 9 microns or less, 8 microns or less, 7 microns or less, 6 microns or less, 5 microns or less, 4 microns or less, 3 microns or less or 2 microns or less) as measured by SEM.

[0055] The particles may include a population of fine particles having an average particle size ranging from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, the particles may include a population of fine particles having an average particle size of 1 to 15 microns (e.g., 1 to 5 microns) as measured by SEM.

[0056] In some embodiments, the particles may include a collection of nanoparticles. For example, in some embodiments, the particles may include a collection of nanoparticles having an average particle size of at least 25 nm (e.g., at least 50 nm, at least 100 nm, at least 150 nm, at least 200 nm, at least 250 nm, at least 300 nm, at least 350 nm, at least 400 nm, at least 450 nm, at least 500 nm, at least 550 nm, at least 600 nm, at least 650 nm, at least 700 nm, at least 750 nm, at least 800 nm, at least 850 nm, at least 900 nm, or at least 950 nm) as measured by SEM. In some embodiments, the particles may include a population of nanoparticles having an average particle size of less than 1 micron (e.g., 950 nm or less, 900 nm or less, 850 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less, or 50 nm or less) as measured by SEM.

[0057] The particles may include a population of nanoparticles having an average particle size ranging from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, the particles may include a population of fine particles having an average particle size of 25 nm to less than 1 micron (e.g., 100 nm to 750 nm), as measured by SEM.

[0058] In some embodiments, the particle population is a monodisperse population of particles. In other embodiments, the particle population is a polydisperse population of particles. In some examples where the particle population is monodisperse, more than 50%, more preferably 60%, and most preferably 75% of the particle size distribution are within 10% of the median particle size.

[0059] In some embodiments, two or more active ingredients can constitute at least 51 mol% of amorphous glass (for example, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol%, at least 75 mol%, at least 80 mol%, at least 85 mol%, at least 90 mol%, or at least 95 mol%). In some embodiments, two or more active ingredients can constitute 99 mol% or less (for example, 95 mol% or less, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less, 60 mol% or less, or 55 mol% or less).

[0060] Two or more active ingredients can be present in amorphous glass in amounts ranging from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, two or more active ingredients can constitute 51 mol% to 99 mol% (e.g., 80 mol% to 95 mol%) of the amorphous glass.

[0061] In some embodiments, two or more amorphous-forming components can constitute at least 1 mol% of the amorphous glass (e.g., at least 5 mol%, at least 10 mol%, at least 15 mol%, at least 20 mol%, at least 25 mol%, at least 30 mol%, at least 35 mol%, at least 40 mol%, or at least 45 mol%). In some embodiments, two or more amorphous-forming components can constitute 49 mol% or less (e.g., 45 mol% or less, 40 mol% or less, 35 mol% or less, 30 mol% or less, 35 mol% or less, 20 mol% or less, 25 mol% or less, 10 mol% or less, or 5 mol% or less).

[0062] Two or more amorphous components can be present in the amorphous glass in amounts ranging from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, two or more amorphous components can constitute 1 mol% to 49 mol% (e.g., 5 mol% to 25 mol% or 5 mol% to 20 mol%) of the amorphous glass.

[0063] Two or more active ingredients and two or more amorphous-forming ingredients can be present in amorphous glass in molar ratios of 1.1:1 to 50:1, for example, 1.1:1 to 25:1, 2:1 to 25:1, 2:1 to 20:1, 4:1 to 20:1, 5:1 to 15:1, or 5:1 to 10:1.

[0064] The two or more active ingredients may include silicon, tin, lead, antimony, germanium, gallium, indium, bismuth, or any combination thereof. In some embodiments, the two or more active ingredients may include silicon, tin, antimony, germanium, or any combination thereof. In some embodiments, the two or more active ingredients may include silicon. In some embodiments, the two or more active ingredients may include tin.

[0065] In some embodiments, the amorphous glass may include SiSn-based glass (e.g., glass containing silicon, tin, optionally one or more additional active ingredients, and two or more amorphous components). In the case of SiSn-based amorphous glass, the two or more active ingredients include silicon and tin, and silicon and tin can be present in a molar ratio of 1.1:1 to 20:1 (e.g., 2:1 to 15:1 or 3:1 to 12:1).

[0066] The two or more amorphous-forming components may include electrochemically inert components that are favorable for glass formation. Suitable amorphous-forming components may include, but are not limited to, transition metals, rare earth metals, or combinations thereof. Examples of suitable amorphous-forming components include iron, aluminum, titanium, copper, nickel, cobalt, manganese, zirconium, yttrium, boron, niobium, molybdenum, tungsten, or any combination thereof. Other possible amorphous-forming components include chromium, tantalum, lanthanum, cerium, and mischmetal (i.e., mixtures of rare earth metals).

[0067] In some embodiments, the amorphous-forming components may include one or more lanthanides. For example, one or more lanthanides may constitute 1 mol% to 25 mol% (e.g., 5 mol% to 20 mol% or 10 mol% to 20 mol%) of the amorphous glass.

[0068] In some embodiments, two or more amorphous components may include one or more Group 4 elements. For example, one or more Group 4 elements may constitute 1 mol% to 15 mol% (e.g., 1 mol% to 10 mol% or 2 mol% to 8 mol%) of the amorphous glass.

[0069] In some embodiments, the amorphous-forming components include two or more amorphous elements, one or more Group 13 elements. For example, one or more Group 13 elements can constitute 1 mol% to 8 mol% (e.g., 2 mol% to 6 mol% or 3 mol% to 4 mol%) of the amorphous glass.

[0070] In some embodiments, amorphous glass includes glass defined by the following formula.

[0071] Si x Sn y 1 AFM a 2 AFM b 3 AFM c 4 AFM d During the ceremony, 1 AFM, 2 AFM, 3 AFM and 4 AFM represents different elements selected from iron, aluminum, titanium, copper, nickel, cobalt, manganese, gallium, indium, zirconium, and yttrium, where x is between 50 and 90, y is between 1 and 40, a is between 0.5 and 20, b is between 0.5 and 15, c is between 0 and 10, and d is between 0 and 10.

[0072] In some embodiments, x can be at least 50 (e.g., at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, or at least 85). In some embodiments, x can be 90 or less (e.g., 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, or 55 or less).

[0073] Depending on the circumstances, x may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, x can be 50 to 90 (e.g., 60 to 80).

[0074] In some embodiments, y can be at least 1 (e.g., at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, or at least 35). In some embodiments, y can be 40 or less (e.g., 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less).

[0075] Depending on the circumstances, y may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, y can be 1 to 40 (e.g., 5 to 20).

[0076] In some embodiments, a can be at least 0.5 (e.g., at least 1, at least 2.5, at least 5, at least 7.5, at least 10, or at least 15). In some embodiments, a can be 20 or less (e.g., 15 or less, 10 or less, 7.5 or less, 5 or less, 2.5 or less, or 1 or less).

[0077] Depending on the circumstances, a may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, a can be 0.5 to 20 (e.g., 2.5 to 15).

[0078] In some embodiments, b can be at least 0.5 (e.g., at least 1, at least 2.5, at least 5, at least 7.5, or at least 10). In some embodiments, b can be 15 or less (e.g., 10 or less, 7.5 or less, 5 or less, 2.5 or less, or 1 or less).

[0079] Depending on the circumstances, b may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, b can be between 0.5 and 15 (e.g., between 2.5 and 10).

[0080] In some embodiments, c can be greater than 0 (e.g., at least 0.5, at least 1, at least 2.5, at least 5, or at least 7.5). In some embodiments, c can be 10 or less (e.g., 7.5 or less, 5 or less, 2.5 or less, 1 or less, or 0.5 or less).

[0081] Depending on the circumstances, c may range from one of the minimum values ​​to one of the maximum values ​​mentioned above. For example, in some embodiments, c can be 0 to 10 (e.g., 2.5 to 7.5).

[0082] In some embodiments, d can be greater than 0 (e.g., at least 0.5, at least 1, at least 2.5, at least 5, or at least 7.5). In some embodiments, d can be 10 or less (e.g., 7.5 or less, 5 or less, 2.5 or less, 1 or less, or 0.5 or less).

[0083] Depending on the circumstances, d may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, d can be 0 to 10 (e.g., 2.5 to 7.5).

[0084] In some examples, amorphous glass is SiSnCeFeAlTi glass (e.g., Si 60 Sn 12 Ce 18 It can contain Fe5Al3Ti2.

[0085] In some examples, amorphous glass is SiSnFeAlTi glass (e.g., Si 73 Sn 15 It can contain Fe6Al4Ti2.

[0086] In some examples, amorphous glass is SiSnAlTi glass (e.g., Si 78 Sn 16 It can include Al4Ti2.

[0087] Particles can be formed by a wide variety of suitable methods. In some embodiments, particles can be formed by pulverizing bulk solid materials. For example, particles can be formed by ball milling or other suitable pulverization methods. In other embodiments, particles can be formed by a template process. In a suitable template process, particle size can be controlled by using a porous membrane or a self-assembled array of spherical particles as a template. For example, the template process may include absorbing a precursor solution containing a metal precursor into the template and calcining the template.

[0088] Optionally, in some embodiments, the particles may further include carbonaceous material disposed on the surface of the particles.

[0089] In some embodiments, the particles may further include carbonaceous material (e.g., residue from the thermal decomposition of a polymer template on which the particles are formed).

[0090] The particles described herein (formed from amorphous glass) can be dispersed in any suitable binder material to form an anode. In some embodiments, the binder may include a polymer binder. The polymer binder may include a conductive polymer, a nonconductive polymer, or a combination thereof. In some embodiments, the anode may include the particles described herein dispersed in an elastomeric polymer binder. Suitable elastomeric polymer binders include polyolefins such as those prepared from ethylene, propylene, or butylene monomers; fluorinated polyolefins such as those prepared from polyaniline or vinylidene fluoride monomers; perfluorinated polyolefins such as those prepared from hexafluoropropylene monomers; perfluorinated poly(alkyl vinyl ethers); perfluorinated poly(alkoxy vinyl ethers) or a combination thereof. Specific examples of elastomeric polymer binders include vinylidene fluoride (PVDF), tetrafluoroethylene and propylene terpolymers, and vinylidene fluoride and hexafluoropropylene copolymers. Examples of commercially available fluorinated elastomers include those sold by Dyneon, LLC in Oakdale, Minnesota, under the product names "FC-2178," "FC-2179," and "BRE-731X."

[0091] In some cases, the binder may include polymer binders such as vinylidene fluoride (PVDF), polyaniline, or combinations thereof. In some embodiments, the polymer binder may include conductive polymers.

[0092] If it is desired to construct a specific anode, the binder can be crosslinked. Crosslinking can improve the mechanical properties of the polymer and / or improve contact between the particles and any conductive diluents that may be present.

[0093] Optionally, a conductive diluent can be added to facilitate electron transfer from particles to the current collector. Examples of conductive diluents include, but are not limited to, carbon, metals, metal nitrides, metal carbides, metal silicides, and metal borides. In some anodes, the conductive diluent may be carbon black, acetylene black, furnace black, lamp black, graphite, carbon fiber, or a combination thereof, such as those commercially available from MMM Carbon of Belgium under the trade names "SUPER P" and "SUPER S," and from Chevron Chemical Corporation of Houston, Texas under the trade name "SHAWANIGAN BLACK." In some cases, the binder may include carbonaceous materials such as carbon black.

[0094] The anode may further include an adhesion promoter that facilitates the adhesion of particles and conductive diluents to the polymer binder. The combination of the adhesion promoter and the polymer binder at least partially accommodates the volume changes that may occur in the alloy composition during repeated lithiation and delithiation cycles. The adhesion promoter may be part of the binder (e.g., in the form of a functional group), or it may be in the form of a coating on the alloy composition, a conductive diluent, or a combination thereof. Examples of adhesion promoters include, but are not limited to, silanes, titanates, and phosphonates described in U.S. Patent Application Publication No. 2003 / 0058240, the disclosure of which is incorporated herein by reference.

[0095] Any suitable electrolyte can be included in the lithium-ion battery. The electrolyte can be in solid or liquid form. Exemplary solid electrolytes include polymer electrolytes such as polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, fluorine-containing copolymers, polyacrylonitrile, or combinations thereof. Exemplary liquid electrolytes include ethylene carbonate, dimethyl carbonate, diethyl carbonate, propylene carbonate, gamma-butyrolactone, tetrahydrofuran, 1,2-dimethoxyethane, dioxolane, or combinations thereof. Electrolytes include lithium electrolyte salts such as LiPF6, LiBF4, LiClO4, LiN(SO2CF3)2, and LiN(SO2CF2CF3)2.

[0096] The electrolyte may include redox shuttle molecules, i.e., electrochemically reversible materials that can be oxidized at the cathode during charging, move to the anode, where they can be reduced to reform an unoxidized (or less oxidized) shuttle species and return to the cathode. Suitable redox shuttle molecules include, for example, those described in U.S. Patent No. 5,709,968 (Shimizu), U.S. Patent No. 5,763,119 (Adachi), U.S. Patent No. 5,536,599 (Alamgir et al.), U.S. Patent No. 5,858,573 (Abraham et al.), U.S. Patent No. 5,882,812 (Visco et al.), U.S. Patent No. 6,004,698 (Richardson et al.), U.S. Patent No. 6,045,952 (Kerr et al.), and U.S. Patent No. 6,387,571 B1 (Lain et al.), as well as PCT published patent application WO 01 / 29920 A1 (Richardson et al.).

[0097] Any suitable cathode known to be used in lithium-ion batteries can be utilized. Some exemplary cathodes in a charged state contain lithium atoms inserted within lithium transition metal oxides such as lithium cobalt dioxide, lithium nickel dioxide, and lithium manganese dioxide. Other exemplary cathodes are disclosed in U.S. Patent No. 6,680,145B2 (Obrovac et al.), which is incorporated herein by reference. That is, the cathode may contain particles containing transition metal particles (e.g., iron, cobalt, chromium, nickel, vanadium, manganese, copper, zinc, zirconium, molybdenum, niobium, or combinations thereof) having a particle size of about 50 nanometers or less, in combination with lithium-containing particles selected from lithium oxide, lithium sulfide, lithium halide (e.g., chloride, bromide, iodide, or fluoride) or combinations thereof. These particles may be used alone or in combination with lithium transition metal oxide materials such as lithium cobalt dioxide.

[0098] In some lithium-ion batteries with a solid electrolyte, the cathode can contain LiV3O8 or LiV2O5. In other lithium-ion batteries with a liquid electrolyte, the cathode can contain LiCoO2, LiCo 0.2 Ni 0.8 It may contain O2, LiMn2O4, LiFePO4, or LiNiO2.

[0099] In some cases, an electrochemical cell can constitute a lithium-ion battery, and the cathode is a lithium-based cathode (e.g., lithium iron phosphate, LiNi 1-x Mn x / 2 Co x / 2O2 (where x = 0.4 or 0.2 in the formula) or LiNi 0.8 Co 0.15 Al 0.05 (Contains O2)

[0100] Lithium-ion batteries can be used as a power source in a wide variety of applications. For example, lithium-ion batteries can be used to power electronic devices such as computers, various portable devices, automobiles, power tools, photographic equipment, and communication equipment. Multiple lithium-ion batteries can be combined to provide battery packs.

[0101] In some embodiments, the electrochemical cell can exhibit an energy density of at least 180 Wh / kg at room temperature.

[0102] In some embodiments, the electrochemical cell exhibits charging rates of 1 to 10 minutes up to 30% of the state of charge (SOC), 1 to 10 minutes up to 50% of the state of charge (SOC), 1 to 10 minutes up to 70% of the state of charge (SOC), and / or 1 to 10 minutes up to 90% of the state of charge (SOC).

[0103] A collection of particles formed from amorphous glass is also provided. Amorphous glass may include glass defined by the following formula.

[0104] Si x Sn y 1 AFM a 2 AFM b 3 AFM c 4 AFM d During the ceremony, 1 AFM, 2 AFM, 3 AFM and 4 AFM represents different elements selected from iron, aluminum, titanium, copper, nickel, cobalt, manganese, gallium, indium, zirconium, and yttrium, where x is between 50 and 90, y is between 1 and 40, a is between 0.5 and 20, b is between 0.5 and 15, c is between 0 and 10, and d is between 0 and 10.

[0105] In some embodiments, x can be at least 50 (e.g., at least 55, at least 60, at least 65, at least 70, at least 75, at least 80, or at least 85). In some embodiments, x can be 90 or less (e.g., 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, or 55 or less).

[0106] Depending on the circumstances, x may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, x can be 50 to 90 (e.g., 60 to 80).

[0107] In some embodiments, y can be at least 1 (e.g., at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, or at least 35). In some embodiments, y can be 40 or less (e.g., 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less).

[0108] Depending on the circumstances, y may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, y can be 1 to 40 (e.g., 5 to 20).

[0109] In some embodiments, a can be at least 0.5 (e.g., at least 1, at least 2.5, at least 5, at least 7.5, at least 10, or at least 15). In some embodiments, a can be 20 or less (e.g., 15 or less, 10 or less, 7.5 or less, 5 or less, 2.5 or less, or 1 or less).

[0110] Depending on the circumstances, a may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, a can be 0.5 to 20 (e.g., 2.5 to 15).

[0111] In some embodiments, b can be at least 0.5 (e.g., at least 1, at least 2.5, at least 5, at least 7.5, or at least 10). In some embodiments, b can be 15 or less (e.g., 10 or less, 7.5 or less, 5 or less, 2.5 or less, or 1 or less).

[0112] Depending on the circumstances, b may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, b can be between 0.5 and 15 (e.g., between 2.5 and 10).

[0113] In some embodiments, c can be greater than 0 (e.g., at least 0.5, at least 1, at least 2.5, at least 5, or at least 7.5). In some embodiments, c can be 10 or less (e.g., 7.5 or less, 5 or less, 2.5 or less, 1 or less, or 0.5 or less).

[0114] Depending on the circumstances, c may range from one of the minimum values ​​to one of the maximum values ​​mentioned above. For example, in some embodiments, c can be 0 to 10 (e.g., 2.5 to 7.5).

[0115] In some embodiments, d can be greater than 0 (e.g., at least 0.5, at least 1, at least 2.5, at least 5, or at least 7.5). In some embodiments, d can be 10 or less (e.g., 7.5 or less, 5 or less, 2.5 or less, 1 or less, or 0.5 or less).

[0116] Depending on the circumstances, d may range from any of the minimum values ​​to any of the maximum values ​​mentioned above. For example, in some embodiments, d can be 0 to 10 (e.g., 2.5 to 7.5).

[0117] In some examples, amorphous glass is SiSnCeFeAlTi glass (e.g., Si 60 Sn 12 Ce 18It can contain Fe5Al3Ti2).

[0118] In some examples, the amorphous glass can contain SiSnFeAlTi glass (e.g., Si 73 Sn 15 Fe6Al4Ti2).

[0119] In some examples, the amorphous glass can contain SiSnAlTi glass (e.g., Si 78 Sn 16 Al4Ti2).

[0120] The particle size and particle size distribution of the particles can vary. In some cases, the particles can have an aspect ratio of 10 or less, such as an aspect ratio of 5 or less or an aspect ratio of 2 or less. In certain embodiments, the particles can be substantially spherical.

[0121] In certain embodiments, the particles include a monodisperse population of particles.

[0122] In some embodiments, the particles can include a population of microparticles. For example, in some embodiments, the particles can include a population of microparticles having an average particle size of 1 micron to 15 microns (such as 1 micron to 5 microns) as measured by scanning electron microscopy (SEM). In other embodiments, the particles can include a population of nanoparticles. For example, in some embodiments, the population of nanoparticles has an average particle size of 25 nm to less than 1 micron (such as 100 nm to 750 nm) as measured by scanning electron microscopy (SEM).

[0123] Two or more active components can constitute 51 mol% to 99 mol% (for example, 80 mol% to 95 mol%) of the amorphous glass. Two or more amorphous forming components can constitute 1 mol% to 49 mol% (for example, 5 mol% to 25 mol%, or 5 mol% to 20 mol%) of the amorphous glass. Two or more active components and two or more amorphous forming components can be present in the amorphous glass at a molar ratio of 1.1:1 to 50:1, for example, 1.1:1 to 25:1, 2:1 to 25:1, 2:1 to 20:1, 4:1 to 20:1, 5:1 to 15:1, or 5:1 to 10:1.

[0124] As a non-limiting exemplification, examples of certain embodiments of the present disclosure are shown below.

Example

[0125] Example 1 Ultra-fast Charging Battery by Design of Materials and Cell Architecture In this example, the influence of the inert matrix composition on the lithiation performance was investigated (Table 1). After identifying the relevant elements in the inert matrix, Si x Sn y composition (Table 2) was changed to confirm the relationship between the Si x Sn y composition and the Li-ion battery anode performance.

[0126]

Table 1

[0127]

Table 2

[0128] Si 60 Sn 12 Ce 18 Starting from Fe5Al3Ti2, the atomic percentage of Si in the amorphous alloy shown in Table 1 gradually increased by incremental removal of each element. According to the electrochemical performance, Si 78 Sn 16Al4Ti2 was shown to exhibit the highest capacity at each charge rate. Therefore, this composition was selected for further processing and optimization. Gradual removal of each element provided insights into the role of each element in lithiation efficiency. Furthermore, removal of Sn from the overall composition dramatically reduced the cell capacity at all rates, suggesting that Sn plays a crucial role in this system. The electrochemical performance of the anode was evaluated with compositions containing 0-94 mol% Si, 0-94 mol% Sn, 0-18 mol% lanthanide elements, 0-8 mol% (e.g., 3-4 mol%) Al, Ga, In or a combination thereof, and 0-10 mol% (e.g., 2-8 mol%) of one or more group IV transition metals.

[0129] Table 1 summarizes the amorphous material compositions investigated in this embodiment. Each amorphous composition generally consists of Si and Sn, which are lithiable and can be used as anodes in Li-ion batteries, within an inert matrix containing Fe, Ti, Al, and / or Ce. Adding inert elements of various atomic radii can induce the formation of amorphous phases, which is beneficial for cycle stability at higher rates. Si-based ternary metal glass alloys composed of Si-M1-M2 (M1 = 20-40 atomic percent of Sn, Al, or a transition metal, M2 = 15-20 atomic percent of lanthanum or cerium) have been reported. In these alloys, Si and Sn function as the main lithium storage centers, while additional transition metals and lanthanides function as elements, enabling the formation of an amorphous matrix due to the mismatch in atomic sizes. The formation of the amorphous matrix prevents the crystallization of Si and mitigates the volume expansion caused by its lithiation. Furthermore, the presence of micro- to nano-sized crystalline regions of Sn embedded within the amorphous matrix can promote efficient lithiation within the electrode by functioning as lithium ion conduction pathways.

[0130] Materials and methods Materials. Polyhydroxybutyric acid porous membranes were prepared by phase inversion of a polymer solution of poly[(R)-3-hydroxybutyric acid] (PHB, Sigma Aldrich) and chloroform (99.9%, Fisher Scientific). Chloroform and ethanol (100%, Decon Labs, Inc., USA) were used as the phase inversion bath solution.

[0131] PHB porous membranes obtained from polystyrene nanospheres were prepared by adding dimethyl carbonate (DMC, Sigma Aldrich) to a PHB solution in ethylene carbonate (EC, Sigma Aldrich) (3:2 w / w). Separately, a suspension containing a 2.6% solid (w / v) aqueous solution of polystyrene nanospheres (100 nm in diameter, Polysciences, Inc., USA) was added to distilled water and Triton X-100 (Acros Organics, USA). Tetrahydrofuran (THF 99.9%, Sigma Aldrich) was used as a solvent for the polystyrene spheres.

[0132] All amorphous metal compositions were prepared using the following reagents: tin(II) chloride (SnCl2, 98%, Sigma-Aldrich Co., Ltd., USA), 3-aminopropyltriethoxysilane (C9H 23NO3Si, ≥98%, Sigma-Aldrich Co., Ltd., USA), aluminum chloride hexahydrate (AlCl3·6H2O, 99%, Sigma-Aldrich Co., Ltd., USA), titanium(IV) butoxide (Ti[O(CH2)3CH3]4, 99%, Acros Organics, USA), iron(III) nitrate nonhydrate (Fe(NO3)3·9H2O, ≥98%, Sigma-Aldrich Co., Ltd., USA) and cerium(III) acetate hydrate (Ce(CH3CO2)3·H2O, 99.9%, Sigma-Aldrich Co., Ltd., USA). The metal salt was dissolved using a mixture of 3.5 g of N,N-dimethylformamide (DMF, MCB Reagents, Germany) and 5 g of distilled water, and 0.5 g of acetic acid (99%, Ricca Chemical Co., USA) as a solvent.

[0133] Synthesis of PHB porous membrane by phase inversion. A polymer solution was prepared by dissolving 6% w / w polyhydroxybutyric acid (Sigma Aldrich) in chloroform (Fisher Scientific) at 90°C for 1 hour with continuous magnetic stirring. A thin film of PHB was obtained by spin-coating the polymer solution onto a steel plate substrate (2500 rpm, 30 seconds). The substrate containing the PHB solution was immersed in a non-solvent bath (ethanol / chloroform, 9:1 v / v) and wet phase inversion was performed. During this process, the non-solvent came into contact with the PHB film. As the concentration of the non-solvent in the film increased, the gelation process began, and a porous film was formed.

[0134] Synthesis of PHB porous membranes using polystyrene nanospheres. PHB was dissolved in ethylene carbonate (EC, Sigma Aldrich) (3:2 w / w) at 120°C for 30 minutes with continuous magnetic stirring. Dimethyl carbonate (DMC, Sigma Aldrich) was added to obtain a viscose solution, and a polymer solution was prepared. Next, a suspension was prepared by adding 0.3 mL of distilled water and 2 μL of TritonX-100 to a 2.6% solid (w / v) aqueous solution of 100 nm diameter polystyrene nanospheres (500 nm diameter spheres were also used to compare different pore sizes). The nanosphere suspension was deposited on a glass substrate and dried in air. Subsequently, the dried nanosphere layer was coated with the PHB solution and dried again in air. When a PHB membrane containing polystyrene nanospheres was added to a tetrahydrofuran (THF 99.9%, Sigma Aldrich) bath for 2 hours to completely dissolve the spheres, a porous membrane was formed.

[0135] Synthesis of bulk amorphous metal alloys. All metal alloy compositions were synthesized using the following procedure. Reagents were added to vials and dissolved in a mixture of DMF, water, and acetic acid. The mixture was sonicated for 10 minutes until all components were dissolved. Three milliliters of the solution were transferred to a quartz boat and heated in a tubular furnace at 700°C for 2 hours under a slightly reducing atmosphere (5% 2, 95% Ar). The boat was then removed from the tubular furnace and rapidly cooled in air. The resulting alloy was ground into a fine powder using a mortar and pestle, or further processed in a DECO-0.4L planetary ball mill (Changsha Deco Equipment Co., Ltd.). Four grams of the as-synthesized material were added to an agate (99.9% SiO2) jar with agate balls in a ball-to-powder ratio of 15:1. The jar was sealed and ground at a rotational speed of 1100 rpm for 75 hours.

[0136] Template synthesis. In template synthesis, the previously obtained porous film is used in a metal solution (e.g., Si 73 Sn 15The samples were submerged in an Al4Ti2Fe6 solution for 24 hours to ensure complete immersion. Subsequently, using a quartz boat, the wetted films were baked at 700°C for 2 hours in a tubular furnace (TF55030A-1, Lindberg / BlueM®) under a reducing atmosphere (5% 2, 95% Ar). Furthermore, amorphous metal alloys (e.g., Si) were used. 73 Sn 15 Samples of Al4Ti2Fe6 were also prepared under the same conditions by directly adding the metal solution to the furnace, without any spatial limitations.

[0137] Material Characterization. The presence of crystalline phases within amorphous metals was investigated using an X-ray diffractometer (XRD, D8 Advance, Bruker) with CuKα (λ=1.54059 Å) radiation. Material morphology was investigated by scanning electron microscopy (SEM, Apreo LoVac High Resolution, FEI), and elemental analysis was performed by energy-dispersive X-ray spectroscopy (EDS). Thermal properties of the material were analyzed by TGA-DTG and DSC techniques. For TGA-DTG analysis, TA Instruments' Q50TGA was used in a flow-through (50 mL) solution. -1 ) Under an N2 atmosphere, temperature range of 25-900°C, 10°C interval -1 Use at the heating rate specified. For DSC analysis, Q20 DSC (TA Instruments) is flowed (50 mL). -1 ) Under an N2 atmosphere, temperature range of 25-600°C, 10°C interval -1 It is used in a heating gradient.

[0138] Electrode preparation. Electrodes used in all electrochemical experiments were prepared by combining pulverized alloys to form a slurry consisting of 80-90 wt% active material, 5-10 wt% carbon black (Carbon Vulcan Black XC-72R), 5-10 wt% polyvinylidene fluoride (PVDF, MTI Corp.), and N-methyl-2-pyrrolidone (NMP, MTI Corp.) as a solvent. The slurry was cast onto a thin copper foil (9 μm thick, MTI Corp.) with a thickness of 0.3 mm using a doctor blade coating system (MSK-AFA I, MTI Corp.). The cast film was dried in a vacuum oven at 100°C for 3-12 hours. Electrodes with a diameter of 12.5 mm were punched out and formed into lumps. These were then transferred to an Ar-filled glove box (mBraun), and O2 (<0.5 ppm) and H2O (<0.5 ppm) were continuously detected.

[0139] Electrochemical Characterization. Electrodes were assembled to form a two-electrode CR2032 coin cell. High-purity lithium metal (0.3 mm thick, Chemetall Foote Corp.) was used as the counter electrode and reference electrode combination. In the case of sodium cells, high-purity sodium metal was used as the counter electrode and reference electrode combination. Celgard™ 2400 immersed in electrolyte was used as a separator. In the case of lithium cells, lithium phosphohexafluoride (LiPF6) in a 1:1 volume mixture of ethyl carbonate and dimethyl carbonate (Purolyte A5 series, Novolyte Technologies) was used as the electrolyte. In the case of sodium cells, sodium phosphohexafluoride (NaPF6) in a 1:1 volume mixture of ethyl carbonate and dimethyl carbonate was used as the electrolyte. All battery experiments were conducted using CR2032 coin cells with amorphous metal as the anode and selected commercially available materials in excess as the cathode. The commercially available cathodes selected were LiFePO4 (LiFePO4, MTI Corp.), lithium nickel cobalt aluminum oxide (NCA, LiNiCoAlO2, Ni:Co:Al=8.15:1.5:0.35, MTI Corp.), and lithium nickel cobalt manganese oxide (LiNiCoMnO2, Ni:Co:Mn=8:1:1, MTI Corp.).

[0140] Chronopotentiometry experiments were performed by increasing the current density at 40.5 mA / g, 81 mA / g, 135 mA / g, 148 mA / g, 183 mA / g, 254 mA / g, 400 mA / g, 405 mA / g, 800 mA / g, 1000 mA / g, 1200 mA / g, 1227 mA / g, 1500 mA / g, 2025 mA / g, and 2382 mA / g. The cutoff potential of the lithium half-cell was 0.005 V to 3 V (relative to Li / Li). + The cutoff potential of the sodium half-cell was 0.005V to 3V (relative to Na / Na). + The total lithium-ion battery cutoff potential was 0.005V to 3V (relative to Li / Li). + ) and 0.005V~4.5V (relative to Li / Li +). Constant current experiments were conducted using a multi-channel VMP3 bipotentiostat (BioLogic, Grenoble, France). All experiments were conducted at room temperature. Cyclic voltammetry (CV) experiments of lithium half-cells were performed at 0.005V~3V (vs. Li / Li). + The experiment was conducted within a potential window of ). The voltage sweep speeds used were 0.1 mV / s, 0.25 mV / s, 0.5 mV / s, 1 mV / s, 2.5 mV / s, and 5 mV / s. The CV experiment of the sodium half-cell was performed at a sweep speed of 35 μV / s, yielding values ​​of 0.005 V to 3 V (vs. Na / Na). + The experiment was conducted using a potential window of ).

[0141] Results of material characterization X-ray diffraction. Figure 1 shows the diffraction patterns for each composition in Table 1, where oxides of each potentially electrochemically active chemical species, as well as additional chemical species corresponding to the peaks, are visible in the diffraction patterns. Original Si 60 Sn 12 Ce 18 The diffraction pattern of the Fe5Al3Ti2 composition shows no peaks indicating amorphous metal. When cerium is removed from the original composition, 39.8 ° , 46.3 ° , 67.7 ° and 81.8 ° A large peak is formed, which may be due to the FeSi intermetallic compound phase that forms between Fe and Si above 500°C. Further removal of the Fe component from the composition causes these large peaks to disappear, and a smaller peak is formed at an angle similar to that of β-Sn. For reference, the peak position of the β-Sn phase is shown by a solid black line at the bottom of the figure. 78 Sn 16 These relatively low-intensity peaks in the Al4Ti2 diffraction pattern are attributed to the formation of crystalline Sn within an otherwise amorphous network. Furthermore, the 26° peak is related to the presence of SnO2 in the alloy. The presence of this type was also confirmed using XPS (see below).

[0142] Finally, Si 94The diffraction pattern of Al4Ti2 shows no peaks, indicating that the resulting composition is amorphous. This is consistent with the pattern of the previous composition, in that all crystalline phases are formed from either Fe or Sn, and therefore, in the absence of these elements, the formation of any crystalline phase that would appear as a peak in the diffraction spectrum is inhibited.

[0143] Si 78 Sn 16 Al4T 2( Scanning electron microscopy and energy-dispersive X-ray spectroscopy of the bulk material. Scanning electron microscopy images of the amorphous metal before cycling were used to gain initial insights into the surface morphology of the particles before casting and lithiation. Since the synthesized product was ground using a mortar and pestle, the resulting product contains particles with a particle size distribution ranging from tens of microns to submicrons in length. Regardless of particle size, each was found to have a flat surface with no pores or further surface features. This is further emphasized by focusing on two larger particles seen in panel a of Figure 2, which indicate the absence of porous structures on the surface. Further images were taken closer to the surface of the larger particles seen in panel b of Figure 2. The surface contains micron-sized fine particles that appear as brighter spots on the surface, although there are no porous structures on the surface. Using a backscatter electron detector, the increased brightness of the fine particles is suggested to be due to their composition being composed of heavier elements, with Sn being the heaviest in this composition.

[0144] Energy-dispersive X-ray spectroscopy was used to determine the elemental distribution across the entire electrode surface. Focusing on the surface shown in panel b of Figure 2, all four constituent elements were scanned. Si showed a uniform distribution across the electrode surface, suggesting an amorphous distribution, except at locations where bright spots were observed in the backscatter SEM image. Al showed a relatively uniform distribution and no clear localization, but, like Si, was not present at locations where bright spots were seen in the SEM. Ti appeared to be uniformly distributed across the electrode, but due to the low atomic percentage in the composition, it was difficult to identify any potential aggregations of Ti in the sample. Finally, Sn showed a relatively uniform distribution across the electrode surface, but where stronger spots were observed in the SEM image, Sn appeared to be localized at the same locations. This indicates that Sn forms aggregates on the surface and exists independently of the rest of the amorphous distribution. This finding was consistent with the diffraction pattern seen in Figure 1, as the lower intensity Sn peaks would otherwise be present within the amorphous signal. The SEM image in panel b of Figure 2 clearly shows that these localizations of Sn also exist beneath the surface, suggesting that microcrystalline regions of Sn can be distributed throughout the entire active particle.

[0145] Si 78 Sn 16 Al4T 2(Scanning electron microscopy and energy-dispersive X-ray spectroscopy of ball-milled materials. To improve anode performance at accelerated discharge rates, the raw material was further processed with a ball mill to minimize the size of the active particles, thereby minimizing the diffusion distance of lithium ions. Ball milling of the raw material dramatically reduced the particle size, reducing the average diameter from 10 μm to 370 nm. The raw material contained the aforementioned large shapes, which prevented rapid diffusion of lithium ions and thus limited the anode's fast charging capability. However, further processing created much smaller shapes within the electrode, with some particles having a diameter of approximately 30 nm. These nano-sized active particles, along with the amorphous nature of the active material, formed a system with much higher conductivity for rapid charge and discharge. Thorough ball milling resulted in aggregation of even smaller particles, but this aggregation was not expected to adversely affect battery performance. Despite ball milling, some particles remained micron-sized, with some having a diameter of 2-3 microns. These larger particles were found to undergo lithiation to a similar degree as the active particles in the electrode before ball milling, due to their larger diameter.

[0146] Electrochemical performance of lithium half-cells The performance of each composition was adjusted. To investigate the rate capability of each composition, constant current charge-discharge tests were performed at current densities ranging from 148 mA / g to 1500 mA / g, as shown in Figure 4A. Since the theoretical capacity properties of the materials were unknown, the C rate was considered to be the time required for the voltage to reach the minimum and maximum values ​​of the window and for the battery to be fully charged or discharged. The current densities corresponding to specific discharge rates ranging from C / 2 to 60C can be seen in the table below. [Table 3]

[0147] The capacitance of each electrode was normalized to the weight of the active material within the electrode only. The weight of the carbon additive and the PVDF binder were not considered as factors in the weight normalization. Si 78 Sn 16It was clear that the Al4Ti2 composition consistently exhibited higher capacity than all other compositions. As shown in Figure 4A, at 148 mA / g, composition 3 showed a specific capacity of 434.8 mA h g-1, which was 29% higher than composition 1, 39% higher than composition 2, and 91% higher than composition 4. As seen in Figure 4A, this trend continued across all current densities. On average across all current densities, composition 3 performed 28% better than composition 1, 54% better than composition 2, and 89% better than composition 4. Furthermore, composition 3 exhibited minimal irreversible capacity loss, with a loss of only 4% after accelerated charge-discharge testing.

[0148] Removing cerium from the initial composition resulted in a noticeable decrease in the overall charge rate. This decrease is most likely due to the presence of the FeSi species observed in the diffraction pattern of composition 2. This crystalline phase can irreversibly alloy with lithium, leading to a dramatic loss of capacity. Subsequent removal of the Fe component from the amorphous metal resulted in a dramatic increase in capacity at all charge rates, even higher than that of the initial composition containing all elements. This change suggests that the presence of crystalline Sn in the sample plays a dramatic role in efficient lithiation, as a peak for crystalline Sn is observed in the diffraction pattern. This composition consistently exhibits high capacity at all charge rates. This more efficient lithiation further suggests that crystalline Sn, when present in the amorphous matrix, can be reversibly lithiated without dramatic, irreversible loss of capacity. Finally, removal of the Sn component from the overall composition resulted in a dramatic decrease in capacity at all charge rates. This indicates that Sn plays a crucial role as an electrochemically active species in lithiation. Removing this species from the overall composition results in the smallest volume among all four compositions.

[0149] To further investigate the role of Sn in the performance of these compositions, the original Si 78 Sn 16The amount of elements in the Al4Ti2 composition was gradually increased from 4% to 94%, and the capacities obtained at the same charge rate were compared. As shown in Figure 4B, as the Sn content gradually increased, the capacity increased up to a 16% composition, and then decreased as the Sn percentage increased to 94%. This change as a function of Sn percentage leads to the conclusion that Sn plays a crucial role in lithiation in this system. As shown in Figure 4C, the composition containing 16% Sn consistently has the highest capacity at almost all charge rates. However, when higher current densities are applied, a tendency for different capacities to occur with gradually increasing Sn percentages emerges. At lower current densities, the capacity increases with the addition of 4% to 8% Sn, with the most dramatic change occurring between 8% and 16%. However, at current densities above 400 mA / g, the capacity decreases slightly with the addition of 4% to 8% Sn, but dramatically increases between 8% and 16%. It should be noted that, with higher percentage Sn compositions such as 78% and 94%, the 78% composition consistently exhibits higher capacity than the 94% composition at lower current densities. However, at current densities above 800 mA / g, the 94% composition exhibits higher capacity than the 78% composition. Relatively speaking, among higher percentage compositions, it should be noted that the 16% Sn composition still exhibits higher capacity at almost all charge rates. The consistent increase in the 16% composition may be due to Sn acting as a central lithium storage site within the electrode. Too little Sn in the electrode results in a dramatic loss of capacity, as seen in the 4% and 8% compositions, but the addition of excess Sn leads to the formation of large crystalline Sn centers rather than microcrystalline centers within an amorphous matrix, as seen in the 16% composition, resulting in the severe capacity degradation seen in pure Sn electrodes. The change in trend as a function of charge rate may be due to the ability of lithium to diffuse throughout the electrode. At lower rates, lithium can access the Sn centers throughout the active particles, but at higher rates, lithium can only reach the Sn particles near the surface. However, regardless of the charge rate, the 16% composition exhibits maximum capacity and therefore contains an amount of Sn that promotes efficient lithiation.

[0150] Performance of Ball Mill Grinding Materials. To effectively compare the performance of pre-treatment and post-treatment, comparative rate-capacity plots were created for untreated amorphous metal and ball mill grinding materials. Long-term cycling performance was performed over a period of 500 cycles at a current density of 1000 mA / g corresponding to a charge rate of 13C. As shown in Figure 5A, the ball mill grinding material exhibits significantly higher capacity in all cycles, thus outperforming the raw material. In the first cycle, the ball mill grinding material showed a capacity of 240.6 mAh / g, while the raw material showed a capacity of 63.8 mAh / g. This difference was evident throughout the 500 cycles, as the ball mill grinding material showed a capacity of 195.4 mAh / g at the 250th cycle and 175 mAh / g at the 500th cycle. For comparison, the raw material showed a capacity of 18.8 mAh / g at the 250th cycle and 18.14 mAh / g at the 500th cycle. The ability of amorphous metals to be efficiently lithium-ionized at a fast charging rate is highlighted by the fact that the processed material exhibits a capacity more than 10 times that of the raw material over a very large number of cycles.

[0151] To further compare treated and untreated amorphous materials, the rate capacity of ball-milled amorphous metal was compared to the performance of untreated amorphous metal. A comparison of the two at increasing high rates is shown in Figure 5B. Initially, at relatively low rates from C / 2 to 2C, the ball-milled material did not perform significantly better than the raw material. This was due to the fact that, regardless of particle size, low rates allowed lithium to diffuse deeply into the active particles. As a result, both the ball-milled material and the raw material could approach the same amount of lithiation sites in the electrode. However, at high rates, the treated material performed significantly better than the raw material. At high rates of 6C to 60C, the ball-milled amorphous metal showed an average performance of 190% better, and an average of 69 mAh / g more than the raw material. This was due to the considerably smaller particle size in the ball-milled material. At higher charging rates, lithium ions could diffuse throughout the nano-sized particles and thus reach all lithiation sites in the active material. However, with larger particles, a high charging rate allows the charge to approach only particles near the surface, resulting in fewer active sites being reached and a lower capacity compared to smaller particles.

[0152] Further results. Si prepared using different synthesis methods. 73 Sn 15 Performance of anodes formed using Fe6Al4Ti2. Figure 6 shows 1 mol L in EC / DMC 1:1 V / V solution. -1 Si recorded at a current density of 6C in LiPF6. 73 Sn 15 Al4Ti2Fe6, Si 73 Sn 15 Al4Ti2Fe6SR1, Si 73 Sn 15 Al4Ti2Fe6-SR2 and Si 73 Sn 15 This plot shows comparative charge / discharge cycle data for Al4Ti2Fe6-SR3.

[0153] The effect of adding amorphous metals to the anode was also evaluated. Specifically, Si73 Sn 15 Anodes were prepared using four different amounts of Al4Ti2Fe6. Figure 7 shows 1 mol L in EC / DMC 1:1 V / V solution. -1 Si at a current density of 6C for electrodes with different masses of active material in LiPF6. 73 Sn 15 This plot shows the volume of Al4Ti2Fe6-SR3. As shown in Figure 7, the volume generally decreased as the amount added increased.

[0154] Si 73 Sn 15 The long-term cycling properties of the anode formed from Al4Ti2Fe6 were also evaluated. As shown in Figures 8, 9A, and 9B, Si 73 Sn 15 The capacity and capacity retention of Al4Ti2Fe6 remained relatively constant over 1000 cycles at a current density of 6C.

[0155] Figures 10A and 10B show 1 mol L in EC:DMC 1:1 V / V solution. -1 In LiPF6, Si 73 Sn 15 Al4Ti2Fe6-SR3 0.3mg (Figure 10A) or Si 73 Sn 15 The rate changes in electrodes fabricated from Al4Ti2Fe6-SR3 1.02 mg (Figure 10B) are shown.

[0156] Figure 11 shows lithium and silicon ions cycled from 3V to 0.005V at 5mV / s, 2.5mV / s, 1mV / s, 0.5mV / s, 0.25mV / s, and 0.1mV / s. 78 Sn 16 This shows the cyclic voltammogram of an Al4Ti2 half-cell.

[0157] Electrochemical performance of sodium half-cells While lithium-ion batteries are the most common type of rechargeable battery, considerable research has been conducted on using sodium as a substitute for lithium. The motivation behind this is the wide availability and ease of obtaining the metal. Lithium is less abundant and often has an uneven distribution on Earth, making it increasingly difficult to meet consumer demand. For this reason, sodium exists as an attractive alternative to lithium in rechargeable batteries. However, sodium has inherent drawbacks that limit its use in commercial batteries. One such drawback is its larger ionic radius compared to lithium (Na). + So, 1.02A, compared to Li + At 0.76A, stress within the electrode may increase. Furthermore, due to the lower reaction rate, it has a smaller capacity and inferior rate capability compared to lithium. A feasible sodium anode must be able to accommodate a large number of sodium ions without undergoing permanent deformation that would prevent further sodiumization.

[0158] To demonstrate the broad applicability of amorphous metals, we cycled them in a sodium half-cell instead of lithium. There were two motivations for this change. The larger ionic radius of sodium generates stress from expansion, but it can be accommodated by the amorphous matrix surrounding the electrochemically active Sn cluster. Furthermore, Sn is Na 15 It has been reported that Sn4 can be reversibly alloyed with sodium up to its maximum sodiumization state, which means that the electrochemically active region of the electrode should be efficiently sodiumized. Si as a cathode cycled at a low C / 24 rate. 78 Sn 16 A cyclic voltammogram of a sodium half-cell containing Al4Ti2 (Figure 12) demonstrates the material's ability to reversibly sodiumize. The charge transferred in each cycle gradually increases with the number of cycles, indicating that more material is accessed as the cell is charged and discharged.

[0159] The first test was conducted on Si 60 Sn 12 Ce18 Fe5Al3Ti2 composition and optimal Si 78 Sn 16 Al4Ti2 compositions were cycled at various rates to determine the amorphous metal rate capacity. Each of the two sets of compositions was cycled at rates of C / 24, C / 10, and C / 3. The results are shown in Figure 13. In the first cycling at C / 24, it was shown that the capacity increased as more material was accessed, and Si 78 Sn 16 The maximum capacity of the Al4Ti2 composition is 104.1 mAh / g, and Si 60 Sn 12 Ce 18 The maximum capacity of the Fe5Al3Ti2 composition was 61.9 mAh / g. Cycling at C / 10 showed a slight decrease in capacity for both compositions, with the maximum value being Si 78 Sn 16 Al4Ti2 has a capacity of 76.1 mAh / g, Si 60 Sn 12 Ce 18 Fe5Al3Ti2 had a capacity of 45.1 mAh / g. Finally, the C / 3 rate also showed a slight decrease in capacity, with the maximum value being Si 78 Sn 16 Al4Ti2 has a capacity of 42.0 mAh / g, Si 60 Sn 12 Ce 18 Fe5Al3Ti2 had a capacity of 24.7 mAh / g. Si was used at all rates. 78 Sn 16 Al4Ti2 is Si 60 Sn 12 Ce 18 It is clearly superior to Fe5Al3Ti2. This is consistent with the lithium-based results, as the Sn centers in the amorphous matrix function as major lithium and sodium storage sites, suggesting that both should be reversible alloying with minimal capacity loss.

[0160] Electrochemical performance of all batteries Lithium iron phosphate. Once the performance of amorphous metals in the half-cells was confirmed, those materials were used as the anode in the entire battery configuration. Instead of using lithium metal as the counter electrode / reference electrode and amorphous metal as the working electrode, alloys were used as both the counter electrode and reference electrode, while simultaneously using a wide variety of common commercially available materials as the working electrode. Common commercially available cathodes used in the entire battery were lithium iron phosphate (LiFePO4), NMC, and NCA. These materials have been confirmed as reliable cathodes that provide reasonable capacity and excellent cycleability, and were therefore selected and combined with amorphous metals to determine the performance of the entire battery.

[0161] LiFePO4 is considered a common candidate as a cathode material for next-generation lithium-ion batteries due to its long-term cycleability, low toxicity, and high abundance as a natural resource. In addition to these advantages, LiFePO4 is being considered for possible fast-charging applications and has been shown to be able to fully charge at rates exceeding 6C. LiFePO4 exists because the most common material is a class of polyanionic compounds for cathodes. When the cathode material is lithiated, lithium ions diffuse through channels along the

[0010] direction, creating a simple 1D lithium transport pathway. LiFePO4 exhibits better thermal stability and higher power capacity than standard lithium cobalt oxide commercially available cathodes. Therefore, LiFePO4 was selected as the first material to combine with the cathode to demonstrate the ability of amorphous metals to cycle when combined with the cathode.

[0162] To begin testing the entire battery configuration, a potential range of 3.5V to 1V was selected for chronopotentiometry testing. Cycling within this potential range showed stable performance, with SEI products forming in the initial cycles and stable charge / discharge cycles continuing. As shown in Figure 14A, the initial charge cycles included a plateau associated with SEI product formation, but all subsequent charge / discharge cycles showed a similar shape. This suggests that the cells operate within the initial potential range of 3.5V to 1V.

[0163] Figure 14B shows the specific capacitance obtained for all cells in this potential window. The capacitance was normalized with respect to both the mass of the active material present in the anode and the sum of the active masses of both the anode and cathode. In the cell, there was an excess of active material mass in the cathode, allowing sufficient charge to accumulate in the cathode and fully charge the anode. The capacitance normalized with respect to the anode mass showed an initial capacitance of 196.3 mAh / g, but a significant decrease in capacitance was observed, with 42% of the capacitance lost by the 50th cycle, resulting in a capacitance of 114.5 mAh / g, and 48% of the capacitance lost by the 100th cycle, resulting in a capacitance of 101.4 mAh / g.

[0164] Chronopotentiometric cycling within a 3.5V to 1V window demonstrated the ability of LiFePO4 and amorphous metals to cycle continuously without immediate electrode degradation and subsequent cell death. These results dramatically expand the operating window by 2V, opening the potential window from 3.5V-1V to 4.5V-5mV. Opening the potential window offers several advantages to battery performance. A wider range allows for more potential to be applied to charging and discharging, potentially increasing specific capacity, and higher voltages ultimately increase the power within the cell. This could be beneficial for certain applications requiring higher power density, such as power tools, transportation systems, and medical devices.

[0165] As shown in Figure 15A, the initial chronopotentiometric cycling within the new potential window showed an initial charging cycle with distinct plateaus at 3.1V and 3.5V. Subsequent cycles showed plateaus at 3.2V in the charging cycle and 2.7V in the discharging cycle, but no plateaus were observed below 2.5V. These plateaus may be due to phase formation in the LiFePO4 cathode where lithium is incorporated into the lattice network. However, no phase formation was observed below 2.5V in the region where the anode lithiates, which also suggests that the anode maintains an amorphous structure through lithiating.

[0166] As shown in Figure 15B, the cell performance in the new potential region was again normalized to the mass of the anode only, and the initial anode capacity was 271.7 mAh / g, which decreased by 37% to 172.7 mAh / g by the 50th cycle, and by 42% to 160.7 mAh / g by the 100th cycle. When normalized to the sum of the anode and cathode masses, the cell showed an initial capacity of 170.4 mAh / g, which decreased by 37% to 108.3 mAh / g by the 50th cycle, and by 41% to 100.8 mAh / g by the 100th cycle.

[0167] Using LiFePO4 as the cathode material, cycleability is demonstrated within both potential windows, meaning that a wider window results in a higher power density within the cell. Considering the power density at each potential window, in the initial range of 3.5V to 1V, the cell is given a density of 490.8 Wh / kg in the initial cycle, decreasing to 286.3 Wh / kg by the 50th cycle and 253.5 Wh / kg by the 100th cycle. In comparison, in the 4.5V to 5mV window, the cell is given an initial power density of 1221.3 Wh / kg, decreasing to 776.3 Wh / kg by the 50th cycle and 722.3 Wh / kg by the 100th cycle. Opening the potential window not only increases the specific capacity but also further increases the power density. By opening the potential window, the specific capacity increases by an average of 149%, and the power density increases by 268%. This cell's ability to cycle across wider windows demonstrates its potential to act as a potential energy source for high-power applications.

[0168] NMC and NCA. While the use of polyanionic compounds in cathodes is being considered, transition metal oxides exist as the most common class of cathode materials, with LiCoO2 being the first and most commercially successful. LiCoO2 is extremely common due to its high theoretical capacity of 274 mAh / g and excellent cycling performance, but it exhibits inherent limitations. The main limitations of LiCoO2 are the low natural abundance, high cost, and relatively high toxicity of cobalt, which constitutes a significant portion of the cathode composition, as well as its poor thermal stability. As a result of these limitations, substitutions in the lattice have been made to reduce the cobalt content of the overall composition. Doping with nickel and Al has been shown to improve the thermal stability and electrochemical performance of the cathode. The result of these substitutions is LiNi 0.8 Co 0.15 Al 0.05 It uses an O2(NCA) cathode, and NCA exhibits a high discharge capacity of 200 mAh / g and has a considerably low cobalt content, making it a common alternative to LiCoO2.

[0169] In addition to NCA, LiLi 0.5 Mn 0.5 LiNi x Co y Mn z O 2(The values ​​obtained for x=0.33,0.68,0.80; y=0.33,0.18,0.10; z=0.33,0.18,0.1) (NMC) are also a common commercial alternative to LiCoO2, as NMC exhibits a reversible capacitance of 234 mAh / g. This commercial cathode allows for high-voltage operation in the high range of 4.5V while maintaining good cycle performance at high rates of 6C. For these reasons, NMC and NCA were selected as additional cathodes to be combined with amorphous metal anodes to further confirm their feasibility as potential commercial anode candidates. During cycling, both NMC and NCA exhibit a higher operating voltage range than LiFePO4, allowing the half-cell to be cycled at high levels of 4.5V. Therefore, a wider potential window than that used in LiFePO4 cycling was applied to the NMC and NCA cells combined with amorphous metal anodes.

[0170] When normalized to the anode mass, the cycling performance of the entire NMC battery shown in Figure 16A shows an initial capacity of 228.6 mAh / g, a 40% loss by the 50th cycle resulting in a capacity of 137.7 mAh / g, and a 46% loss by the 100th cycle resulting in a capacity of 124.1 mAh / g. Alternatively, the entire NCA battery shown in Figure 16B, when normalized to the anode mass, shows an initial capacity of 366.9 mAh / g, a 63% decrease by the 50th cycle resulting in a capacity of 135.6 mAh / g, and a 65% decrease by the 100th cycle resulting in a capacity of 127.3 mAh / g. Note that both NMC and NCA cells show considerable capacity degradation over 100 cycles, but the capacity stabilizes after 20 cycles. In NCA all-cells, the capacity degradation from cycle 20 to 100 is only 6%, compared to 15% in NMC cells. This initial degradation may be due to the larger diameter of the active material particles in the anode, which hinders the ability of lithium ions to diffuse from the solid. Reducing the diameter of the active particles could potentially mitigate this dramatic degradation in the first cycle.

[0171] The compositions and methods of the appended claims are not limited to the specific compositions and methods described herein, which are intended to be illustrative of two or three aspects of the claims. Any functionally equivalent compositions and methods are included within the claims. Various modifications of compositions and methods, in addition to those indicated and described herein, are included within the appended claims. Furthermore, while only a representative composition and method step is specifically described herein, other combinations of compositions and method steps, even if not specifically described, are included within the appended claims. Thus, while steps, elements, components, or combinations of components may be explicitly or hereafter referred to herein, other combinations of steps, elements, components, and components are included even if not explicitly mentioned.

[0172] As used herein, the term “comprising” and its variations are used synonymously with the term “including” and its variations, and are open and non-restrictive. While various embodiments have been described herein using the terms “comprising” and “including,” more specific embodiments of the invention can and are disclosed using the terms “essentially consisting of” and “consisting of” instead of “comprising” and “including.” Unless otherwise noted, all figures representing shapes, dimensions, etc., used herein and in the claims should be interpreted in light of significant figures and common rounding practices, and should not be understood as an attempt to limit, at least, the application of the doctrine of equivalents to the claims.

[0173] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the disclosed invention pertains. Publications cited herein and materials from which they are cited are incorporated more specifically by reference. Preferred embodiments of the present invention include the following: [1] An anode comprising particles formed from amorphous glass formed from a mixture containing two or more active ingredients and two or more amorphous-forming ingredients. [2] The anode according to [1], wherein the particles include a collection of fine particles. [3] The anode according to [2], wherein the collection of fine particles has an average particle size of 1 to 15 microns, for example, 1 to 5 microns, when determined by scanning electron microscopy (SEM). [4] The anode according to [1], wherein the particles include a collection of nanoparticles. [5] The anode according to [4], wherein the group of nanoparticles, when determined by scanning electron microscopy (SEM), has an average particle size of 25 nm to less than 1 micron, for example, 100 nm to 750 nm. [6] The anode according to any one of [1] to [5], wherein the particles include a monodisperse collection of particles. [7] The anode according to any one of [1] to [6], wherein the two or more active ingredients constitute 51 mol% to 99 mol% of the amorphous glass, for example, 80 mol% to 95 mol% of the amorphous glass. [8] The anode according to any one of [1] to [7], wherein the two or more amorphous-forming components constitute 1 mol% to 49 mol% of the amorphous glass, for example, 5 mol% to 25 mol% of the amorphous glass or 5 mol% to 20 mol% of the amorphous glass. [9] The anode according to any one of [1] to [8], wherein the two or more active ingredients and the two or more amorphous-forming ingredients are present in the amorphous glass in a molar ratio of 1.1:1 to 50:1, for example, 1.1:1 to 25:1, 2:1 to 25:1, 2:1 to 20:1, 4:1 to 20:1, 5:1 to 15:1, or 5:1 to 10:1.

[10] The anode according to any one of [1] to [9], wherein the two or more active ingredients include silicon, tin, lead, antimony, germanium, gallium, indium, bismuth, or any combination thereof.

[11] The anode according to any one of [1] to

[10] , wherein the two or more active ingredients can include silicon.

[12] The anode according to any one of [1] to

[11] , wherein the two or more active ingredients can include tin.

[13] The anode according to any one of [1] to

[12] , wherein the amorphous glass includes a SiSn-based glass.

[14] The anode according to

[13] , wherein the two or more active ingredients include silicon and tin, and the silicon and tin are present in a molar ratio of 1.1:1 to 20:1, for example, 2:1 to 15:1 or 3:1 to 12:1.

[15] The anode according to any one of [1] to

[14] , wherein the two or more amorphous-forming components include iron, aluminum, titanium, copper, nickel, cobalt, manganese, zirconium, yttrium, boron, niobium, molybdenum, tungsten, or any combination thereof.

[16] The anode according to any one of [1] to

[15] , wherein the two or more amorphous-forming components include one or more lanthanides.

[17] The anode according to

[16] , wherein one or more lanthanides constitute 1 mol% to 25 mol% of the amorphous glass, for example, 5 mol% to 20 mol% of the amorphous glass or 10 mol% to 20 mol% of the amorphous glass.

[18] The anode according to any one of [1] to

[17] , wherein the two or more amorphous-forming components include one or more Group 4 elements.

[19] The anode according to

[18] , wherein one or more Group 4 elements constitute 1 mol% to 15 mol% of the amorphous glass, for example, 1 mol% to 10 mol% of the amorphous glass or 2 mol% to 8 mol% of the amorphous glass.

[20] The anode according to any one of [1] to

[19] , wherein the two or more amorphous-forming components include one or more Group 13 elements.

[21] The anode according to

[20] , wherein one or more Group 13 elements constitute 1 mol% to 8 mol% of the amorphous glass, for example, 2 mol% to 6 mol% of the amorphous glass or 3 mol% to 4 mol% of the amorphous glass.

[22] The amorphous glass includes the glass defined by the following formula, according to any one of [1] to

[21] : Si x Sn y 1 AFM a 2 AFM b 3 AFM c 4 AFM d During the ceremony, 1 AFM, 2 AFM, 3 AFM and 4 AFM represents different elements selected from iron, aluminum, titanium, copper, nickel, cobalt, manganese, gallium, indium, zirconium, and yttrium, respectively. x is between 50 and 90. y is between 1 and 40, a is between 0.5 and 20. b is between 0.5 and 15. c is between 0 and 10, and d is between 0 and 10.

[23] The amorphous glass is Si 60 Sn 12 Ce 18 Fe 5 Al 3 Ti 2 An anode according to any one of [1] to

[22] , including SiSnCeFeAlTi glass such as the above.

[24] The amorphous glass is Si 73 Sn 15 Fe 6 Al 4 Ti 2 An anode according to any one of [1] to

[22] , including SiSnFeAlTi glass such as the above.

[25] The amorphous glass is Si 78 Sn 16 Al 4 Ti 2 An anode according to any one of [1] to

[22] , including SiSnAlTi glass such as the above.

[26] The anode according to any one of [1] to

[25] , wherein the particles are formed by ball mill grinding.

[27] The anode according to any one of [1] to

[25] , wherein the particles are formed by a template step.

[28] The anode according to

[27] , wherein the templating step uses a porous membrane as a template for controlling the particle size.

[29] The anode described in any of

[27] to

[28] , wherein the templating process includes the following: The process involves absorbing a precursor solution containing a metal precursor into a template, and Burn the aforementioned template.

[30] The anode according to any one of [1] to

[29] , wherein the particles have an aspect ratio of 10 or less, for example, an aspect ratio of 5 or less or an aspect ratio of 2 or less.

[31] The anode according to any one of [1] to

[30] , wherein the two or more amorphous-forming components include an inert component.

[32] The anode according to any one of [1] to

[31] , wherein the particles further comprise a carbonaceous material disposed on the surface of the particles.

[33] The anode according to any one of [1] to

[32] , wherein the particles are dispersed in a binder.

[34] The anode according to

[33] , wherein the binder comprises a polymer binder such as vinylidene fluoride (PVDF), polyaniline, or a combination thereof.

[35] The anode according to any one of

[33] to

[34] , wherein the binder comprises a conductive polymer.

[36] The anode according to any one of

[33] to

[35] , wherein the binder comprises a carbonaceous material such as carbon black.

[37] The anode according to any one of [1] to

[36] , wherein the particles react with an active ion selected from the group consisting of lithium ions, sodium ions, potassium ions, or combinations thereof, under conditions normally encountered during the charging and discharging of a battery containing the active ion, and the active ion can be stored.

[38] An electrochemical cell comprising an anode, a cathode, and an electrolyte disposed between the anode and the cathode, as described in any of [1] to

[37] .

[39] The electrochemical cell according to

[38] , wherein the electrochemical cell includes a lithium-ion battery and the cathode includes a lithium-based cathode.

[40] The cathode is lithium iron phosphate, LiNi 1-x Mn x / 2 Co x / 2O 2 (where x = 0.4 or 0.2 in the formula) or LiNi 0.8 Co 0.15 Al 0.05 O 2 An electrochemical cell as described in

[39] , including the following:

[41] The electrochemical cell according to any one of

[39] to

[40] , wherein the electrochemical cell exhibits an energy density of at least 180 Wh / kg at room temperature, for example, an energy density of 180 Wh / kg to 3,500 Wh / kg at room temperature.

[42] The electrochemical cell according to any one of

[38] to

[41] , wherein the electrochemical cell exhibits a charging rate of 1 to 10 minutes to 30% of the state of charge (SOC), a charging rate of 1 to 10 minutes to 50% of the state of charge (SOC), a charging rate of 1 to 10 minutes to 70% of the state of charge (SOC), and / or a charging rate of 1 to 10 minutes to 90% of the state of charge (SOC).

[43] A group of particles formed from amorphous glass, wherein the amorphous glass includes glass defined by the following formula: Si x Sn y 1 AFM a 2 AFM b 3 AFM c 4 AFM d During the ceremony, 1 AFM, 2 AFM, 3 AFM and 4 AFM represents different elements selected from iron, aluminum, titanium, copper, nickel, cobalt, manganese, gallium, indium, zirconium, and yttrium, respectively. x is between 50 and 90. y is between 1 and 40, a is between 0.5 and 20. b is between 0.5 and 15. c is between 0 and 10, and d is between 0 and 10.

[44] The group according to

[43] , wherein the group of particles includes a group of fine particles.

[45] The group of fine particles according to

[44] , wherein the group of fine particles has an average particle size of 1 to 15 microns, for example, 1 to 5 microns, when determined by scanning electron microscopy (SEM).

[46] The group according to

[43] , wherein the group of particles includes a group of nanoparticles.

[47] The group of nanoparticles according to

[46] , wherein the group of nanoparticles, when determined by scanning electron microscopy (SEM), has an average particle size of 25 nm to less than 1 micron, for example, 100 nm to 750 nm.

[48] ​​The group according to any one of

[43] to

[47] , wherein the diameter of the group of particles is monodisperse.

[49] The group according to any one of

[43] to

[48] , wherein the particles have an aspect ratio of 10 or less, for example, an aspect ratio of 5 or less or an aspect ratio of 2 or less.

Claims

1. It contains particles formed from amorphous glass, which is formed from a mixture containing two or more active ingredients and two or more amorphous-forming ingredients. The two or more active ingredients comprise 80 mol% to 99 mol% of the amorphous glass, and the two or more active ingredients comprise silicon and tin, and optionally one or more of lead, antimony, germanium, gallium, indium, bismuth, or any combination thereof; An anode wherein the two or more amorphous-forming components comprise 1 mol% to 20 mol% of the amorphous glass, the two or more amorphous-forming components comprise iron, aluminum, titanium, copper, nickel, cobalt, manganese, zirconium, yttrium, boron, niobium, molybdenum, tungsten, or any combination thereof, and the two or more amorphous-forming components comprise one or more lanthanides.

2. The anode according to claim 1, wherein the particles include a collection of fine particles.

3. The anode according to claim 2, wherein the collection of fine particles has an average particle size of 1 to 15 microns when determined by scanning electron microscopy (SEM).

4. The anode according to claim 1, wherein the particles include a collection of nanoparticles.

5. The anode according to claim 4, wherein the group of nanoparticles has an average particle size of 25 nm to less than 1 micron when determined by scanning electron microscopy (SEM).

6. The anode according to any one of claims 1 to 5, wherein the particles include a monodisperse collection of particles.

7. The anode according to any one of claims 1 to 6, wherein the two or more active ingredients constitute 80 mol% to 95 mol% of the amorphous glass.

8. The anode according to any one of claims 1 to 7, wherein the two or more amorphous-forming components constitute 5 mol% to 20 mol% of the amorphous glass.

9. The anode according to any one of claims 1 to 8, wherein the two or more active ingredients and the two or more amorphous-forming ingredients are present in the amorphous glass in a molar ratio of 4:1 to 50:

1.

10. The anode according to any one of claims 1 to 9, wherein the silicon and the tin are present in a molar ratio of 1.1:1 to 20:

1.

11. The anode according to any one of claims 1 to 10, wherein one or more lanthanides constitute 1 mol% or more of the amorphous glass.

12. The anode according to any one of claims 1 to 11, wherein the two or more amorphous-forming components include one or more Group 4 elements.

13. The anode according to claim 12, wherein one or more of the aforementioned Group 4 elements constitute 1 mol% to 15 mol% of the amorphous glass.

14. The anode according to any one of claims 1 to 13, wherein the two or more amorphous-forming components include one or more Group 13 elements.

15. The anode according to claim 14, wherein one or more Group 13 elements constitute 1 mol% to 8 mol% of the amorphous glass.

16. The anode according to any one of claims 1 to 15, wherein the amorphous glass includes SiSnCeFeAlTi glass.

17. The anode according to any one of claims 1 to 16, wherein the particles have an aspect ratio of 10 or less.

18. The anode according to any one of claims 1 to 17, wherein the two or more amorphous-forming components include an inert component.

19. The anode according to any one of claims 1 to 18, wherein the particles further comprise a carbonaceous material disposed on the surface of the particles.

20. The anode according to any one of claims 1 to 19, wherein the particles are dispersed in a binder.

21. The anode according to claim 20, wherein the binder comprises a polymer binder selected from the group consisting of vinylidene fluoride (PVDF), polyaniline, and combinations thereof.

22. The anode according to any one of claims 20 to 21, wherein the binder comprises a conductive polymer.

23. The anode according to any one of claims 20 to 22, wherein the binder comprises a carbonaceous material.

24. The anode according to any one of claims 1 to 23, wherein the particles react with an active ion selected from the group consisting of lithium ions, sodium ions, potassium ions, and combinations thereof, under conditions normally encountered during the charging and discharging of a battery containing the active ion, and can store the active ion.

25. An electrochemical cell comprising an anode, a cathode, and an electrolyte disposed between the anode and the cathode, as described in any one of claims 1 to 24.

26. The electrochemical cell according to claim 25, wherein the electrochemical cell includes a lithium-ion battery and the cathode includes a lithium-based cathode.

27. The cathode is lithium iron phosphate, LiNi １－ｘ Mn ｘ／２ Cox / 2O ２ (wherein the formula, x = 0.4 or 0.2) or LiNi ０．８ Co ０．１５ Al ０．０５ O ２ The electrochemical cell according to claim 26, including the following:

28. The electrochemical cell according to any one of claims 25 to 27, wherein the electrochemical cell exhibits an energy density of at least 180 Wh / kg at room temperature.

29. The electrochemical cell according to any one of claims 25 to 28, wherein the electrochemical cell exhibits a charging rate of 1 to 10 minutes to 30% of the state of charge (SOC), a charging rate of 1 to 10 minutes to 50% of the state of charge (SOC), a charging rate of 1 to 10 minutes to 70% of the state of charge (SOC), and / or a charging rate of 1 to 10 minutes to 90% of the state of charge (SOC).

30. A method for forming particles formed from amorphous glass, which is formed from a mixture containing two or more active ingredients and two or more amorphous-forming ingredients, The two or more active ingredients comprise 80 mol% to 99 mol% of the amorphous glass, and the two or more active ingredients comprise silicon and tin, and optionally one or more of lead, antimony, germanium, gallium, indium, bismuth, or any combination thereof; The two or more amorphous-forming components comprise 1 mol% to 20 mol% of the amorphous glass, and the two or more amorphous-forming components comprise iron, aluminum, titanium, copper, nickel, cobalt, manganese, zirconium, yttrium, boron, niobium, molybdenum, tungsten, or any combination thereof, and the two or more amorphous-forming components comprise one or more lanthanides. Here, the particles are formed by ball milling.

31. A method for forming particles formed from amorphous glass, which is formed from a mixture containing two or more active ingredients and two or more amorphous-forming ingredients, The two or more active ingredients comprise 80 mol% to 99 mol% of the amorphous glass, and the two or more active ingredients comprise silicon and tin, and optionally one or more of lead, antimony, germanium, gallium, indium, bismuth, or any combination thereof; The two or more amorphous-forming components comprise 1 mol% to 20 mol% of the amorphous glass, and the two or more amorphous-forming components comprise iron, aluminum, titanium, copper, nickel, cobalt, manganese, zirconium, yttrium, boron, niobium, molybdenum, tungsten, or any combination thereof, and the two or more amorphous-forming components comprise one or more lanthanides. Here, the particles are formed in a template formation step.

32. The method according to claim 31, wherein the template preparation step controls the particle size using a porous membrane as a template.

33. The aforementioned templating process, Absorption of a precursor solution containing a metal precursor into a template, and Burning the template The method according to claim 31, including the method described in claim 31.

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