KR101833663B1 - High performance electrodes, materials, and precursors thereof - Google Patents

Abstract

High performance electrodes, electrode materials and precursors thereof are provided herein. Methods for their preparation are also provided herein.

Description

[0001] HIGH PERFORMANCE ELECTRODES, MATERIALS, AND PRECURSORS THEREOF [0002]

[Cross reference]

This application claims the benefit of US Provisional Patent Application No. 62 / 254,418, filed November 12, 2015, and US Provisional Patent Application No. 62 / 312,871, filed March 24, 2016, U.S. Provisional Patent Application No. 62 / 354,366, filed in the name of the applicant, each of which is incorporated herein by reference in its entirety.

[0001]

Field of the Invention The present invention relates to an electrode, particularly to a cathode of a lithium ion battery, a battery and a battery including the electrode, and to their manufacture.

The battery includes one or more electrochemical cells, e.g., a cell generally comprising a cathode, an anode and an electrolyte. Lithium-ion batteries are high energy density batteries that are quite commonly used in consumer electronics and electric vehicles. In a lithium ion battery, lithium ions generally migrate from the cathode to the anode during discharging and vice versa during charging. In the as-manufactured and discharged state, the lithium ion battery often contains a lithium compound (e.g., lithium metal oxide) at the cathode (anode) and another material, typically carbon, at the anode (cathode).

In certain embodiments, it is contemplated herein to provide a thin layer electrode, e.g., a thin layer electrode including a battery electrode and / or an electrode material (e.g., a lithium ion battery cathode material and / or an electrode) Systems and processes for producing materials and / or electrodes are provided. In some instances, such materials and / or electrodes have very good capacity, good capacity retention, high volume energy density (and high total density), and / or other advantages discussed herein. An alternative approach to achieving higher performance materials and electrodes is to achieve a very limited and gradual success due to some attempts to result in catastrophic failures and / or incompatible and incommensurable products and processes It is coming. In some embodiments, the present disclosure provides products and processes suitable for high throughput fabrication and production of high performance materials and electrodes, including roll-to-roll processing, such as those described in more detail herein. / RTI >

In certain embodiments, a process is provided herein for producing an electrode material, the process comprising generating a plume or aerosol from a fluid stock, wherein the fluid reservoir is conductive (e.g., carbon ) Inclusion (e. G., Graphene inclusion component) and an electrode active (e. G., SiO _x ) inclusions. In certain embodiments, the plume or aerosol is generated using a suitable technique, such as an electrospray technique. In some embodiments, the process further comprises generating a plume or aerosol in the presence of a high velocity gas. In certain instances, the high velocity gas facilitates fine dispersion of the plume or aerosol particulates, which in turn facilitates controlled, uniform deposition of the inclusion portions on the substrate surface. In some instances, the flow direction of the gas and the plume / aerosol is in the same general direction (e.g., with a directional average within 15 degrees, 10 degrees, 5 degrees, etc., relative to each other). Also provided herein are the fluid compositions described herein, the aerosols and plumes described herein, and other systems, process steps, intermediates, and the like described herein.

In some embodiments, such systems and processes are configured to facilitate high throughput electrospray using a single or banked nozzle system. In certain embodiments, the system and process are configured for DC voltage (V _DC ) or AC voltage (V _AC ) electrospray, such as gas-controlled DC voltage (V _DC ) or AC voltage (V _AC ) electrospray . In some embodiments, the processes and systems provided herein may be used to produce electrode precursor materials, electrode materials, uniform electrodes (e.g., on a current collector), such as uniform electrodes having uniform thickness, capacitors, component distribution, / RTI > and / or < / RTI >

In some instances, ejecting a charged fluid reservoir from an electrospray nozzle produces a fluid jet that is split to form a plume containing a plurality of droplets (or plume particulates). In certain embodiments, such a droplet is such that as it moves toward the current collector, droplets close to the current collector are made to dry (i.e., contain less fluid medium) (or even completely dry) than droplets close to the nozzle, , And drying of the various states (e.g., where more drying droplets contain less fluid medium than solid inert materials). In some instances, the plume includes droplets (e.g., closest to the collector surface, in particular), wherein all of the fluid medium is evaporated. In various embodiments, the plume (or portion thereof) provided herein comprises less than or equal to about 80 weight percent fluid, less than or equal to about 60 weight percent fluid, less than or equal to about 40 weight percent fluid, less than or equal to about 20 weight percent fluid, % Or less, or about 5% or less by weight of the fluid. In a preferred embodiment, the plume droplets are broken down to a sufficient size to reduce or minimize the number of inclusions contained within each droplet (especially near the collector surface). In a particular example, reducing and / or minimizing the number of inclusions in each droplet facilitates an excellent distribution of inclusions throughout the plume, particularly close to the current collector. In some instances, an excellent distribution of inclusions in the plume facilitates an excellent distribution of the inclusions collected on the current collector. In particular, silicon-containing electrode materials suffer from poor performance characteristics, such as poor capacitor retention during cycling, such as formation of a solid electrolyte interface (SEL) layer, milling, and the like. (E. G., Silicon and / or silicon oxide containing) particles in which the silicon material is to be protected from the electrolyte and the grinding action, for example, by minimizing SEI formation during degradation, (E. G., Graphene) components that capture and / or degrade particles during lithiation / de-lithization cycles. In certain embodiments, compositions and processes suitable for providing such results are provided herein.

Other atomization techniques are generally insufficient to adequately divide and decompose the droplets of the plume and, in order to provide a dispersion with good uniformity, in particular a plurality of inclusion types, such as the electrode active species, For example, in a system comprising a clathron type (e.g., used interchangeably with a graphene component herein), to provide an excellent distribution of the encapsulant material in the plume and on the collector body It is insufficient. Instead, a typical atomization technique is observed to produce particle agglomeration, including co-agglomeration by poor dispersion uniformity and control, and even without such agglomeration, the active electrode / carbon system, especially including the silicon active material, Exhibit insufficient or nonexistent performance characteristics.

In certain embodiments, the process herein may be used to separate plumes or aerosols into high velocity gases (e.g., ≥0.1 m / s, ≥0.5 m / s, ≥1 m / s, ≥5 m / s, (E. G., Electrospraying a fluid storage) at a rate of at least < / RTI > 20 m / s, ≥20 m / s, ≥25 m / s, ≥50 m / s, or other speeds as provided herein. In some instances, the electrostatically charged fluid reservoir is injected into the stream of high velocity gas. In certain embodiments, the high velocity gas further facilitates fragmentation (e.g., decomposition) of droplets formed during electrospray of the fluid reservoir. In some embodiments, droplets of the plume may contain less than 100 inclusions (e. G., On average) of less than 100 inclusions (e. G., Clusters (s) ), Less than 50 inclusions, less than 20 inclusions, less than 10 inclusions, and the like. In certain embodiments, the current collector is spaced a distance d from the atomizing nozzle, and droplets of the plume away from the current collector into d / 2, d / 3, or d / 4 may have (e.g., on average) About 50 inclusive inclusions, about 20 incusions, up to about 10 inclusions, up to about 5 inclusions, and the like. In a particular example, d is the average distance between the first outlet of the nozzle and the substrate surface. In some instances, good dispersions of droplets and low concentrations of encapsulant facilitate the formation of well dispersed and well-controlled multicomponent systems, such as those described herein.

In certain embodiments, a process is provided herein for making an electrode material (e.g., a silicon-carbon electrode material), an electrode (e.g., a silicon-carbon electrode), or a precursor of an electrode material or electrode. In certain embodiments, the electrode material, the electrode, or a precursor thereof may be an electrode active material (e.g., silicon, silicon oxide, or a combination thereof), such as particles comprising the active material Particles). ≪ / RTI > In certain embodiments, the process includes electrospraying a fluid storage, or creating an electrostatically charged plume from a fluid storage (e.g., by electrospraying the fluid storage).

In certain embodiments, the step of electrospraying the fluid storage or creating the electrostatically charged plume of the fluid storage comprises the steps of (i) providing a fluid stock to the first inlet of the first conduit of the electrospray nozzle , Wherein the first conduit is surrounded by a wall having an inner surface and an outer surface along the length of the conduit and the first conduit has a first outlet, and (ii) providing a voltage to the electrospray nozzle (E. G., Thereby providing an electric field). In some embodiments, the fluid reservoir comprises a plurality (i. E., More than one) of electrode active material (e.g., silicon) containing particles, a plurality of carbon inclusions (e.g., And fluid media (including, for example, an aqueous medium, such as water). In certain embodiments, the plurality of electrode active material (e.g., silicon) containing particles is less than 100 microns (e.g., from about 0.5 microns to about 20 microns, such as from about 1 microns to about 10 microns) One or more average dimensions (e. G., A minimum dimension) of less than 50 microns, less than 20 microns, less than 10 microns, 0.2 microns to 10 microns, or less than 0.2 microns Or an average minimum dimension). In some embodiments, the carbon inclusions of the fluid stock and / or the aggregated (first) composition are oxidative graphene components (e. G., Graphene oxide). In certain embodiments, the carbon inclusions (e.g., the (first) graphene component) comprise at least 50 wt% carbon (e.g., from about 60 wt% to about 80 wt% Of carbon). In a further or alternative embodiment, the carbon inclusions (e.g., the (first) graphene component)) comprise from about 5 wt% to about 50 wt% oxygen (e.g., About 10% to about 40% oxygen by weight). Generally, as used herein, the wt% of the carbon inclusions is the weight percentage of the carbon element (e.g., carbon, oxygen, hydrogen, etc.) that is carbon based on the element.

In certain embodiments, the processes and systems described herein are suitable for high throughput of overloaded fluid storage. In addition, in some embodiments, a high concentration of carbon (e.g., graphene) components is desirable to facilitate good coverage of the electrode active material, good uniformity of the film (e.g., thickness, dispersion, etc.), and the like. In certain embodiments, the fluid reservoir provided herein comprises at least 0.1 weight percent graphene, at least 0.5 weight percent graphene, or at least 1 weight percent graphene, such as at least 2 weight percent graphene, (For example, from about 10% to about 20% by weight, up to about 20% by weight, up to about 15% by weight, up to about 10% by weight) of graphene, %, Etc.). In certain embodiments, the fluid reservoir comprises from about 2% to about 15% (e.g., from about 10% to about 15%) graphene components.

In certain embodiments, the fluid reservoir comprises less than 30% by weight of electrode active material (e.g., silicon) containing particles. In a more specific embodiment, the fluid reservoir comprises less than 20% by weight of electrode active material (e.g., silicon) containing particles. In yet another more particular embodiment, the fluid reservoir comprises about 0.2% to about 10% by weight of electrode active material (e.g., silicon) -containing particles. In some instances, higher loading particles and / or carbon inclusions are possible, for example, when the electrospray process is performed by a gas stream. In certain embodiments, the fluid reservoir comprises particles containing at least about 1% by weight (e.g., about 2.0% by weight or more) of electrode active material (e.g., silicon). In certain embodiments, the fluid stock comprises particles containing at least about 5% by weight of electrode active material (e.g., silicon). In a more particular embodiment, the fluid reservoir comprises about 5 wt% to about 20 wt% of the electrode active material (e.g., silicon) containing particles. In a further or alternative embodiment, a particle-to-carbon inclusion containing an electrode active material (e.g., silicon) in a fluid storage or other composition (e.g., a collector and / or heat treated composition) For example, at least 1: 5, at least 1: 3, or at least 1: 2 (e.g., up to 10: 1). In certain embodiments, the weight ratio of the electrode active material (e.g., silicon) -containing particles to the carbon inclusions (e.g., graphene component) (eg, within the fluid storage and / or composition herein) From about 1: 10 to about 10: 1, from about 1: 3 to about 5: 1, from about 1: 2 to about 3: 1, from about 2: 3 to about 2: In a more specific embodiment, the weight ratio is at least 1: 3, at least 1: 1, and the like. In certain embodiments, at least 50% by weight of the solid particulate contained in the fluid reservoir comprises a clathrate and graphene inclusions (graphene components) that are electrode active material particulates. In certain embodiments, the solid particulates contained in the fluid reservoir, such as at least 70 wt%, at least 80 wt%, at least 90 wt%, and the like, include clathrates and graphene inclusions, which are electrode active material particulates. In a preferred embodiment, at least 95% by weight of the solid particulate contained in the fluid reservoir comprises clathrate and graphene inclusions (graphene component), which are electrode active material particulates.

In certain embodiments, the processes provided herein may be performed on a substrate (e.g., a metal foil) using a composition (e. G., A deposit or film resulting from electrospray of a fluid storage as described herein (E.g., a film that is a layer of a material such as that produced by the deposition technique described in U.S. Patent Application Serial No. 10 / ) Includes a plurality of electrode active material (e.g., silicon) -containing particles and a plurality of carbon inclusions (e.g., (first) graphene component) such as those described herein in a fluid reservoir. In certain embodiments, the fluid of the fluid reservoir is partially or completely removed (e.g., by evaporation during an electrospray process). In certain embodiments, the composition or deposit is a carbonaceous web, I pray comprises Yes inclusions containing a plurality of electrode active material secured within pinseong web (e.g., Si0x particles, such as micro-particles described herein) including a plurality of yes pinseong Inclusion component.

Any suitable substrate is optionally used. In some examples, the substrate is a grounded substrate or is positioned between a plume generating nozzle and a grounded substrate. In certain embodiments, the substrate has a surface that lies in an opposing relationship to the plume generating nozzle outlet (e.g., there is a "line of sight " between the nozzle outlet and the substrate surface). In certain embodiments, the opposing substrate is directly opposite the nozzle (e.g., configured in a nozzle conduit, e.g., orthogonal to that illustrated in FIG. 2). In another particular embodiment, the opposing substrate is angled or offset from directly facing the nozzle. In some embodiments, the substrate is fixed to the conveyor system or is part of the system. In certain embodiments, the substrate is attached to, or is part of, a conveyor belt. In some instances, the substrate may be a metal (e.g., a foil such as a foil such as copper, aluminum, etc.) or other collector type material (e.g., where the process is used to make the anode material directly on the current collector) , Or a substrate on which the electrode material is easily removed (e.g., where the process is used to make the anode powder material).

In some embodiments, the process provided herein can be used to chemically and / or thermally (for example, at least partially deoxidize a highly-oxygenated first graphene component, e.g., graphene oxide) And < / RTI > In certain embodiments, the process described herein comprises heat treating the current collector composition (e.g., above 100 DEG C) to provide a second (e.g., thermally treated) composition. In certain embodiments, the second composition comprises a plurality of electrode active material (e.g., silicon) containing particles and a plurality of carbon inclusions (e.g., (second) graphene component) The carbon inclusions of the (heat treated) composition comprise a greater weight percentage of carbon and a lower weight percentage of oxygen than the carbon enclosure of the fluid reservoir. In certain embodiments, the carbon inclusion of the treated (second) composition is a reduced graphene graphene component. In certain embodiments, the carbon inclusions (e.g., (second) graphene component) of the treated composition (e.g., thermally) comprise at least about 90 wt% carbon and at least about 0.1 wt% Of oxygen. In certain embodiments, the chemical and / or thermal treatment is optionally performed while the current collector is being formed on the substrate or after the current collector is removed from the substrate.

In certain embodiments, the electrospray process described herein is a gas-assisted or gas-controlled electrospray process. In some embodiments, the fluid reservoir provided herein is electrosprayed by a gas stream. In certain embodiments, the fluid reservoir described herein is injected into the gas stream during electrospray. In some embodiments, the process of producing an electrostatically charged plume from a fluid storage further comprises providing a pressurized gas to a second inlet of a second conduit of the nozzle described herein. In certain embodiments, the second conduit has a second inlet and a second outlet, wherein at least a portion of the first conduit is located within the second conduit (i.e., at least a portion of the second conduit It is located in a cheap relationship). In certain embodiments, the gap between the outer wall of the inner conduit and the inner wall of the outer conduit is sufficient for sufficient dissociation of the charged fluid (jet) ejected from the nozzle (e.g., to provide the plume or aerosol dispersion described herein) So as to facilitate the high velocity gas at the nozzle. In some embodiments, the conduit gap is from about 0.01 mm to about 30 mm, such as from about 0.05 mm to about 20 mm, from about 0.1 mm to about 10 mm, and the like. In certain embodiments, the gas stream (at the second outlet, for example) is at a high velocity, such as at least 1 m / s, such as greater than 5 m / s, greater than 10 m / s, greater than 20 m / And has a speed higher than that.

In some examples, the process provided herein comprises compressing the pooled and / or heat treated compositions described herein. In certain embodiments, the aggregated and / or heat treated composition has a density of about 0.5 g / cc or greater per cubic centimeter, such as from about 0.5 g / cc to 2 g / cc (e.g., 0.7 g / cc to 2 g / cc). < / RTI > In various embodiments, the composition that is collected and / or heat treated and / or compressed has a thickness (e.g., on the substrate) of about 1 mm or less, or about 200 microns or less.

In some embodiments, the collected (first) composition comprises a plurality of electrode active material containing (e.g., silicon containing) particles and a plurality of carbon inclusions (e.g., (first and / or oxidized) ). In certain embodiments, the compositions provided herein (e.g., pre- and / or post-heat treated compositions) comprise an electrode active material-containing particle immobilized within a carbonaceous web (e.g., a graphene web). In some embodiments, the web defines one or more pockets (e.g., graphene pockets), and one or more electrode active material-containing particles are formed in the pockets. In certain embodiments, the collected (first) composition comprises a plurality of graphene envelopes, wherein the graphene envelope comprises an inner surface and an outer surface, wherein the inner surface defines a graphene pocket. In a more specific embodiment, one or more electrode active material containing (e.g., silicon containing) particles are configured in the graphene pocket. In certain embodiments, the graphene envelope comprises at least one carbon occlusion of the aggregated (first) composition (e.g., the oxidized graphene component (s)). In certain embodiments, the graphene pocket (s) comprise (e. G., On average) one or more electrode active material-containing particles constructed therein. In a more specific embodiment, the graphene pocket comprises more than one (e.g., 1.05 or more) active electrode-containing particles configured on an average. In some embodiments, the graphene pocket comprises 1 to 200 or 1 to 100 electrode active material-containing (e.g., silicon-containing) particles constructed therein (e.g., on average) 100, 1.01 < n? 200, 1.05 < n? 100, etc. where n is the number of electrode active material-containing particles constituted in the envelope. In a more specific embodiment, the graphene pocket (s) may comprise 1-50 (e.g., 1-5 or 2-5) internal (e.g., 1 < (for example, silicon-containing) particles of an electrode active material of n? 50, 1? n? 5, 2? n? 5.

In some embodiments, the (second) composition (e.g., film) treated (e.g., thermally) comprises a plurality of electrode active material containing (e.g., silicon containing) particles and a plurality of carbon inclusions (E.g., thermally) reduced oxide graphene component). In certain embodiments, the composition provided herein (e.g., pre- and / or post-heat treated composition) comprises an electrode active material-containing particle immobilized within a carbonaceous web (e.g., a graphene web). In some embodiments, the web defines one or more pockets (e.g., graphene pockets), and one or more electrode active material-containing particles are formed in the pockets. In certain embodiments, the (thermally) treated (second) composition comprises a plurality of graphene envelopes, wherein the graphene envelope comprises an outer surface and an inner surface, wherein the inner surface defines a graphene pocket. In a more specific embodiment, one or more electrode active material containing (e.g., silicon containing) particles are configured in the graphene pocket. In certain embodiments, the graphene envelope or pocket wall comprises at least one oxidized graphene component (s) that is reduced (e. G., Thermally) to a carbon occlusion of the treated (second) composition . In certain embodiments, the graphene pocket comprises 1-100 electrode active material-containing (e.g., silicon-containing) particles constructed therein (e.g., on average). In a more particular embodiment, the graphene pocket (s) may contain from 1 to 50 (e.g., 1-5 or 2-5) electrode active materials configured internally (e.g., on average) Containing silicon) particles.

In certain embodiments, the electrode active material-containing (e.g., silicon-containing) particles have an average aspect ratio of from 1 to about 100, such as from 1 to about 10. In additional or alternative embodiments, the electrode active material containing (e.g., silicon containing) particles may have an average dimension (or average) of about 10 microns or less, such as about 200 nm to about 10 microns, or about 1 micron to about 5 microns Minimum dimension).

In some embodiments, the carbon inclusions provided herein (e. G., Two-dimensional carbon inclusions such as graphene components) provide an average dimension of the electrode active material containing (e.g., silicon containing) At least one average dimension at least equal to (e.g., in the example where electrode active material-containing particles of higher aspect ratio (e.g.,> 2,> 5,> 10, etc.) Long side length), width and / or length) (i. E., A measure of the average dimension within the carbon inclusions of the process or composition provided herein). In certain embodiments, the carbon inclusions provided herein have an average size (or average minimum dimension) of the electrode active material-containing particles of > 1x (e.g.,> 1.1x,> 1.2x,> 1.5x,> 2x, 3x, > 4x, etc.). In certain embodiments, the carbon inclusions (e. G., Graphene components) provided herein can be at least 5 times the average dimension (or average minimum dimension) of the electrode active material containing (e.g., silicon containing) (E. G., Width and / or length) of at least about 10 times, or at least about 100 times greater. In certain embodiments, the carbon inclusions (e.g., graphene components) have an average thickness of about 100 nm (nanometers) or less, such as about 50 nm or less, about 20 nm or less, about 10 nm or less and the like. In certain embodiments, the thickness of the carbon inclusions is about 1 nm or about 1 nm to about 10 nm, or about 3-5 nm. In certain embodiments, the carbon inclusion or graphene component provided herein comprises at least one layer thereof (e.g., a graphene component layer) (e.g., each graphene layer comprises graphene, graphene oxide , Reduced graphene oxide, and the like). In certain embodiments, the graphene component provided herein comprises from about 1 to about 25 layers thereof on average. Similarly, in some embodiments, the graphene envelope described herein comprising such a carbon inclusion or graphene component includes such thickness and / or number of layers therein. In some embodiments, the carbon inclusions (e.g., two-dimensional carbon encapsulants, such as graphene components) can be at least about 0.5 microns, at least about 1 micron, at least about 5 microns, from about 1 micron to about 100 microns, (E.g., side dimensions, width, and / or length) of about 5 microns to about 50 microns.

In some embodiments, (a) an inclusion (e.g., microstructured and / or nanostructured) containing an active material (e.g., an electrode active material such as silicon) and (b) There is provided a method of manufacturing an electrode (or electrode material) comprising a carbon component (generally referred to as an electrode material). In a particular embodiment, the method comprises generating electrostatically charged plumes comprising droplets from a plurality (e.g., micro and / or nanoscale) particles and / or fluid reservoirs. In a more particular embodiment, such a plume is produced by providing a fluid reservoir to a first inlet of the first conduit of the electrospray nozzle (e.g., by applying a voltage to the electrospray nozzle). In a particular embodiment, the process includes applying a voltage to a nozzle (e.g., a wall of a first conduit). In a more particular embodiment, the voltage provides an electric field (e.g., at the first outlet, such that the fluid storage is ejected as a jet and / or a plume from a nozzle, e.g., a first outlet thereof). In some embodiments, the first conduit having the first outlet is surrounded by a wall having an inner surface and an outer surface over the length of the conduit. In some embodiments, the fluid reservoir comprises a nanostructured inclusion containing liquid (e. G., Electrode active material) and a liquid medium (e. G., Water). In a more particular embodiment, the fluid reservoir further comprises a carbon inclusion (e. G., The same or different from the carbon content of the electrode and / or the electrode material). In some embodiments, the method further comprises collecting the deposit (e.g., film) onto a substrate (e.g., a conductive substrate such as the current collector disclosed herein). In certain embodiments, the deposit comprises a nanostructured inclusion containing (a) an active material and (b) a carbon component, such as an anchoring material (E.g., carbon webs such as lapping, trapping, and / or enveloping).

In some embodiments, an electrode comprising (e.g., made or prepared by the method disclosed herein) and / or an electrode comprising an inclusion (e.g., including electrode active material) coated (or wrapped) Or electrode material is provided. That is, in some embodiments, a carbon web (e.g., comprising an electrode active material) immobilized within a carbon web (e.g., a carbon web comprising a carbon such as those disclosed herein, such as graphene and / An electrode, an electrode material, or precursor thereof, comprising a nanostructured inclusion is provided.

In certain embodiments, compositions provided herein (e.g., pre- and / or post-heat treated compositions) comprise an electrode active material-containing particle immobilized within a carbonaceous web (e.g., a graphene web). In some embodiments, the web defines one or more pockets (e.g., graphene pockets) within which one or more electrode active material-containing particles are disposed. In some embodiments, the graphene web comprises a plurality of graphene component sheets (e.g., a graphene sheet, a graphene oxide sheet, a reduced graphene oxide sheet, or a graphene component sheet) that form a layer having a surface area larger than the surface area of a single sheet, A combination thereof). In some cases, the graphene moieties overlap, overlap, adjoin, interact or interact with each other (e.g., through non-covalent bonding forces). In certain embodiments, the carbonaceous (e.g., graphene) film comprises a continuous web defining therein a plurality of carbonaceous pockets. In some embodiments, the continuous web extends throughout the composition to provide a continuous self-supporting film. In another embodiment, the carbonaceous web does not have interconnects with, for example, a second graphene pocket structure and forms a coating or a wrap around one or more electrode active material containing particles in a single graphene pocket. Figures 5 and 19 show a graphene web with high interconnections between graphene pockets, while Figure 20 shows a more disconnected graphene web with few interconnections between graphene pockets.

As shown in the drawings (e.g., Figs. 5, 19, etc.), a good covering ratio of the electrode active material is provided by the graphene web. In some embodiments, the film or composition provided herein has an externally exposed surface (e.g., including the top surface and the other exposed surface of the material illustrated herein), and the externally exposed surface is primarily a carbonaceous material . In a particular case, the electrode active material (e.g., SiOx) has little external exposure in the film or composition. In some cases, this is important to maximize electrode performance characteristics, for example by minimizing grinding and / or SEI formation. In some embodiments, the compositions, films, or (coated) particles provided herein contain less than 20% of the electrode active material or SiOx on a surface area basis. In a preferred embodiment, the compositions, films, or (coated) particles provided herein contain less than 10% of the electrode active material or SiOx on a surface area basis. In a more preferred embodiment, the compositions, films, or (coated) particles provided herein contain less than 5% of the electrode active material or SiOx on a surface area basis. In some embodiments, the compositions, films, or (coated) particles provided herein are graphene based on surface area of at least 80% (e.g., characterizing the graphene component disclosed herein). In a preferred embodiment, the compositions, films, or (coated) particles provided herein are at least 90% graphene based on surface area. In a more preferred embodiment, the compositions, films, or (coated) particles provided herein are at least 95% graphene on a surface area basis.

Also provided are compositions as disclosed in the methods herein. Such compositions are prepared by any suitable method as disclosed herein. In a particular embodiment, an anode material, an anode and precursors thereof are provided.

In certain embodiments, a plurality of electrode active material (e.g., silicon) -containing particles and a plurality of carbon inclusions (e.g., reduced oxide graphene components for the anode and anode materials, or graphene for the precursors of the anode and anode materials, Oxide component) is provided.

In a particular embodiment herein, a composition comprising a plurality of electrode active material (e.g., silicon) containing particles and a plurality of carbon inclusions (e.g., graphene component, oxidized graphene component, reduced oxidized graphene component, etc.) do. In a particular embodiment, the carbon inclusion is an oxidative graphene component. In another particular embodiment, the carbon inclusion is a graphene component (e. G., A reduced graphene graphene component). In some embodiments, the composition comprises a plurality of silicon-carbon composite domains. In a particular embodiment, the silicon-carbon composite domain comprises an envelope (e.g., graphene) envelope, wherein the envelope comprises an outer surface and an inner surface, and the inner surface defines an envelope pocket. In some embodiments, at least one of the plurality of electrode active material (e.g., silicon) -containing particles is disposed within the envelope pocket. In some embodiments, the envelope comprises at least one of a plurality of carbon inclusions (e.g., graphene component, oxidized graphene component, etc.). In some embodiments, there is provided a composition comprising graphene oxide and a plurality of silicon-containing particles, wherein the graphene oxide is arranged to form a plurality of graphene oxide envelopes, wherein the plurality of silicon-containing particles comprise a plurality of graphene oxide envelopes . In some embodiments, there is provided a composition comprising reduced graphene oxide and a plurality of silicon-containing particles, wherein the reduced graphene oxide is arranged to form a plurality of reduced graphene oxide envelopes, wherein the plurality of silicon- Are disposed in a plurality of reduced graphene oxide envelopes. Also provided is such an envelope (e. G., A graphene envelope) containing a plurality of particles (e.g. comprising an electrode active material such as silicon).

In a particular embodiment, the carbon inclusion is an oxidative graphene component. In a more particular embodiment, the oxidized graphene component is a graphene oxide (e.g., comprising from about 1 to about 25 layers of graphene oxide per inclusion particle). In certain embodiments, the oxidized graphene component comprises at least 10 wt% oxygen (e.g., from about 10 wt% to about 50 wt% oxygen). In certain embodiments, the oxidized graphene comprises at least about 40 weight percent carbon, such as at least about 50 weight percent carbon (e.g., from about 60 weight percent to about 90 weight percent carbon). In certain embodiments, the graphene oxide component or the graphene component (e.g., reduced graphene oxide) comprises less than about 10 weight percent oxygen, such as from about 0.1 weight percent to about 10 weight percent oxygen.

In some embodiments, the electrode active material-containing particles used in the compositions and methods herein comprise silicon and / or silicon oxide (SiOx, where 0 < x < 2). In a particular embodiment, the silicon-containing particles comprise semi-stoichiometric silicon oxide (i.e., SiOx, where 0 <x <2). In some embodiments, the particles disclosed herein, such as those comprising SiOx, have a thickness of less than or equal to about < RTI ID = 0.0 &gt; 0% < ). &Lt; / RTI &gt; The description herein of inclusions comprising SiOx, unless otherwise stated, includes inclusions (e.g., inclusions may include elemental silicon (Si) and quasi-stoichiometric and / or fully oxidized silicon oxides 0.0 &gt; x) &lt; / RTI &gt; In a particular embodiment, the silicon-containing particles comprise at least about 50 weight percent silicon (e.g., elemental silicon (Si)) (e.g., average). In some embodiments, such particles also include SiOx (e.g., where 0 &lt; x &lt; 2). In a particular embodiment, such particles include both Si and SiOx (e.g., SiOx is present on the surface of the particle). In certain embodiments, the silicon-containing particles comprise from about 0.1 wt% to about 25 wt% (e.g., from about 1 wt% to about 10 wt%) of SiOx (e.g., average). In certain embodiments, the average dimension (e.g., total average dimension) of the particles is at least about 10 nm, such as at least about 200 nm. In a particular embodiment, the average dimension is from about 200 nm (0.2 micron) to about 20 microns, such as from about 1 to about 10 microns, from about 0.5 microns to about 5 microns, or from about 1 micron to about 5 microns. In certain embodiments, the particles have at least one dimension (e.g., length, width, diameter, length, minimum dimension, etc.) having an average size of at least about 10 nm, such as at least about 200 nm. In a particular embodiment, the average dimension is from about 200 nm (0.2 micron) to about 20 microns, such as from about 1 to about 10 microns, from about 0.5 microns to about 5 microns, or from about 1 micron to about 5 microns. In some embodiments, the average aspect ratio of the particles is at least 1, such as from 1 to about 100, from 1 to about 10, and the like.

(E. G., Average) size (e.g., length, width, or length and width) of the carbon inclusions (e. G., Graphene component or graphene component) (E.g., average) size of the minimum dimensions (e.g., height, width, length, thickness, etc.) of the particles In a particular embodiment, the (e.g., average) size of the carbon inclusion (s) (e.g., graphene component (s) or oxide graphene component (s)) is less than the average size of the minimum dimension of the particle 2 to about 20 times greater.

(E. G., A graphene component or an oxidized graphene component) and particles (e. G., Silicon, e. G. Electrode active material) in a particle weight ratio of 1: 5 or more, for example, 1: 3 or more, or 1: 2 or more. In a particular embodiment, the carbon inclusion is an oxidative graphene component and the weight ratio of the particles (e.g., silicon) to the oxidized graphene component (e.g., graphene oxide) is from about 1: 5 to about 5: 1, 1: 1 to about 5: 1, or from about 1: 1 to about 3: 1. In a particular embodiment, the ratio of particles (including silicon, for example) to oxide graphene components (e.g., graphene oxide) is from about 3: 2 to about 5: 1. In certain embodiments, the compositions provided herein comprise an electrode active material such as at least 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, and the like. In certain instances, the pre-heat treatment composition has a lower weight percent than the post-heat treatment composition (e.g., heat treatment results in loss of oxygen and molecular weight and mass as the carbonaceous inclusions such as graphene oxide are reduced). In certain embodiments, no more than about 80 wt.%, No more than about 85 wt.%, No more than about 90 wt.%, No more than about 95 wt.% Active material is optionally included. In a particular embodiment, the pre-heat treatment composition comprises about 30% to about 80% by weight of the electrode active material (e.g., SiOx). In a further or alternative embodiment, the post-heat treatment composition comprises about 50% to about 95% by weight of the electrode active material (e.g., SiOx). In certain embodiments, the compositions provided herein comprise a clathrate material (such as a graphene component) having a carbon content of at least 5 wt%, at least about 10 wt%, at least about 30 wt%, and the like. In some embodiments, a clathrate material (e.g., a graphene component) is included that comprises about 80 wt% or less, about 70 wt% or less, about 50 wt% or less, about 30 wt% or less of carbon, and the like. In a particular embodiment, the pre-heat treatment composition comprises a clathrate material (e.g., graphene component) that comprises from about 20 wt% to about 80 wt% carbon. In a further or alternative embodiment, the post-heat treatment composition comprises a clinking material (e.g., a graphene component) that comprises from about 10% to about 50% by weight of carbon.

In certain embodiments, the envelope (e.g., graphene envelope) comprises about 1 to about 10 particles (e.g., including silicon and / or other electrode active material) (e.g., average). In particular embodiments, the envelope (e.g., graphene envelope) comprises from about 2 to about 5 particles (e.g., including silicon and / or other electrode active material) (e.g., average).

Also provided herein are various compositions prepared by the methods herein, which can be prepared by the methods herein, or otherwise disclosed in the methods herein. In some cases, films, plumes or aerosols, fluid reservoirs, coated particles, and the like described herein are provided herein. In particular, in certain embodiments, films disclosed herein as deposits and / or coated particles disclosed in such films are provided herein. In some embodiments, the deposit or film disclosed herein is optionally removed from the substrate to provide a powder, such as a free flowing powder, comprising electrode active material particles coated with a carbonaceous web (e.g., a graphene web) as disclosed herein . In some embodiments, such as where the carbonaceous web has a high degree of interconnection between the pockets defined thereby, the composition removed from the substrate may be further processed to form a plurality of pockets (e.g., Reducing the particle size in the powder by disassembling the web) or by milling, crushing or crushing the materials disclosed herein.

In certain embodiments, the anode powder material provided herein may be processed to form an electrode (e. G., A lithium ion battery anode (anode)) by processing the anode powder material provided herein (e. G., By removing a film produced according to the method herein, ). In a particular embodiment, the powder is made into an electrode in combination with a binder (e.g., on a conductive substrate (e.g., collector)). Any suitable binder such as polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), ethylene propylene diene monomer (EPDM) rubber, acrylonitrile-butadiene rubber (NBR) In a further or alternative embodiment, the anode material is combined with other electrode active materials such as graphite. In some embodiments, the electrode may comprise at least 5 wt% (e.g., at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 30 wt%, at least 50 wt% Material. Any suitable amount of binder and / or other active material (e.g., graphite) is optionally combined with the active material (e.g., powder thereof) provided herein. In a particular embodiment, the binder is present in the electrode in an amount from about 0.1% to about 10% by weight. In some embodiments, the other electrode active material (e.g., graphite) may be present in the electrode in an amount of from about 1% to about 99%, such as from about 5% to about 95%, from about 10% to about 90% Lt; / RTI &gt;

In particular embodiments, composite particles (e.g., silicon-carbon composite particles) comprising an electrode active material-containing particle (e.g., silicon-containing particle) and a carbonaceous web (e.g., graphene web) are provided. In certain embodiments, the web comprises a graphene component as disclosed herein (e.g., comprising greater than 50 wt% carbon and between about 0.1 wt% and about 50 wt% oxygen). As in the films disclosed herein, in some embodiments, the web defines one or more pockets (the pocket (s) are disposed within the web). In a preferred embodiment, the web is well coated with the electrode active material-containing particles such that less than 10% (e.g., less than 5%, less than 3%, etc.) of the outer surface of the composite particle is the material of the electrode active material- Fig. In a further or alternative preferred embodiment, at least 80% (e.g., at least 90%, at least 95%, at least 97%, etc.) of the outer surface of the composite particle comprises a graphene web. In a further or alternative embodiment, the particles include large amounts of active material to maximize or improve electrode performance characteristics (e.g., capacity). In some embodiments, the composite particles comprise at least 30 wt% of the electrode active material (or at least 30 wt% of the particles) (e.g., at least 50 wt%, at least 70 wt%, such as at most about 95 wt%). In certain embodiments, a small amount of carbonaceous web component (e. G., Graphene web) is utilized to coat and protect the electrode active (e. G., SiOx) and provide good conductivity for compositions comprising the composite particle . In some embodiments, the composite particles comprise less than about 70 weight percent carbonaceous (e.g., graphene) web (e.g., less than about 50 weight percent, less than about 40 weight percent, less than about 25 weight percent, By weight to about 10% by weight). In some embodiments, the composite particles disclosed herein comprise exactly one pocket disposed therein. In another embodiment, the composite particles optionally include more than one pocket disposed therein (e.g., wherein the carbonaceous web defines and connects a plurality of pockets). In certain embodiments, the structural characteristics, such as diameter, length, aspect ratio, etc., of the composite particles closely match the characteristics of the wrapped active particles, particularly when the composite particle comprises single active particles and a single pocket. Thus, in some embodiments, the characteristics of the composite particles are optionally as set forth herein for active particles. For example, in some embodiments, the aspect ratio of the composite particles disclosed herein is from 1 to about 100 (depending, for example, on the aspect ratio of the active particle (s) disposed in the carbonaceous web thereof). In some embodiments, larger composite particles are also contemplated, such as the presence of multiple pockets and / or active particles in the composite particles. Other characteristics of the particles and their component parts are as described herein for the films and / or deposits provided herein and vice versa.

In some embodiments, the volume of the pocket disclosed herein is greater than the volume of particle (s) disposed therein. In certain cases, particularly when Si and / or SiOx expands during the lithium substitution reaction, an excess of pocket volume is desirable. In some cases, during expansion, the excess volume allows the particles to expand, reducing the likelihood of the web coating becoming dislocated and / or reducing the overall volume expansion of the electrode material. In certain embodiments, the void space in the pocket is greater than 3% (e.g., greater than 5%, greater than 10%, greater than 20%, etc.) by volume of the electrode active material containing particle (s) disposed therein.

BRIEF DESCRIPTION OF THE DRAWINGS These and other objects, features, and characteristics of the systems and / or methods disclosed herein, as well as the function and method of operation of the related elements of the structure, as well as combinations of parts and manufacturing economics will become more apparent from the following description and appended claims , All of which form part of this disclosure. It should be clearly understood, however, that the drawings are for the purpose of illustration and description only and are not to be construed as limiting the present invention. As used in this specification and the appended claims, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. In addition, unless stated otherwise, the values and characteristics described for the individual components herein also include a description of the values and properties as an average of such plurality (i. Likewise, the description of average values and properties herein also includes the description of individual values and characteristics such as those applied to a single component herein.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows an electrode comprising a carbon web for fixing nanostructures to a substrate.
Figure 2 illustrates an exemplary illustration of a gas controlled electrospray system and process provided herein.
Figure 3 shows an illustrative illustration of a process in which the graphene component fixes the nanostructures to a substrate.
Figure 4 shows an exemplary illustration of a plurality of carbon inclusions (graphene components) collectively forming a carbon web that fixes the nanostructures to the substrate.
5 is an exemplary illustration of a microscopic image of an exemplary carbon web securing an electrode active material to a substrate.
Figure 6 shows an exemplary fixation process of a composite nanofiber with a carbon web comprising a graphene component (e.g. comprising a carbon matrix in which an electrode active material is embedded).
Figure 7 shows exemplary non-capacitive data for an exemplary electrode comprising a carbon web comprising a graphene component and a composite nanofiber (including a carbon matrix in which the silicon nanoparticles are embedded) immobilized on a current collector will be.
Figure 8 shows an exemplary electrospray nozzle arrangement used in the manufacture of the specific electrodes and electrode materials provided herein.
Figure 9 shows exemplary non-capacitive data for an exemplary electrode comprising a carbon web comprising a graphene component and silicon nanoparticles immobilized on a current collector.
10 shows exemplary coulombic efficiency data for several exemplary electrodes comprising a carbon web comprising a graphene component and silicon nanoparticles immobilized on a current collector.
Figure 11 shows an exemplary non-capacitive electrode for several exemplary electrodes provided herein comprising a carbon web comprising a graphene component and a composite nanofiber (including a tin-embedded carbon matrix) fixed on the current collector Data.
Figure 12 shows an exemplary cyclic voltammetric (CV) curve for several exemplary electrodes comprising a carbon web comprising a graphene component and a silicon nanoparticle immobilized on a current collector.
Figure 13 shows an image of a substrate coated with active material and carbon inclusion using several techniques including the exemplary techniques disclosed herein.
Figure 14 shows an example effect of folding an image of a substrate coated with an active material and a carbon inclusion, and such a coated substrate using the exemplary techniques disclosed herein.
15 illustrates an example of a lithium ion battery cathode comprising a carbon web containing a graphene component and silicon nanoparticles immobilized on a collector, as compared to other lithium ion battery cathodes comprising silicon nanoparticles and graphene components And non-capacity data.
Figure 16 shows exemplary impedance data for various electrodes.
Figure 17 is a graphical illustration of an exemplary electrode for several exemplary electrodes provided herein comprising a carbon web comprising a graphene component and a composite nanofiber (including a carbon matrix with silicon nanoparticles embedded therein) Non-capacity data.
FIG. 18 illustrates exemplary, non-capacitive data for an exemplary electrode comprising a carbon web comprising a graphene component and a nanostructure comprising SiOx immobilized on the current collector.
Figure 19 shows exemplary microscale particles comprising the active material in (a) original form and (b) and (c) coated with carbon (at various zoom levels).
Figure 20 shows an exemplary deposit (electrode) provided herein using microstructured active materials in combination with the carbon provided herein (upper left: a larger view of the uncompressed deposit; upper right: compressed Lower left: less magnified view of uncompressed deposit; lower right: less magnified view of condensed deposit).
Fig. 21 demonstrates that compression of deposits can greatly reduce the thickness of the electrode deposit (e. G., Can reduce the thickness of deposit by more than two times).
Figure 22 shows the specific capacitance of the exemplary electrode provided herein.
Figure 23 illustrates the capacity retention of a half cell fabricated using the exemplary anode material described herein.
Figure 24 illustrates the cycling efficiency of a semi-conductor fabricated using the exemplary anode material described herein.
Figure 25 illustrates the capacity of an exemplary half-cell using an SiOx inclusion on the anode during cycling.
Figure 26 shows the capacity retention and cycling efficiency of a full cell fabricated using the high loaded exemplary anode material described herein.
27 shows various SEM images of silicon oxide microparticles coated with carbon nanofibers.
Figure 28 shows a SEM image showing good coverage of silicon microparticles using larger graphene components (at varying zoom levels).
Figure 29 shows a SEM image showing poor coverage of silicon microparticles using smaller graphene components (at varying zoom levels).
Figure 30 illustrates an exemplary graphene oxide (GO) structure.
31 illustrates an exemplary reduced graphene oxide (rGO) structure.
32 shows the phase of the deposit (panel A) formed after 30 seconds of gas-controlled electrospraying of the graphene oxide stock and the phase of the deposit formed after 30 seconds of electro-spraying of the airless graphene storage (panel B).
33 shows the phase of the deposit (panel A) formed after one minute of gas-controlled electrospray of the graphene oxide storage and the phase of deposition (panel B) formed after one minute of electrospray of airless graphene storage.
Figure 34 illustrates an exemplary cross-sectional (microtome) SEM of a graphene web trapping carbon and silicon fibers in a graphene pocket (the lower panel is zoomed in more than the upper panel).

In certain embodiments of the present disclosure, systems and methods are provided for the production of electrode materials and / or electrodes (e.g., thin film electrode deposits, for example, on a current collector), and other deposits comprising the components described herein. In some embodiments, the electrode comprises an electrode active material (e.g., silicon containing material) and a carbonaceous material (e.g., nanostructured carbon) (e.g., a graphene component such as reduced graphene oxide).

A method of making a silicon-carbon electrode material is provided that comprises electrospraying a fluid reservoir comprising an electrode active material and a carbonaceous material such as those described herein. In certain embodiments, the method (e. G., Electrospray) comprises preparing an electrostatically charged plume from a fluid storage.

In some embodiments, provided herein are methods of making an electrode, an electrode material, or an electrode precursor material. Generally, the method includes electrospraying a fluid stock (e.g., including a carbon material and an electrode active material in a liquid medium such as an aqueous medium, e.g., water). In some embodiments, electrospraying a fluid reservoir may be accomplished by applying a voltage thereto (e.g., applying a direct current voltage (V _DC ) or alternating voltage (V _AC ) to an electrospray nozzle such as that provided herein ). In a specific embodiment, application of a voltage to the nozzle (e.g., inducing the formation of a jet or plume from a fluid reservoir applied to the nozzle) is created. Such as at least about 0.01 mL / min, at least about 0.05 mL / min, at least about 0.1 mL / min, at least about 0.2 mL / min, or at least about 0.01 mL / min to about 10 mL / min, A fluid reservoir is provided in the nozzle.

In a specific embodiment, the fluid reservoir is electrosprayed with a gas (e. G., A control gas flow). In certain embodiments, the fluid reservoir and the gas exit the atomizing nozzle in the same direction. In some cases, the direction in which the fluid reservoir and the gas are ejected from the electrospray nozzle is within about 30 degrees relative to each other, or more preferably within about 15 degrees relative to each other (e.g., within about 10 degrees relative to each other, or Within about 5 degrees). In certain embodiments, the fluid reservoir and the gas are arranged to be coaxially discharged from the nozzle, or are substantially coaxial. In some cases, the driving force of the electrospray can be improved by combining the driving force of the electric field gradient with the high velocity gas by the arrangement and method described herein. In some cases, the batches described herein allow for throughputs of up to tens or even hundreds of times greater than simple electrospray fabrication, and can be used for high viscosity and / or high load (e.g., to the carbon and silicon inclusion materials described herein) The fluid can be atomized. In addition, in some cases, such electrospray techniques and systems provided herein enable the production of materials (e.g., electrodes, electrode materials, and electrode precursor materials) that are highly uniform. Conversely, other or conventional electrospray is generally not commercially available for many applications, for example due to non-uniform dispersion of droplet and droplet filler and non-uniform deposition of droplets, especially for high load systems. Also, in some cases, the throughput of other or conventional electrospray systems is not sufficient to be commercially useful in some applications. However, where applicable, other suitable techniques (e. G., Electrospray techniques utilizing fluid storage and / or inclusions provided herein) are optionally employed in the manufacture of the electrodes or deposits described herein.

In some cases, a plume containing a plurality of droplets (e. G., A droplet solution, droplet suspension, and / or droplet in an electrospray plume herein) of the fluid reservoir (e.g., using the method and / Or solid particles), or a jet that is subsequently transformed into a plume containing a plurality of droplets is formed. In certain instances, a plume containing a plurality of droplets is formed by electrospray (e.g., using the methods and / or systems provided herein) of a fluid reservoir as provided herein. In some cases, microfluidic (e. G., Micron or nanoscale droplets) with a uniform size distribution is formed in the manner described herein (e. G., Especially compared to standard electrospray techniques). In certain cases, this uniformity allows for greater control of deposit formation, such as thickness, thickness uniformity, compositional uniformity (e.g., within a composite), and the like. In certain embodiments, the films provided herein have an average thickness d _f of about 10 mm or less, such as about 5 mm or less, about 2 mm or less, or about 1 mm or less. In certain embodiments, such as where the film is used as a direct immersion electrode, the thickness of the film may be less than about 500 microns (micrometers), such as less than about 250 microns, less than about 200 microns, less than about 100 microns, , About 1 micron, about 5 microns, about 10 microns, 25 microns, 50 microns, 100 microns, etc.). In certain embodiments, the films provided in the present application is the thinnest portion of the _{film> d f / 10,> d} f / 5,> d f / 4,> d f / 3,> uniform thickness as d _f / 2 or the like Good sex. In a further or alternative embodiment, the thickest portion of the film is <10 xd _f , <5 xd _f , <3 xd _f , <2 xd _f , <1.5 xd _f , <1.2 xd _f , In a preferred embodiment, the minimum thickness of the film is d _f greater than 0.9 (more preferably greater than 0.95 _f d) and the maximum thickness is less than 1.1 d _f of the film (and more preferably less than 1.05 d _f).

In some cases, electrospray techniques (e. G., Provided herein) facilitate the formation of high-capacity electrodes such as those described herein. FIG. 2 illustrates an illustrative example of a gas control electrospray system 200 provided herein.

In some embodiments, the gas control system (and method) provided herein may be used to control the flow of fluid from a nozzle 202 (e.g., coaxially arranged as shown in Figure 2) (E.g., using V _DC or V _AC ) with a gas (shown with a downward arrow) having a controlled flow such as that shown in FIG. In some embodiments, along with the flow of air, the droplet 203 proximal to the nozzle may have more (e.g., in some cases, due to controlled airflow at the nozzle end 204) And is much smaller as the droplet 205 (droplet that is distal to nozzle 206 and / or proximal to current collector 207) moves away from the nozzle toward the current collector. In some embodiments, such a small dispersion uniformity (e.g., uniformity in size, horizontal distribution, etc.) provides a deposit 208 with significantly improved uniformity in dispersion, thickness, etc. of inclusions. 3, a uniform dispersion of the active material and the carbon material in the fluid reservoir and the resultant electrospray plume can be achieved using a carbon material (e.g., graphene, GO, rGO Sheet), thereby promoting the lapping of the active material nano structure 303. 4, additional deposition of the carbon material 402 and the active nanostructure 403 includes a plurality of active material nanostructures 405 that are wrapped and / or secured in the web of carbon material 402 Gt; 405 &lt; / RTI &gt; Figure 4 also shows a plurality of graphene envelopes comprising an outer surface and an inner surface. The graphene envelope optionally comprises at least one graphene component as shown in Fig. In addition, the various graphene components of the compositions described herein are part of one or more of the graphene envelopes described herein. Also, as shown, in some cases, the outer surface of one graphene envelope or portion thereof optionally forms a portion of the inner surface of the adjacent graphene envelope. Also, in some embodiments, the inner surface of the graphene envelope defines a graphene envelope pocket as shown in Fig. In certain embodiments, within the graphene envelope, at least one particle comprising an electrode active material is disposed within the graphene envelope pocket. Figure 5 shows an image of an exemplary electrode provided herein, comprising an electrode active material wrapped in a carbon web, or a plurality of graphene envelopes in which an electrode active material (as shown by Figure 4) is disposed .

The fluid reservoir provided herein (e.g., for electrospray) includes any suitable components. In a specific embodiment, the fluid reservoir comprises a liquid medium and an electrode active material or precursor thereof. In a specific embodiment, the fluid reservoir comprises a liquid medium, an electrode active material or precursor thereof, and a carbon material (e.g., a carbon that is a carbon such as the graphene component described herein).

Specifically, in certain embodiments, a fluid reservoir is provided in a first inlet of a first conduit of an electrospray nozzle in the method described herein. In some embodiments, the first conduit has an inlet and an outlet, and is surrounded by a wall having an inner surface and an outer surface along the length of the conduit.

In some embodiments, the fluid reservoir comprises a carbon inclusion material and a silicon inclusion material. Other additional inclusion materials are optionally included.

Any suitable silicon-containing clustering material is optionally used. In general, the silicon inclusion material comprises a silicon electrode active material (e.g., Si, SiOx, etc.) or a precursor thereof. In certain embodiments, the silicon material comprises a plurality of structures comprising a silicon material. In a specific embodiment, the silicon material is a silicon material that is active at an electrode, such as a cathode in a lithium ion battery. In a more specific embodiment, the silicon material comprises, by way of non-limiting example, silicon elements and / or silicon oxides (e.g. having the formula SiOx, where 0? X <2, Or 0 < x < 1). In a specific embodiment, x is from 0 to about 1.5. Any suitable encapsulation structure, such as fibers, particles, sheets, rods, and the like, is optionally employed.

Generally, the silicon containing inclusion structure is micron or less than 1 micron in size, such as a nanoscale structure. In certain embodiments, the silicon-containing inclusions provided herein have an average dimension of less than 100 microns, such as less than 50 microns, or less than 30 microns. In more specific embodiments, the silicon containing inclusions have an average dimension of less than 25 microns, less than 2 microns, less than 15 microns, less than 10 microns, and the like. In certain embodiments, the silicon containing inclusions have an average dimension of at least 200 nm, for example, from about 200 nm to about 10 microns. In another embodiment, clusters that are nanostructured, such as those having an average dimension of about 200 nm or less, such as about 10 nm to about 200 nm, are preferred. In certain embodiments, the silicon-containing inclusions have a high aspect ratio (length divided by width), such as being present in the form of fibers or rods, or a low aspect ratio, such as being present in spherical form. In some embodiments, the silicon containing inclusions have an average aspect ratio of from about 1 to about 100 or more. In specific embodiments, the silicon containing inclusions have an average aspect ratio of from 1 to about 50, or from 1 to about 20, or from 1 to about 10. In some embodiments, where the silicon containing inclusions have an aspect ratio of at least about 10, the silicon containing inclusions provided herein have at least one average dimension less than 100 microns, such as less than 50 microns, or less than 30 microns. In more specific embodiments, the silicon containing inclusions have an average dimension of less than 25 microns, less than 2 microns, less than 15 microns, less than 10 microns, and the like. In certain embodiments, the silicon containing inclusions have an average dimension of at least one of at least 200 nm, for example, from about 200 nm to about 10 microns. In other embodiments, the silicon-containing inclusions may have an average dimension of at least about 200 nm, such as from about 10 nm to about 200 nm (e.g., an average diameter of from about 10 nm to about 200 nm, High aspect ratio nanofibers or nanorods up to 10 times, up to 100 times, or more). In some cases where a larger structure is used, a larger droplet is necessarily formed upon electrospray in accordance with the method described herein.

In certain embodiments, the silicon containing inclusions used herein further comprise additional materials (e.g., as a composite) such as carbon (e.g., amorphous and / or crystalline carbon). For example, Figures 6 and 7 illustrate a silicon containing inclusion containing a carbon matrix impregnated therein with an electrode silicon active material. The silicon-containing inclusions described herein may optionally comprise any suitable amount (e. G., On average) of at least about 30 weight percent electrode silicon active, at least about 50 weight percent electrode silicon active, at least about 70 weight percent electrode silicon active, (E. G., Si and / or &lt; RTI ID = 0.0 &gt; SiOx). &Lt; / RTI &gt;

Any suitable carbon encapsulant material is optionally employed in the fluid reservoir. In certain embodiments, the carbon material is any suitable carbon material, such as a nanostructured carbon material. In some cases, the carbon material is a carbon sheet, a carbon ribbon, or the like. In a specific embodiment, the carbon inclusion material is a graphene component, such as graphene, or an analogue thereof, such as graphene, or graphene in which one or more carbon atoms thereof are replaced by one or more additional atoms such as oxygen, halide, hydrogen, Generally, the graphene or graphene component herein may be used in combination with other components, such as those described and illustrated herein, such as honeycomb grating structures (in some cases, such as non-pristine graphene, graphene oxide, reduced graphene oxide, (E. G., Having 1-25 layers) with the same specific defect (which may contain the same specific defect therein). In a specific embodiment, the graphene component is a graphene oxide component. In some cases, the carbon material is or comprises a graphene component such as graphene, graphene oxide, reduced graphene oxide, or combinations thereof. In a specific embodiment, the oxidized graphene component is replaced by oxygen such as a carbonyl (C = O) group, a carboxyl group (e.g., a carboxylic acid group, a carboxylate group, a COOR group such as R being a C1- ), An OH group, an epoxy group, an ether (-O-) group or the like. Figure 30 shows an exemplary oxidized graphene component (graphene oxide) structure comprising COOH, OH, epoxide, ether, and carbonyl groups. Other graphene oxide structures are also contemplated herein. In certain embodiments, the oxidized graphene component (or graphene oxide) comprises greater than about 60% (e. G., 60% to 99%) carbon. In a more specific embodiment, the oxidized graphene component comprises about 60 wt% to about 90 wt% carbon, or about 60 wt% to about 80 wt% carbon. In further or alternative specific embodiments, the oxidized graphene component comprises less than or equal to about 40 weight percent oxygen, such as from about 10 weight percent oxygen to about 40 weight percent oxygen, less than or equal to about 35 weight percent oxygen, less than about 1 weight percent, To 35% by weight of oxygen and the like. In some preferred embodiments, the oxidized graphene component comprises sufficient dispersion of the graphene sheet in the aqueous medium and sufficient oxygen to promote the opening. In some embodiments, the total% of carbon and oxygen does not constitute 100% of the graphene component or analog and the remaining mass is hydrogen (and / or, for example, ) Nitrogen). &Lt; / RTI &gt; In addition, the graphene component used in the methods and materials used herein optionally includes a pristine graphene sheet, or a defective graphene sheet such as one or more internal and / or external rings that are oxidized and / or apertured.

In certain embodiments, the fluid reservoir (and / or the electrodes and materials described herein) is coated with an electrode active material (e.g., silicon containing particles) and a carbon inclusion (e.g., graphene) 10 or more, such as about 1: 5 or more, about 1: 2 or more, about 1: 1 or more, and the like. In a preferred embodiment, the resulting &lt; RTI ID = 0.0 &gt; (e. G., &Lt; / RTI &gt; In order to improve this without increasing the capacity of the electrode material, it is preferable that the ratio of the active material to the carbon material is higher. In some embodiments, the weight ratio of active to inclusive inclusions in the fluid stock is from about 1: 1 to about 1000: 1, for example, about 2: 1. In some embodiments, the weight ratio of electrode active material to carbon inclusion is from about 1:10 to about 20: 1. In certain embodiments, the weight ratio of the electrode active material to the carbon inclusion is from about 1: 2 to about 10: 1, such as from about 1: 1 to about 5: 1, or from about 2: 1 to about 4: In certain embodiments, in some instances where a similar ratio of active material to carbon inclusions is provided for the materials and electrodes described herein, but the carbon inclusion material (e.g., graphene) is reduced (for example, Higher ratios for the materials and electrodes herein are also contemplated due to the weight loss resulting from the reduction process (due to the removal of oxygen from the carbon inclusion material).

The fluid reservoirs provided herein include any suitable amount of electrode active material. In a specific embodiment, the concentration of the inclusion containing the electrode active material and / or the electrode active material provided in the fluid reservoir is at least about 0.05% by weight, such as from about 0.1% to about 25% by weight, at least about 0.2% About 10 wt%, about 0.5 wt% to about 5 wt%, about 1 wt% to about 3 wt%, about 2 wt%, and the like.

The carbon inclusions (e.g., graphene components) and the active material (or precursor thereof) are included in the fluid reservoir at any suitable concentration. Generally, concentrations are desired to increase or maximize the throughput while avoiding clogging of the nozzle system and / or unwanted aggregation of the inclusion material, resulting in clogging. In some embodiments, the graphene component may be stored in a fluid storage (e.g., in an amount that is small enough to allow for good dispersion and unpacking of the graphene sheet (e.g., to reduce or minimize folding of the graphene sheet on top of each other) It is included in water. In certain embodiments, the fluid reservoir contains a clutane (e.g., a graphene component such as GO) that is at least about 0.01 weight percent carbon. In certain embodiments, the fluid stock comprises at least about 0.01% by weight of active material (e.g., silicon-containing particles). In a more specific embodiment, the fluid reservoir comprises a clutane (e.g., a graphene component such as GO) having from about 0.1 wt% to about 10 wt% carbon. In some embodiments, the fluid reservoir comprises a clutane (e.g., a graphene component such as GO) that is from about 1 wt% to about 5 wt% carbon. In a more specific embodiment, the fluid stock comprises from about 0.1% to about 30% by weight of active material (e.g., silicon-containing particles). In some embodiments, the fluid stock comprises from about 0.2 wt% to about 20 wt% (e.g., from about 0.2 wt% to about 10 wt%) of active material (e.g., silicon-containing particles). In some embodiments, the fluid reservoir comprises about 1 wt% to about 15 wt% (e.g., about 5 wt% to about 10 wt%) of active material (e.g., silicon-containing particles).

In certain embodiments, the method further comprises reducing the graphene component (e. G., Reducing its oxygen content). In some embodiments, the methods herein involve heat or chemically reducing the graphene component. In certain embodiments, the reduced graphene component is reduced graphene oxide. In some embodiments, the reduced graphene component or the reduced graphene oxide is optionally modified with oxygen (e.g., as described for graphene oxide wherein the weight percent of oxygen is less than the% oxygen by weight of the graphene component of the fluid stock) (Pristine, or defective, such as containing one or more open internal rings, etc.). Generally, the reduced graphene component (e. G., Reduced graphene oxide (rGO)) can be removed by, for example, heat (e. G., In an inert (e. G., Nitrogen, argon, (For example, by treating with hydrazine, hydrogen plasma, urea or the like) by irradiation (for example, by heating at a temperature of 200 ° C or higher under a hydrogen gas mixed with a gas, a hydrogen gas and the like) Lt; RTI ID = 0.0 &gt; partially &lt; / RTI &gt; or completely reduced by other mechanisms (e. 31 illustrates various exemplary reduced graphene oxide (rGO) structures. As can be seen, the structure is defective (or absent) with (or without) other existing atoms (e.g., hydrogen and / or oxygen including oxidized structures such as those discussed and illustrated herein) ), Is the basic two-dimensional honeycomb lattice structure of graphene. In various embodiments, the reduced graphene component or the reduced graphene oxide is present in an amount of at least about 60% (e.g., 60% to 99%), such as at least about 70%, at least about 75% , At least about 85 wt%, at least about 90 wt%, or at least about 95 wt% (e.g., up to about 99 wt%) carbon. In certain embodiments, the reduced graphene component (e. G., RGO) is less than or equal to about 35 weight percent (e.g., from 0.1 weight percent to 35 weight percent) (For example, from about 0.1 wt% to about 25 wt%), or up to about 20 wt%, up to about 15 wt%, up to about 10 wt% (e.g., up to about 0.01 wt% Up to 1% by weight of oxygen). In a specific embodiment, the reduced graphene component (e. G., RGO) comprises from about 0.1% to about 10%, such as from about 4% to about 9%, from about 5% to about 8% And the like. In some embodiments, the total% of carbon and oxygen does not constitute 100% of the reduced graphene component and the remaining mass is any suitable amount, such as hydrogen, or other materials discussed herein for the non- Atoms.

In certain embodiments, the carbon inclusions (e.g., graphene components) utilized in the fluid reservoir and materials herein have any suitable dimensions. In some embodiments, the carbon inclusions are two-dimensional materials such as graphene components (e.g., graphene oxide, reduced graphene oxide, graphene, etc.). In certain embodiments, the two-dimensional material (e.g., graphene component) has a first dimension and a second dimension (e.g., length and width), the average dimension of which is the average dimension of the material. In some embodiments, the active inductance has a three-dimensional (e. G., Length, width, height, or diameter and length for rods / fibers for particles) with an average dimension. In some embodiments, the carbon inclusions utilized are of sufficient size to coat or wrap the active material, such as an envelope or web, during electro-spray deposition. In a specific embodiment, the average dimension of the (e. G., Two-dimensional) carbon inclusions is equal to or greater than the average dimension of the active quartz. In certain embodiments, larger carbon inclusions provide the ability to wrap or encapsulate multiple active materials, such as Cluj. In some embodiments, the average dimension of the carbon inclusions is from about 0.1 to about 500 times the average dimension of the active quartz. In a specific embodiment, the average dimension of the carbon inclusions is from about 1 to about 200 times the average dimension of the active quartz. In a more specific embodiment, the dimensions of the carbon inclusions may range from about 5 times to about 25 times, for example, about 10 times (for example, about 10 times) the average size of the active material, to be. In other specific embodiments, the dimensions of the carbon inclusions may range from about 50 to about 250 times the average dimension of the active material (e.g., the electrode active material clut is an average dimension of about 200 nm or less), such as about 100 It is a ship. In some embodiments, the average dimension of the two-dimensional carbon inclusions is from about 1 micron to about 20 microns (e.g., from about 5 microns to about 10 microns).

In certain embodiments, a graphene component (e. G., Graphene oxide) is used in the fluid storage, and after the electrospray of the fluid storage, the collected deposit is heated to a temperature of, for example, (E.g., from about 150 ° C to about 350 ° C, from about 200 ° C to about 300 ° C, to about 200 ° C, to about 250 ° C, or to any suitable temperature) to at least partially reduce the graphene oxide Reducing the percentage of oxygen relative to carbon in the oxide. In some embodiments, the heat treatment of the graphene web retracts the graphene web around the grains enclosed within the graphene pocket. In some embodiments, the shrunk web further protects the particles therein by reducing or minimizing, for example, the space in the envelope through which the electrolyte can be trapped (e. G., By further minimizing electrolyte interactions with the particles) do. In certain embodiments, the pocket, e.g., the retracted pocket, has its own flexibility, which allows the particle to have its own flexibility, for example in a pocket (e.g., at least 200% of its original volume, at least 300% (E.g., at least 400%, etc.) (e.g., reacting with silicon to allow the particles to expand without unnecessary exposure to electrolyte that can form a fatal SEI layer when silicon is lithiated). In some embodiments, void volume in the interior of the retracted pocket (volume in the envelope not occupied by the internal particles) is at least 10%, at least 20% (e.g., %, At least 30%, at least 50%, and so on. In certain embodiments, the volume void volume inside the pocket is in any suitable volume, such as less than 100%, less than 50%, less than 25%, less than 10%, etc., of the volume of the internal particles. In various other embodiments, any other suitable technique is used, as the case may be, to reduce graphene oxide after deposition. In some cases, the reduction of graphene oxide after deposition (e. G., In some cases, by increasing the conductivity of the carbon inclusions) improves the performance characteristics of the material. For example, the various figures provided herein show that in some cases, the materials provided herein exhibit improved performance (e.g., non-capacity) in the case of graphene oxide (rGO) reduced compared to graphene oxide (GO) Characteristics are described. However, in some cases, such as where water is used as the liquid medium of the fluid reservoir, it is desirable to use graphene oxide (GO), for example, for improved solubility / dispersibility and processing facilities. In some embodiments, the method of the present invention omits the reducing step, e.g., a graphene component suitable for the electrode material is used directly in the fluid storage.

In certain embodiments, the liquid medium comprises any suitable solvent or suspending agent. In some embodiments, the liquid medium is only used as a vehicle and is eventually removed, for example, by evaporation during the electrospray process and / or drying of the deposit. In some embodiments, the liquid medium is an aqueous medium. In certain embodiments, the liquid medium is selected from the group consisting of water, alcohols (e.g., n-, tert-, sec- or iso-butanol), (e.g. n- or iso-) propanol, ethanol, , Or a combination thereof), tetrahydrofuran (THF), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), or combinations thereof. In more specific embodiments, the liquid medium comprises water.

In a method of manufacturing a material or electrode according to an embodiment of the present invention, the fluid reservoir containing the inclusions of the nanostructures, the carbon inclusions, and the water comprises (dispersed) The solution may be formed by mixing the solution with an encapsulant of a nanostructure containing a silicon active material.

In some cases, if the amount of graphene component in the (dispersed) solution is too low, the inclusion of the nanostructure (e.g., silicon active) can be effectively applied to the carbon web including the graphene component of the electrode or electrode material Can not be wrapped. Thus, in some of these cases, the properties of the electrode may deteriorate. In some cases, the gas-driven systems and methods described herein allow for the formation of an aerosol or plume having sufficient carbon (e.g., graphene) components to provide excellent formation of a protected electrode material (e.g., SiOx) Which may not be possible using conventional techniques. In certain embodiments, the viscosity of the fluid reservoir is at least 200 centipoise (cP), such as at least 500 cP, at least 1000 cP, at least 2000 cP, at least 2,500 cP, at least 3,000 cP, at least 4,000 cP, , Up to 20,000 cP, up to about 10,000 cP, etc.). In preferred embodiments, the viscosity of the fluid reservoir is from about 2,000 cP to about 10,000 cP.

In some embodiments, a method is provided herein for producing materials and electrodes (e.g., a thin layer deposit thereof) provided herein, which method comprises contacting the fluid storage provided herein with a gas (e.g., a controlled gas RTI ID = 0.0 &gt; flow). &Lt; / RTI &gt; In certain embodiments, the fluid and gas are ejected from the atomizing nozzle in a similar direction. In some cases, the discharge directions of the fluid reservoir and the gas from the atomizing nozzle are within about 30 degrees of each other, or more preferably within about 15 degrees of each other (e.g., within about 10 degrees of each other or about 5 degrees Within. In certain embodiments, the fluid reservoir and the gas are configured to be dispensed from the nozzle in a coaxial configuration. In some instances, the configurations and methods described herein allow for improved driving force of the electrospray by summing the driving forces of the electric field gradient with high velocity gas. In some instances, the compositions and methods described herein have provided some improvement in the material properties described herein, for example, as described in the Figures.

In some cases, electrospraying of the fluid reservoir (e.g., using the method and / or system provided herein) induces the formation of a jet, resulting in a plume containing a plurality of droplets. In some cases, electrospraying of a fluid reservoir as provided herein (e.g., using methods and / or systems provided herein) leads to the formation of a plume containing a plurality of droplets (e.g., (Collectively referred to herein to include droplet solutions, droplet suspensions, and / or solid particles in electrospray plumes). In some cases, the methods described herein lead to the formation of small droplets (e.g., nanoscale droplets) with a very uniform size distribution.

In certain embodiments, the methods provided herein include electrostatically charged plumes comprising a plurality of particles and / or droplets (e. G., A region of air comprising a plurality of particles and / or droplets dispersed therein) Section). &Lt; / RTI &gt; In certain embodiments, the plurality of particles and / or droplets are nanoscale particles and / or non-particles. In more specific embodiments, the plurality of particles and / or droplets have an average diameter of about 100 microns or less, about 50 microns or less, about 30 microns, about 20 microns or less, about 15 microns, or about 10 microns or less. In more specific embodiments, the plurality of particles and / or droplets have an average diameter of about 5 microns or less, for example, about 1 micron or less. In certain embodiments, the size of the particles and / or droplets is very uniform, wherein the standard deviation of the particle and / or droplet size is about 50% or less of the average size of the particle and / or droplet (e.g., , About 40% or less, about 30% or less, about 20% or less, about 10% or less (e.g., about 10 cm or more from the nozzle, At least about 20 cm, at least about 25 cm).

In some embodiments, the fluid reservoir, jet, and / or plume may include a fluid (e.g., water), an inclusion (e.g., of a micro or nano-structure) Includes. In certain embodiments, the compositions provided herein include a fluid (e.g., water), an inclusion (e.g., of a micro or nano-structure) comprising an active material, and a plurality Jet, or fluid reservoir. In various embodiments, the individual droplets optionally include either or both of the active material and / or the carbon inclusions. In addition, some or all of the droplet fluid (s) may be evaporated during the electrospray process (e.g., prior to deposition). In various embodiments, the concentration of the inclusion described herein, or the inclusion material in the composition comprising it, is generally greater than the concentration of such material in the fluid storage, or even in a jet (if evaporation of the fluid is initiated) Higher. In certain embodiments, the composition comprising a droplet or droplet has an inclusion concentration of at least 1.5x, at least 2x, at least 3x, at least 5x, at least 10x, etc. of the concentration of the droplet or composition / plume containing it For example, the inclusions comprise at least 70 wt%, at least 80 wt%, at least 90 wt%, or even 100 wt% of the droplet or composition / plume containing it.

In certain embodiments, the plume, and / or the particles and / or droplets thereof, may comprise particles (e.g., micro-and / or nanoparticles) containing a carbon inclusion (e.g., graphene component) and / / Or nano-particles). In some embodiments, the droplet includes both carbon-containing clusters and electrode active material-containing inclusions. In certain embodiments, the droplet comprises one of carbon-containing clusters or electrode active-material containing encuvings. In various embodiments, the plumes provided herein include either or both types of two types of droplets, as the case may be. In certain embodiments, the plume (e.g., particles and / or droplets thereof) further comprises a liquid medium (e.g., if the liquid medium of the fluid storage is not completely evaporated). In some cases, controlled airflow allows for increased rate and uniformity in dispersion and decomposition of jets and plumes, while increasing deposition uniformity and performance characteristics, which allows increased fluid storage rate. In certain embodiments, the fluid reservoir is maintained at a rate of from about 0.01 to about 10 mL / min, such as from about 0.05 mL / min to about 5 mL / min, or from about 0.5 mL / min to about 5 mL / min (For example, when a DC voltage V _DC is applied to the electrospray system). In some cases, use of an alternating current configuration allows higher throughput (e.g., when an alternating voltage (V _AC ) is applied to the electrospray system). In certain embodiments, the fluid reservoir is at least about 0.1 mL / min, such as from about 0.1 mL / min to about 25 mL / min, at least about 0.3 mL / min, at least about 0.5 mL / min, / min, at least about 2.5 mL / min, or at least about 5 mL / min.

In certain embodiments, a method as described herein includes providing a fluid reservoir to a first inlet of a first conduit of an electrospray nozzle, wherein the first conduit is connected to the conduit by a wall having an inner surface and an outer surface, And the first conduit has a first outlet. In certain cases, the walls of the first conduit form a capillary or other structure. In some cases, the first conduit is cylindrical, but the embodiments herein are not limited to this configuration.

Figure 8 illustrates a typical atomizing nozzle arrangement 800 and 830 provided herein. In some embodiments illustrated by two nozzle components 800 and 830, the nozzle device includes a nozzle component including a first (inner) conduit, the first conduit having a first wall having an inner surface and an outer surface, (Or supply) end 802 (e.g., fluidly connected to the first supply chamber and configured to receive a fluid storage), and the first conduit (e.g., And 832 and first outlet ends 803 and 833, respectively. Generally, the first conduit has first diameters 804 and 834 (e.g., an average diameter measured to the inner surface of the wall surrounding the conduit). In a further case, the nozzle component includes a second (outer) conduit, the second conduit is surrounded by a second wall (805 and 835) having an inner surface and an outer surface along the length of the conduit, (Or supply) ends 806 and 836 fluidly connected to a second supply chamber and configured to receive a gas, e.g., high velocity or pressurized gas (e.g., air), and a second inlet And outlet ends 807 and 837. In some cases, the second inlet (supply) ends 806 and 836 are connected to the supply chamber. In some cases, the second inlet (supply) ends 806 and 836 are connected to the second supply chamber via a supply component. 8 depicts connection supply components (e.g., tubes) 813 and 843 (not shown) for fluidly connecting supply chambers (not shown) to inlet supply components 815 and 845, which are fluidly connected to the inlet ends of the conduits ). &Lt; / RTI &gt; While this figure illustrates such a configuration for an external conduit, such configuration is also contemplated for the interior and any intermediate conduits. Generally, the first conduit has first diameters 808 and 838 (e.g., an average diameter measured to the inner surface of the wall surrounding the conduit). The first and second conduits have any suitable shape. In some embodiments, the conduit may be of a cylindrical (e.g., circular or elliptical), prismatic (e.g., octagonal prism), conical (e.g., truncated cone- (E.g., circular or elliptical), pyramidal (e.g., truncated pyramids, such as truncated octagonal prisms), and the like. In certain embodiments, the conduit is cylindrical (e.g., when the conduit and the wall surrounding the conduit form a needle). In some cases, the walls of the conduit are parallel, or within about one or two degrees parallel (e.g., when the conduit forms a cylinder or a prism). For example, the nozzle arrangement 800 may include a plurality of nozzles (not shown) for walls on opposite sides of the conduit, as shown by (e.g., 801a / 801b) and (805a / 805b) with parallel walls 801 and 805 Or parallel to the central longitudinal axis 809). In other embodiments, the wall of the conduit is not parallel (e.g., as when the conduit forms a cone (e.g., a truncated cone) or a pyramid (e.g., a truncated pyramid) Wider at the inlet end than at the outlet end). For example, the nozzle arrangement 830 may be configured for a wall on the opposite side of the conduit, as shown by a first conduit (e. G., 831a / 831b) with a parallel wall 831, (E.g., parallel to the longitudinal axis 809) and a second conduit (e. G., 835a / 835b) having a non-parallel wall 835, And is not parallel or angled with respect to the central longitudinal axis 809). In certain embodiments, the walls of the conduit are within about 15 degrees of parallel (e.g., as measured relative to the central longitudinal axis, or half of the angle between the opposites of the wall), or within about 10 degrees of parallelism . In certain embodiments, the walls of the conduit are within about 5 degrees of parallel (e.g., within about 3 degrees or less than about 2 degrees of parallelism). In some cases, conical or pyramidal conduits are used. In these embodiments, the diameter for the conduit without parallel walls refers to the average width or diameter of the conduit. In certain embodiments, the angle of the cone or pyramid is less than or equal to about 15 degrees (e.g., the average angle of the conduit side / wall measured relative to the central longitudinal axis or the facing conduit side / wall), or less than or equal to about 10 degrees to be. In certain embodiments, the angle of the cone or pyramid is less than or equal to about 5 degrees (e.g., less than or equal to about 3 degrees). In general, the first conduits 801 and 831 and the second conduits 805 and 835 have conduit overlap lengths 810 and 840, wherein the first conduit is located within the second conduit (the first and / 2 for at least a portion of the length of the conduit). In some cases, the outer surface of the first wall and the inner surface of the second wall are separated by conduit gaps 811 and 841. In some cases, the first outlet end protrudes beyond the second outlet end by a projection length 812 and 842. In some cases, the ratio of the conduit overlap length to the second diameter is any suitable amount, such as the amount described herein. In a further or alternative case, the ratio of the projecting length to the second diameter is any suitable amount, such as, for example, about 1 or less, such as the amount described herein.

8 also shows cross-sections 850, 860, and 870 of the various nozzle components provided herein. Each includes a first conduit 851, 861 and 871 and a second conduit 854, 864, and 874. As discussed herein, in some cases, the first conduit is surrounded by a first wall 852, 862, and 872 having an inner surface and an outer surface along the length of the conduit, Along the length of the conduit by means of the second walls 855, 865 and 875, In general, the first conduit has any suitable first diameters 853, 863, and 864 and any suitable second diameters 856, 866, and 876. The cross-sectional shape of the conduit may be any suitable shape and, in some cases, at different points along the conduit. In some cases, the cross-sectional shapes of the conduits are circular (851/854 and 871/874), elliptical, polygonal (861/864), and the like.

In some instances, the coaxial gas-controlled electrospray provided herein with coaxially configured nozzles provided herein may include providing a first conduit or fluid storage along a first longitudinal axis, and providing a second conduit or gas For example, a pressurized or high velocity gas) (e. G., And an electrospray of fluid storage in the process). In certain embodiments, the first and second longitudinal axes are the same. In other embodiments, the first and second longitudinal axes are different. In certain embodiments, the first and second longitudinal axes are within 500 microns of each other, within 100 microns, within 50 microns, and so on. In some embodiments, the first and second longitudinal axes are aligned within 15 degrees, within 10 degrees, within 5 degrees, within 3 degrees, within 1 degree, etc. of each other. 8 illustrates a cross-section of a nozzle component 870 having an inner conduit 871 that is off-center (or does not share a central longitudinal axis) with the outer conduit 874. As shown in FIG. In some cases, the conduit gap (e. G., The measurement between the outer surface of the inner wall and the inner surface of the outer wall) is averaged in some cases - the diameter of the inner surface of the outer wall 876, 872 by the bisection of the difference. In some cases, the shortest distance between the inner surface of outer wall 876 and the outer surface of inner wall 872 is the longest distance between the inner surface of outer wall 876 and the outer surface of inner wall 872 At least 10% (e.g., at least 25%, at least 50%, or any suitable percentage) of the distance.

In some embodiments, the fluid reservoir has any suitable rate. Additionally, the methods and systems described herein allow for the manufacture of electrospray deposits using highly viscous (and, for example, highly loaded) fluid reservoirs, if desired. For example, in some embodiments, the fluid reservoir used in the systems and methods of the present invention has a viscosity of at least about 0.5 centipoise (cP), such as at least about 5 cP, or from about 1 cP to about 10 poise Lt; / RTI &gt; In more specific embodiments, the viscosity is from about 10 cP to about 10 poise.

In some embodiments, the method may include providing a voltage (e.g., V _DC or V _AC ) to the electrospray nozzle, such as the electrospray nozzle provided herein, or the system provided herein may provide . In certain embodiments, a voltage is provided to an inner conduit (e.g., a wall thereof). In certain embodiments, application of a voltage to the nozzle provides an electric field to the nozzle (e.g., at the outlet of its internal conduit). In some cases, the electric field induces the formation of a "cone" (e.g., a Taylor cone), and ultimately a jet and / or plume, at the nozzle (e.g., at the outlet of its internal conduit). In some cases, after formation of the cone, the jets and / or plumes are broken down into small and highly charged liquid droplets (or particles) and are dispersed, for example, due to coulombic repulsion. As used herein, droplets and particles are interchangeably referred to herein as particles in which droplets (including, for example, a liquid medium of a fluid reservoir) or dried particles (e.g., If evaporated during the process).

In some embodiments, any suitable voltage (e. G., Direct current or alternating voltage) is applied (e. G., To the nozzle). In certain embodiments, the applied voltage is from about 8 kV _DC to about 30 kV _DC , for example from about 10 kV _DC to about 25 kV _DC . In other specific embodiments, the applied voltage is greater than about 10 kV _AC (e.g., the voltage means the mean square root voltage (V _rms )). In more specific embodiments, the applied voltage is greater than about 20 kV _AC , e.g., greater than about 30 kV _AC . In some specific embodiments, the applied voltage is from about 10 kV _AC to about 25 kV _AC . In certain embodiments, the power supply system is configured to provide a voltage to the nozzle. In some embodiments, the alternating voltage (V _AC ) has any suitable frequency, such as greater than about 25 Hz, for example, from about 50 Hz to about 500 Hz. In more specific embodiments, the frequency is from about 60 Hz to about 400 Hz, for example, from about 60 Hz to about 120 Hz, or from about 60 Hz to about 250 Hz.

In some embodiments, the voltage applied to the nozzle is from about 8 kV _DC to about 30 kV _DC . In certain embodiments, the voltage applied to the nozzle is from about 10 kV _DC to about 25 kV _DC . In other embodiments, the voltage applied to the nozzle is greater than about 10 kV _AC (e.g., greater than about 15 kV _AC , or about 20 kV _AC to about 25 kV _AC ). In some embodiments, the ac voltage (V _AC ) has a frequency from about 50 Hz to about 350 Hz.

In certain embodiments, the method provides pressurized gas to an external inlet of an external conduit of an electrospray nozzle. In some embodiments, the outer conduit is surrounded by an outer wall having an inner surface along the length of the conduit, and the outer conduit has an outer conduit inlet and an outer conduit outlet. In some cases, the pressurized gas is provided from a pressurized canister, by a pump, or by any other suitable mechanism. Generally, as a result of the provision of the pressurized gas to the inlet of the outer channel, the high velocity gas is discharged from the outlet of the outer channel of the atomizing nozzle.

Any suitable gas pressure or gas velocity is optionally employed in the method and / or system of the present disclosure. In certain embodiments, the gas pressure applied (e.g., at the inlet of the outer channel) is greater than about 15 psi. In more specific embodiments, the gas pressure is at least about 20 psi, at least about 25 psi, at least about 35 psi, at least about 45 psi, or any other suitable pressure. In certain embodiments, the velocity of the gas in the nozzle (e.g., the outlet of its outer channel) is greater than about 0.5 m / s, greater than about 1 m / s, greater than about 5 m / s, greater than about 10 m / , At least about 25 m / s. In more specific embodiments, the velocity is greater than or equal to about 50 m / s. In more specific embodiments, the velocity is greater than about 100 m / s, such as greater than about 200 m / s, or greater than about 300 m / s. In certain embodiments, the gas is any suitable gas including, for example, air, oxygen, nitrogen, argon, hydrogen, or combinations thereof.

In certain embodiments, the inner and outer conduits have any suitable diameter. In some embodiments, the diameter of the outer conduit is from about 0.1 mm to about 10 mm, for example, from about 1 mm to about 10 mm. In more specific embodiments, the diameter of the outer conduit is from about 0.1 mm to about 5 mm, for example, from about 1 mm to about 3 mm. In certain embodiments, the diameter of the inner conduit is from about 0.01 mm to about 8 mm, such as from about 0.5 mm to about 5 mm, such as from about 1 mm to about 4 mm. In systems using V _AC , even larger diameters (for example, an inner diameter of at least 2.5 cm, an outer diameter of about 1.05 times the inner diameter, at least about 1.1 times the inner diameter, etc.) . Generally, as discussed herein, the inner conduit is disposed within the outer conduit, preferably along the same axis, although some offset configuration is also considered to be within the scope of this disclosure. In some embodiments, the outer wall surrounds the outer conduit, and the outer wall has an inner surface (e.g., defining an outer conduit). In some embodiments, the average distance between the outer surface of the inner wall and the inner surface of the outer wall (referred to herein as the conduit gap) is any suitable distance. In certain instances, the conduit gap is at least about 0.1 mm, such as at least about 0.5 mm, or at least about 1 mm. In certain embodiments, the gap is small enough to promote high velocity gas in the nozzle and facilitate sufficient collapse of the charged fluid (jet) ejected from the nozzle (e.g., small enough droplet size in the plume and on the collection substrate and To provide sufficiently uniform inclusion dispersion). In some embodiments, the conduit gap is from about 0.01 mm to about 30 mm, such as from about 0.05 mm to about 20 mm, from about 0.1 mm to about 10 mm, and the like. In more specific embodiments, the conduit gap is from about 0.5 mm to about 5 mm. In some embodiments, the inner conduit and the outer conduit extend along the same or similar longitudinal axis, and the length of both the inner and outer conduits extending along the axis is the conduit overlap length. In some embodiments, the inner conduit length, outer conduit length, and conduit overlap length are greater than about 0.1 mm, such as from about 0.1 mm to about 100 mm, or greater. In certain embodiments, the inner conduit length, outer conduit length, and conduit overlap length are from about 0.5 mm to about 100 mm, such as from about 1 mm to about 100 mm, from about 1 mm to about 50 mm, from about 1 mm To about 20 mm, and the like. In certain embodiments, the ratio of the conduit overlap length to the first diameter is from about 1 to about 100 (e.g., about 10), or from about 0.1 to about 10, such as from about 0.1 to about 5, It is about 10. In some embodiments, the inner conduit is longer than the outer conduit, and the inner conduit projects beyond the outer conduit, for example, as shown in FIG. In some embodiments, the protrusion length is from about -0.5 mm to about 1.5 mm, for example, from about 0 mm to about 1.5 mm, or about 0 mm.

In certain embodiments, the methods of the present invention comprise collecting nano sized particles and / or droplets of the plume on a substrate and / or the system of the present invention is configured to perform the collection as described above. In certain embodiments, the collection of such small particles / droplets allows the formation of a uniform deposit on the substrate. In addition, if a small size of particles and / or droplets formed by the systems and methods described herein are provided, deposits with thin and / or uniform layers can be formed and excellent control of their thickness can be achieved. In some embodiments, the substrate is located opposite the outlet of the nozzle.

As discussed herein, the methods and systems described herein permit excellent control of the thickness of the films or deposits provided and described herein. In some embodiments, the film or deposit provided herein is a thin film or deposit, for example, having an average thickness of less than about 1 mm, for example, from about 1 micron to about 1 mm. In certain embodiments, the deposit has a thickness of less than or equal to about 500 microns, for example, from about 1 micron to about 500 microns, from about 1 micron to about 250 microns, or from about 10 microns to about 200 microns, To about 20 microns, and the like. In addition, the methods and systems described herein permit not only the production of thin layer deposits, but also the production of highly uniform thin layer films or deposits. In some embodiments, the film or deposit provided herein has an average thickness, wherein the thickness deviation is less than 50% of the average thickness, for example less than 30% of the average thickness, or less than 20% to be.

In certain embodiments, the process provided herein further comprises the step of compressing (e.g., calendering or otherwise compressing) the film or deposit (electrosprayed deposit) provided herein. In certain embodiments, the pressing of the deposit provides increased electrode density and / or a thin electrode, which, in some cases, provides an improved energy density per unit volume of the electrode. In certain embodiments, the energy density per unit volume of the electrode is improved by at least 1.1 times, for example, at least about 1.2 times, at least about 1.25 times, or at least 1.5 times, e.g., up to at least about two times. In certain embodiments, the energy density per volume (of the anode) provided herein is at least about 500 mAh / cubic centimeter (cc), such as at least about 750 mAh / cc, at least about 1000 mAh / cc, In certain embodiments, such a compacting step may be performed at a microstructure (e.g., about 1 micron or more, such as about 2 microns or more, or about 2 micro to about 100 microns, for example) Or &lt; / RTI &gt; herein), and the dimensions (or, for example, the average dimensions). In certain cases, the squeezing of an electrode material comprising a micro-scale electrode active material increases the density of the material because the micro-scale structure may leave a larger void (e.g., compared to the nanoscale structure) in the deposition process Especially useful. In some embodiments, the film or deposit is squeezed to a thickness of about 90% or less, about 80% or less, about 70% or less, about 60% or less, or about 50% or less of the thickness of the pre-squeezed deposit. Figure 20 illustrates exemplary deposits provided herein using microstructured active materials in combination with the carbon provided herein. As similarly illustrated in Fig. 19, the carbon component provides a good coating of the particles illustrated in Fig. As can be seen in Figure 20, in some cases, when the graphene component has an average dimension (e. G., An average of length and / or width) close to the average dimension of the particles in size, the particles enclosed within the carbon envelope (E. G., Relative to the relatively larger graphene component of Figure 19). As illustrated enlarged in the upper left perspective, deposits as produced are not optimally packed and leave a large number of voids. The enlarged view of the compression set (upper right) shows the increased density and fewer voids of deposit during compression. Similarly, it can be seen that the pressed deposits (lower right) have increased density compared to deposits (lower left) as produced. Figure 21 shows that pressing of the deposit significantly reduces the thickness of the electrode deposit (e.g., reduces the thickness of the deposit to a maximum of two times or more).

Further, in some embodiments, any additive in the fluid reservoir can be used to minimize clogging, for example, of an electrospray nozzle (and / or other system components) and to provide a good distribution of any inclusions in the resulting deposit To ensure uniformity, and / or to be dissolved and / or well dispersed prior to electrospray for other purposes. In certain embodiments, the fluid reservoir is agitated prior to being provided to the nozzle (e.g., its internal conduit inlet), or the system may be agitated (e.g., through an inlet of the internal conduit of the electrospray nozzle provided herein, Such as a mechanical stirrer or sonic system in conjunction with a fluid storage reservoir connected to the fluid reservoir (not shown).

In other embodiments, electrodes and / or electrode materials, including, for example, the component parts described herein, can be prepared by electrospraying a fluid storage, optionally including a nanostructured inclusion containing a liquid medium and an electrode active material, Followed by electrospraying a second fluid stock comprising a liquid medium and a carbon inclusion (e.g., a nanostructured carbon inclusion, such as the graphene component described herein). In some embodiments, the process is repeated until the desired loading amount and / or thickness is achieved, as the case may be. Further, in some embodiments, for example, the electrodes and / or electrode materials provided herein may optionally include a liquid medium, a nanostructured inclusion containing an electrode active material, and a carbon inclusion (e.g., nanostructured (E. G., A carbonaceous inclusion, such as the graphene component described herein), followed by a liquid medium and a carbon inclusion (e. G., A nanostructured carbon inclusion, e. Graphene component) of the second fluid stock. In some cases, the subsequent process of electrospraying the second fluid reservoir facilitates binding an increased amount of electrode active material on a substrate (e.g., a current collector), which in some cases can lead to, for example, By reducing the capacitance loss, the performance of the electrode and / or the electrode material can be improved. Such fluid reservoirs include any suitable components, concentrations, and the like, such as those described for the various fluid reservoirs described herein.

In certain embodiments, the substrate is any suitable substrate (e.g., a polished substrate, or a substrate positioned between an electrospray nozzle and a polished plate). In some embodiments, the collected deposits are optionally removed from the substrate to provide a powdered material. In certain embodiments, the deposit is optionally removed before or after a subsequent (e. G., Thermal reduction) treatment (e. G., Thereafter the powdered electrode material is provided). In some embodiments, when the electrode material is produced directly on the current collector, the substrate is a current collector material (e.g., a metal, such as copper or aluminum, foil or sheet). In this case, any reductive (e.g., thermal reduction) treatment is optionally performed without removing the deposited material from the substrate.

In certain embodiments herein, there is provided an electrode or electrode material comprising a carbon inclusion and a clut that is an active material. In certain embodiments, the carbon inclusion is a two-dimensional carbon-containing clathrate or graphene, for example, as described herein. In certain embodiments, the active inductance is a micro-or nano-structure comprising a structure comprising an electrode active material, such as silicon and / or silicon oxide (SiOx) as described herein.

In certain embodiments, the carbon inclusions have dimensions as described herein. In certain embodiments, the carbon inclusions may have a nanoscale (e.g., less than 2 microns, less than 1 micron, or less than 200 nanometers) structure to any one or more dimensions, such as nanostructured fibers, , And / or the like). In certain embodiments, the electrode active material is a silicon material (e. G., An active electrode, e. G., A cathode electrode material in a lithium ion battery).

In some cases, the materials or film / deposits provided herein (e. G., Electrode material deposited on the current collector) may have a high density (e.g., greater than about 0.4 g / cm ^3, greater than about 0.5 g / cm ³ , (E.g., from about 0.7 g / cm ³ to about 2 g / cm ³ ) (e.g., greater than about 1 g / cm ^3, greater than about 1.5 g / cm ³ , etc.), flexible, and / . As discussed herein, in some embodiments, calendared films are used to provide additional increased density of the film. In certain embodiments, such materials or films / deposits are suitable for any number of energy storage applications, such as, for example, cathode electrodes in lithium ion batteries.

In various embodiments, the electrode (e. G., Electrode deposit) comprises a carbon material and a silicon material. In certain embodiments, the carbon material (e.g., nanostructured) may include a graphene component, a structure or an analog (e.g., graphene (e.g., graphene sheet and / or graphene nanoribbon) Oxide, reduced graphene oxide, etc.).

In some embodiments, the silicon material (e.g., micro- or nano-structured) may be a carbon (e.g., graphene) matrix, a web (e.g., a graphene matrix or web, Or analogs), and / or are distributed within and / or on the envelope. In certain embodiments, the carbon web (including, for example, its envelope) comprises at least about 25 weight percent (e.g., at least about 50 weight percent, at least about 60 weight percent, at least about 75 weight percent, %, At least about 90 wt%, or at least about 95 wt%) graphene component. In certain embodiments, the silicon material comprises a plurality of nanostructures (e.g., having such nanoscale dimensions (e.g., less than 2 microns, with an average dimension of less than 1 micron) comprising silicon material in any one or more dimensions, Structures, such as nanostructured fibers, particles, sheets, rods, and / or the like). In some embodiments, the silicon material comprises a plurality of larger structures, such as microstructures (e.g., less than 100 microns, less than 50 microns, less than 30 microns, preferably less than 25 microns, less than 20 microns, less than 15 microns, Micron, etc., e.g., with an average dimension of up to about 200 nm). Other descriptions of suitable electrode active materials and / or silicon containing or base materials, inclusions, or structures are set forth herein. Also, in some instances, larger structures, such as larger droplets or particles, are essentially formed upon electrospray in accordance with the process described herein.

0임)를 포함한다. 특정 실시양태에서, 본원에 기재된 조성물, 물질, 및 전극에 포함된 규소 물질 및/또는 인클루전은 규소(규소 원소), 예컨대 결정질 규소를 포함한다. 일부 실시양태에서, 본원에 제공되는 규소 함유 입자는 40 중량% 이상의 규소 전극 활물질(예를 들어, SiOx, 예를 들어, 상기 식에서, 0 ≤ x < 2 임)을 포함한다. 특정 실시양태에서, 본원에 제공되는 규소 함유 물질은 50 중량% 이상(예를 들어, 60 중량% 이상, 70 중량% 이상, 80 중량% 이상 등)의 규소 전극 활물질(예를 들어, SiOx)를 포함한다. 일부 실시양태에서, 본원에 제공되는 규소 함유 입자는 40 중량% 이상의 전극 활성 규소(Si)를 포함한다. 특정 실시양태에서, 본원에 제공되는 규소 함유 입자는 50 중량% 이상(예를 들어, 60 중량% 이상, 70 중량% 이상, 약 70 중량% 내지 약 80 중량%, 80 중량% 이상 등)의 규소(Si)를 포함한다. 특정 실시양태에서, 규소(Si)의 양이 많을수록, 리튬화의 지연을 최소화하기 위해 더 적은 양의 SiOx(상기 식에서 0 < x ≤ 2임)가 바람직하다. 도 25는 사이클링 동안 애노드에서의 SiOx 인클루전을 사용한 예시적인 반전지의 용량을 예시하고 있다.In certain embodiments, the silicon material contained herein comprises an active material at the cathode in an electrode, e.g., a lithium ion battery, such as a silicon element, and / or silicon oxide (e.g., having the formula: SiOx, 0? X <2, for example, 0? X? 1.5, 0 <x <1, or x

0). In certain embodiments, the compositions, materials, and silicon materials and / or encapsulants included in the electrodes described herein comprise silicon (silicon elements), such as crystalline silicon. In some embodiments, the silicon-containing particles provided herein comprise at least 40% by weight of silicon electrode active material (e.g., SiOx, e.g., where 0? X <2). In certain embodiments, the silicon-containing material provided herein comprises a silicon electrode active material (e.g., SiOx) in an amount of at least 50 wt% (e.g., at least 60 wt%, at least 70 wt%, at least 80 wt% . In some embodiments, the silicon-containing particles provided herein comprise at least 40% by weight of electroactive silicon (Si). In certain embodiments, the silicon-containing particles provided herein may comprise at least 50 wt% (e.g., at least 60 wt%, at least 70 wt%, at least about 70 wt% to about 80 wt%, at least 80 wt% (Si). In certain embodiments, the greater the amount of silicon (Si), the lesser amount of SiOx (where 0 < x &lt; 2) is preferred to minimize the delay of lithiation. Figure 25 illustrates the capacity of an exemplary half-cell using SiOx inclusions at the anode during cycling.

In certain embodiments herein, a plurality of active electrode clusters (e.g., silicon-containing particles) and a plurality of carbon inclusions (e.g., graphene components such as reduced graphene oxide components, such as rGO) (Or substance) is provided. In certain embodiments, aggregates of carbon inclusions (e.g., graphene components) form a web comprising a web, a plurality of carbon envelopes (e.g., graphene envelope), or a plurality of carbon envelopes. In certain embodiments, each envelope comprises at least one (e.g., two or more) carbon in clusters (e.g., a graphene component, such as a reduced graphene oxide component, such as rGO). Generally, each envelope includes an inner surface and an outer surface, and the inner surface defines an envelope pocket. In some cases, each carbon inclusion forms, as the case may be, all or part of one or more envelopes, for example as illustrated in Fig. In certain cases, the outer surface of one envelope is all or part of the inner surface of the second envelope. In various embodiments, the web and / or envelope taken with the electrode active material comprises a plurality of complex domains in the composition or material. In certain embodiments, the complex domain comprises an envelope and an active material (e.g., an inclusion, such as a particle thereof).

In certain embodiments, compositions or materials are provided that comprise a graphene component, such as an oxidized graphene component (e.g., graphene oxide). In certain embodiments, the compositions or materials herein comprise a plurality of graphene envelopes, wherein the graphene envelope comprises at least one oxidizing graphene component (e.g., graphene oxide). In some embodiments, such compositions or materials are precursor materials for the electrode materials described herein. In certain embodiments, such precursor materials are converted to electrode materials through reduction reaction conditions such as thermal, chemical, or other processes described herein. In certain embodiments, the oxidized graphene component comprises an oxygen such as a carbonyl group, a carboxyl group (e.g., a carboxylic acid group, a carboxylate group, a COOR group such as wherein R is C1-C6 alkyl, Epoxide groups, and / or other functionalized graphene components. In certain embodiments, the oxidized graphene component (or graphene oxide) comprises about 60% or more carbon (e.g., 60% to 99%). In a more specific embodiment, the oxidized graphene component comprises about 60 wt% to about 90 wt% carbon, or about 60 wt% to about 80 wt% carbon. In a further or alternative embodiment, the oxidized graphene component comprises less than or equal to about 40 weight percent oxygen, such as from about 10 weight percent oxygen to about 40 weight percent oxygen, less than or equal to about 35 weight percent oxygen, % By weight oxygen, and the like.

In some embodiments, the weight ratio of the electrode active material or silicon-containing particles to the carbon inlets of the composition or material (e.g., precursor material comprising, for example, graphene oxide) is from about 1:10 to about 20: 1. In certain embodiments, the weight ratio of the electrode active material or silicon containing particles to the carbon inclusions is from about 1: 4 to about 10: 1, such as from about 1: 2 to about 5: 1, or from about 1: to be.

In another particular embodiment of the invention, there is provided a composition or material comprising a graphene component, such as a reduced graphene oxide component (e. G., Reduced graphene oxide). In certain embodiments, the compositions or materials herein comprise a plurality of graphene envelopes, wherein the graphene envelope comprises at least one (oxidized or reduced oxidized) graphene component (e. G., Reduced graphene oxide) . In some embodiments, such compositions or materials are electrode materials made from the precursor materials described herein. In certain embodiments, such electrode materials are converted from precursor materials through reduction reaction conditions, e.g., thermal, chemical, or through the processes described herein. In certain embodiments, the (e. G., Reduced oxidized) graphene moiety comprises an oxygen such as a carbonyl group, a carboxyl group (e. G., A carboxylic acid group, a carboxylate group, a COOR group, Alkyl, etc.), -OH groups, epoxide groups, and / or other functionalized graphene moieties. The oxidized graphene component generally contains less oxidation, while in some cases there are oxidized graphene components, residual oxidation and defects. In certain embodiments, the graphene component (e. G., Reduced graphene oxide) comprises at least about 60% (e.g., 60% to 99%), such as at least about 70% At least about 80 weight percent, at least about 85 weight percent, at least about 90 weight percent, or at least about 95 weight percent (e.g., up to about 99 weight percent or more) carbon. In certain embodiments, the graphene component (e.g., rGO) is less than or equal to about 35 weight percent (e.g., 0.1 weight percent to 35 weight percent) oxygen, such as less than or equal to about 25 weight percent , From about 0.1 wt% to about 25 wt%), or up to about 20 wt%, up to about 15 wt%, up to about 10 wt% (e.g., at least about 0.01 wt%, at least about 0.1 wt% Weight percent, etc.) of oxygen. In certain embodiments, the graphene component (e.g., rGO) comprises from about 0.1 wt% to about 10 wt%, such as from about 4 wt% to about 9 wt%, from about 5 wt% to about 8 wt% Of oxygen.

In certain embodiments, when a carbon inclusion material (e.g., a graphene component) is reduced, for example, a higher ratio of electrode active material or silicon-containing particles to the carbon inclusions may be used for the compositions, materials, And electrodes. In some embodiments, the weight ratio of the electrode active material or silicon-containing particles to the carbon inlets of the composition or material (e.g., electrode material comprising reduced graphene oxide, for example) is from about 1: 5 to about 20: 1 . In certain embodiments, the weight ratio of the electrode active material or silicon containing particles to the carbon inclusions is from about 1: 2 to about 20: 1, such as from about 1: 1 to about 10: 1, or from about 2: 1 to about 9: to be.

In certain embodiments, the compositions, materials, and electrodes of the electrodes described herein comprise a clathrate (or a precursor thereof) in any suitable number of active materials in the pockets thereof. In some embodiments, the individual envelopes include one or more inclusions therein. In certain embodiments, the individual envelopes include two or more (e.g., 2-10, 2-5, etc.) inclusions therein. In certain instances, for example, larger inclusions (e.g., micro-structured inclusions having a particle size (or average size), such as an average of greater than about 200 nm, such as from about 1 micro to about 10 microns) , There may be a small number of inclusions, such as from about 1 to about 10, or from about 2 to about 5, or from 1 to 10, such as from 2 to 5, inclusions in the individual envelope, &Lt; / RTI &gt; In some cases, for example, in the case of smaller enculphinations (e.g., for example, one or more nanostructured inclusions having an average dimension of less than 200 nm), more encapsulations, (E.g., about 50 to about 200, e.g., about 100), or 1 to 1000 (e.g., 50 to 20, e.g., about 100) Lt; / RTI &gt;

Further, in some embodiments, there are provided herein an article of manufacture comprising a silicon / carbon deposit as described herein, for example a thin film deposit, which may be made or prepared according to the process described herein. In certain embodiments, a conductive substrate (e.g., a current collector) is provided herein that includes a substrate, such as an electrode or deposit described herein, on the surface thereof. Also provided herein is an apparatus, for example, an energy storage device including a battery, such as a lithium ion battery containing such a material as described herein.

In certain embodiments, there is provided herein an electrode (or, for example, a lithium ion battery comprising such an electrode) comprising a carbon web binding a plurality of nanostructured inclusions, wherein the nanostructured encapsulant The electrode material includes an electrode active material (e.g., a negative electrode active material such as the silicon material described herein). Fig. 1 illustrates an electrode deposit 101 on the current collector 104. Fig. As illustrated, the electrode may comprise a carbon web 102 that binds a plurality of electrode active nanostructures 103. As illustrated in Figure 1, in some cases, a carbon material 102, such as a carbon sheet or ribbon (e.g., graphene, graphene oxide (GO), reduced graphene oxide (rGO) Pin analogue) surrounds and binds the electrode active nanostructure 103. In some cases, the carbon material 102 binding the electrode active material 103 prevents the electrode active material 103 from interacting with the electrolyte, and prevents the electrode active material 103 from being crushed. Also, in some cases, for example, when a low electron conductive electrode active material is used, the carbon material 102 promotes electronic conductivity at the electrode.

In some embodiments, the electrode active material can be a particulate encapsulant (e. G., Nanoscale - e.g., less than about 2 microns in one or more dimensions - microparticles (e.g., nanoparticles of less than about 2 microns in all dimensions, And nanofibers and nanofibers that are less than about 2 microns in size and less than about 2 microns in two dimensions), or other small dimensions having an average dimension, such as less than 30 microns, less than 20 microns, less than 15 microns, Nano-particles (e. G., Nanoparticles) are included in the form of or in the form of structural particles (e. G., Particles, rods or other structural components) Less than about 500 nm, less than about 250 nm, or less than about 100 nm. In more specific embodiments, one or more dimensions (e.g., Is about 50 nm or less, or about 25 nm or less, or about 10 nm or less, or about 5 nm to about 10 nm, or any other suitable size. In some specific embodiments, High aspect ratio structures are in the form of high aspect ratio structures, such as nanorods or nanofibers. In certain embodiments, the high aspect ratio structures are in the range of about 2 microns or less, such as about 1 micron, about 0.5 micron, or about 0.1 micro to about 0.2 micron High aspect ratio structures have an aspect ratio of at least about 10, at least about 20, at least about 25, or at least about 50, such as at most about 250. In certain embodiments, the high aspect ratio structure The second dimension is about 50 microns or less, such as about 1 micron to about 50 microns, about 2 micro to about 25 microns, etc. Figure 19 shows a cross- (E. G., SiOx) coated with (e. G., Graphene oxide) (at various magnification levels) coated with (b) and (c). As can be seen from the image, very good coverage of the particles with carbon was achieved. 19, the use of graphene components having average dimensions (length and / or width) greater than the average or minimum dimensions (e.g., diameter or length, width, height) (E. G., Provides a carbon envelope surrounding multiple particles). &Lt; / RTI &gt; Also, Figure 28 illustrates good coverage of silicon microparticles using larger graphene components (at varying magnification levels), while Figure 29 illustrates the use of smaller graphene components ) &Lt; / RTI &gt; in the case of a silicon microparticle. As illustrated in FIG. 29, when a smaller graphene component is used, many of the silicon microparticle components remain unprotected by the graphene component (some of which are visible in the rounded section).

In certain embodiments, the electrode active material can be a high energy capacity material (e.g., a higher capacity than graphite, e.g.,> 400 mAh / g,> 500 mAh / g,> 750 mAh / g,> 1000 mAh / Or more). In certain embodiments, the electrode active material is not graphite (non-graphite). In some embodiments, the electrode active material comprises a material having a high volumetric expansion upon lithiumation (e.g.,> 150%, or> 200%). In some cases, the electrode active material includes Si, Ge, Sn, Co, Cu, Fe, any oxidation state thereof, or any combination thereof. In certain embodiments, the anode or high energy capacity material comprises Si, Ge, Sn, Al, oxides thereof, carbides thereof, or alloys thereof. In certain embodiments, the anode or high energy capacity material is selected from the group consisting of SiOx (e.g., 0? X? 2 or 0 <x <1.5 in the above formula), SiO _a N _b C _c (for example, where a / 2 + 3b / 4 + c is less than or equal to about 1), Sn, SnOx (e.g., 0 < x < 2 or 0 &lt; x &lt; 1.5), Si, Al, Ge, or Si alloys.

In certain embodiments, the carbon material is any suitable carbon material, such as a nanostructured carbon material. In some cases, the carbon material is a carbon sheet, a carbon ribbon, or the like. In certain instances, the carbon material is or comprises a graphene component, such as graphene, graphene oxide, reduced graphene oxide, or combinations thereof. In certain embodiments, the graphene oxide comprises an oxygen such as a carbonyl group, a carboxyl group (e.g., a carboxylic acid group, a carboxylate group, a COOR group such as wherein R is C1-C6 alkyl, Side groups, and / or other functionalized graphenes. In some embodiments, the reduced graphene oxide is optionally graphene (including, for example, one or more open inner rings, etc.) functionalized with oxygen as described for graphene oxide . In general, the reduced graphene oxide rGO can be removed, for example, by thermally (e.g., heating to a temperature above 200 C), chemically (e.g., with hydrazine, hydrogen plasma, urea, etc.) For example, by using a strong pulse light), as a graphene oxide material that is partially or totally reduced. In various embodiments, the graphene oxide, or reduced graphene oxide, provided herein can have, for example, at least about 60% (e.g., 60% to 99%) carbon and up to about 35% (E.g., 1% to 35%) oxygen, for example, about 75% or more (e.g., 75% to 99%) carbon and up to about 25% (e.g., 1% to 25% (E. G., In weight percent). In some embodiments, the total percentage of carbon and oxygen does not constitute 100% of the graphene analogue with an additional mass comprising any suitable atom, such as hydrogen (and / or nitrogen, for example). In certain embodiments, graphene oxide is used in a fluid storage, and after electrospraying of the fluid storage, the collected deposits are heated to a temperature of about &lt; RTI ID = 0.0 &gt; 100 C & (E.g., at a temperature in the range of about 200 to about 350, about 200 to about 300, about 200, about 250, or any suitable temperature) Reducing the percentage of oxygen). In various other embodiments, any other suitable technique is used to reduce the graphene oxide after deposition, as the case may be. In some cases, the reduction of graphene oxide after deposition improves the performance characteristics of the material (e.g., in some cases, increasing the conductivity of the carbon inclusions). For example, the various figures provided herein show that, in some cases, materials provided herein exhibit improved performance (e. G., No capacity) using graphene oxide (rGO) reduced relative to graphene oxide (GO) To demonstrate the characteristics of the product. In some cases, however, it is preferred to use graphene oxide (GO) for its improved solubility / dispersibility and ease in processing when, for example, water is used as the liquid medium of the fluid reservoir.

In some embodiments, inclusions (e.g., fluid reservoirs, droplets, and / or inclusions in electrodes or deposits) comprise complexes of electrode active materials. In certain embodiments, the inclusions further comprise a second material (e.g., carbon, ceramic, etc.). In some embodiments, the inclusions are nanoscale inclusions, such as nanofibers, nanorods, or nanoparticles. In certain embodiments, the encapsulant comprises a composite comprising a carbon and a silicon material (e.g., a material having the formula SiOx, wherein 0 &lt; x &lt; = 2, or other active silicon material as described herein) For example, nanofibers). In certain embodiments, these materials are optionally prepared according to any suitable technique, and exemplary techniques thereof are described in U.S. Patent Application No. 14 / 382,423 entitled "Silicon Nanocomposite Nanofibers", entitled "Carbon and Carbon Precursors in Nanofibers" U.S. Patent Application No. 14 / 457,994, entitled &quot; Silicon-Carbon Nanostructured Composites &quot;, and U.S. Patent Application No. 62 / 111,908, entitled &quot; Which is incorporated herein by reference. For example, in certain embodiments, nanostructures comprising an electrode active material provided herein can be prepared by dispersing silicon nanoparticles (i.e., silicon and, in some cases, nanoparticles comprising the oxide thereof) (E. G., Gas-assisted electrospinning) the fluid stock and carbonizing the product (e. G., Nanofibers). In some embodiments, the inclusion is a carbon nanostructure (e.g., a carbon nanotube or a hollow carbon nanofiber) into which the silicon material described herein (e.g., silicon or the SiOx material described herein) is implanted. Figure 23 shows capacity retention and Figure 24 shows the cycling efficiency of a semi-conductor fabricated using an exemplary silicon-carbon composite fiber material as an active electrode containing an incultual material among the anode materials described herein.

Figure 6 illustrates an electrode / deposit 601 provided herein and an inclusion of a composite nanostructure (e.g., nanoparticles) comprising a carbon matrix 606 in which silicon inclusions (e.g., nanoparticles) 607 in the process are embedded , Nanofibers) 603 are shown. As shown, a carbon web (e.g., a carbon web including a carbon sheet) 602 fixes the encapsulant (e.g., nanofibers) 603 of the nanostructure to, for example, the current collector 604. FIG. 7 shows non-capacity data of this exemplary material (e.g., nanofiber composite (nanofibers) (e.g., silicon nanoparticles) in which the SiOx domain is embedded). Figure 17 shows a nanocomposite (nanofiber) composite with a carbon inclusion, including graphene oxide (GO) and reduced graphene oxide (rGO), such as silicon nanocrystals embedded in a carbon matrix , &Lt; / RTI &gt; including the SiOx domain). &Lt; RTI ID = 0.0 &gt;

Figure 11 shows non-capacity data of another exemplary material (e.g., a composite of nanostructures comprising Sn intercalated within a carbon matrix). As shown, high capacity and excellent cycling properties are demonstrated.

In another exemplary embodiment, the nanostructures comprising the electrode active material provided herein can be prepared by dispersing a silicon precursor in a fluid storage (e.g., a fluid storage having a polymer and a liquid medium / solvent) radiation (e. g., gas-assisted electrospinning) and Sikkim carbonizing the product (e.g., nano-fiber) (e.g., which in some case, for example, having the formula of SiOx or SiO _a N _b c _c described herein Which also serves to calcine the silicon precursor with an active silicon material). FIG. 18 illustrates non-capacity data in a full cell of, for example, an exemplary material made or prepared according to the above technique (e.g., a composite of nanostructures comprising SiOx intercalated within a carbon matrix). As shown, a high capacity is demonstrated with very good cycling properties.

In another exemplary embodiment, an inclusion (e.g., nanostructure) comprising an electrode active material provided herein comprises an inclusion of the inclusion of an electrode active material (e.g., nanostructure) or an electrode active material . In various instances, the materials are prepared for inclusion in the electrode or deposit, or are obtained and used from commercial sources.

In certain embodiments, an inclusion (e. G., Micro- or nanostructured) comprising an electrode active material provided herein may comprise particles (e. G., Microparticles or nanoparticles) comprising an active silicon material such as SiOx Nanoparticles). In certain embodiments, the active silicon material is silicon (Si). In some embodiments, the inclusions (e.g., nanostructures) are silicon nanoparticles. Figure 9 shows non-capacity data in a full cell using silicon nanoparticles (as nanostructures containing the electrode active material) and graphene oxide (as a carbon inclusion material). As shown, high capacity with excellent cycling properties is demonstrated. Figure 15 is a plot of the specific capacity of an exemplary material comprising a nanostructure including an electrode active material (e.g., silicon nanoparticles) and a carbon inclusion (e.g., graphene oxide sheet) and a comparative material (electrode made by drop casting) Lt; / RTI &gt; As can be seen, even at higher fill rates, the negative electrode material prepared according to the methods described herein has a much higher specific capacity than electrode materials made using drop cast techniques, but otherwise includes similar components. Also, as shown, even at higher charge rates, the negative electrode material produced according to the methods described herein has a much higher specific capacity than electrode materials made using non-gas controlled electrospray techniques, &Lt; / RTI &gt; Also, in some cases, as shown, the materials provided herein have significantly improved capacity retention rates than electrode materials made using drop cast and non-gas controlled electrospray techniques. Figure 16 shows the improved impedance values of the anode made according to the technique (e.g., gas-controlled electrospray), as compared to other anodes made with similar components.

Figure 10 shows the coulombic efficiency values of the exemplary lithium ion battery cathodes (anodes) provided herein using silicon nanoparticles and various carbon inclusions (e.g., graphene oxide and reduced graphene oxide). As shown, the materials provided herein exhibit excellent coulombic efficiency. Figure 12 shows a cyclic voltammetry (CV) curve of directly deposited silicon nanoparticles and graphene oxide or reduced graphene oxide on an electrode. In certain cases, high coulombic efficiency (η c) value, particularly the value of the first cycle coulombic efficiency while it is important for battery application of commercially available (η c = Q _out / Q _in, where Q _out is a discharge cycle The amount of charge leaving the battery, and Q _in is the amount of charge entering the battery during the charge cycle). In some instances, the poor first cycle Coulomb efficiency of the anode results in a capacitance loss and / or capacity mismatch between the anode and the cathode. For example, if the anode irreversibly loses over 15% of its capacity during the first cycle, there may be a large capacity mismatch between the anode and the cathode. In some cases, an excess of electrode material is optionally used to make up for mismatch, but a typical commercial battery application requires a first cycle Coulomb efficiency of about 85% or more for a lithium ion battery anode material. In certain embodiments, the electrode and / or electrode material (e.g., film) provided herein has a first cycle Coulomb efficiency of at least about 80%, more preferably at least about 85%. In a more preferred embodiment, the electrode and / or electrode material (e.g., film) provided herein has a first cycle Coulomb efficiency of at least about 88%, more preferably at least about 90%.

In certain embodiments, a thin layer electrode (e.g., including the electrode material provided herein) deposited on a current collector is provided herein. In some embodiments, the electrode is preferably attached to the current collector. In a specific embodiment, the electrode is formed by folding the electrode / current collector two or more times (e.g., three times or more, four times or more) at an angle of 90 degrees or more (For example, the percentage of separation of the electrode from the current collector based on the area) is less than 10% (for example, less than 5%, less than 3%, less than 1%, etc.) . Figure 13 shows images of various nanostructured electrode active materials and carbon housings, such as those coated with those described herein. Electrodes 1301 deposited on the current collector using a drop cast technique, electrodes 1302 deposited on the current collector using slurry coating / doctor blade technology, and electrospray techniques described herein, And electrodes 1304, 1305 and 1306, respectively, which are folded electrodes. As shown, in some cases, as shown in Fig. 14, an electrode having a smooth and / or uniform surface having an excellent covering ratio as compared with an electrode of drop casting, for example, having a poor covering ratio and a separation ratio at the time of folding Are provided herein. 14 shows an image of an electrode folded repeatedly (1402) and an image of its front side 1403 and back side 1404 as an electrode 1401 deposited on a current collector using an electrospray technique . As shown, in some embodiments, despite severe folding, the electrode maintains its structure well, with minimal peeling, or without peeling.

In some embodiments, a relatively small amount of carbon inclusion is needed to form a carbon web that fixes the electrode material and / or the electrode active material. In certain instances, this low carbon loading requirement enables not only a high capacity of the electrode active material, but also a very high capacity of the entire electrode. In addition, if a carbon inclusion configured to fix the active material (e.g., to the current collector) is included, the electrode will contain a very high concentration of active material, e.g., no need to use additional binder (e.g., Containing electrode is formed), a filler and the like need not be used. In some instances, such high concentrations of electrode active material in the electrodes and / or electrode materials provided herein enable the production of electrodes with the desired capacity while using very small amounts of material. In some cases, the methods provided herein may not only produce a high capacity material, but also provide a thin electrode material having very good uniformity and very low defect properties (e.g., defects may result in reduced capacity during cycling) It is well designed to manufacture.

In some embodiments, the carbon inclusion comprises less than about 20 weight percent (e.g., less than about 10 weight percent, less than about 5 weight percent, or about 0.5 weight percent to about 3 weight percent) of deposits, or less than about 20 weight percent (I. E., An additive of the non-liquid medium component of the fluid storage) of the fluid storage (e. G., Up to about 10%, up to about 5%, or from about 0.5% to about 3%).

In some embodiments, the weight ratio of inclusions (e.g., microstructures and / or nanostructures) to carbon inclusions (e.g., in fluid reservoirs, deposits, and / or materials provided herein) 8: 2 to about 999: 1, such as about 85:15 to about 995: 5, about 9: 1 to about 99: 1. In certain embodiments, the percentage of inclusions (e.g., microstructures and / or nanostructures) comprising an active material in an electrode or electrode material is greater than or equal to about 25 weight percent, such as greater than or equal to about 50 weight percent, greater than or equal to about 75 weight percent, About 80 wt% or more, about 85 wt% or more, about 90 wt% or more, about 95 wt% or more, and the like. Also, in some embodiments, the amount of active material in the electrode or electrode material may be greater than or equal to about 20 wt%, such as greater than about 40 wt%, greater than about 50 wt%, greater than about 60 wt%, greater than about 70 wt% Or more, about 90 wt% or more, and the like.

In certain embodiments, the electrode is a thin layer electrode (e. G., Deposited on a current collector). In certain embodiments, the electrode has a thickness of about 500 microns or less, such as about 250 microns or less, about 200 microns or less, about 25 microns to about 500 microns, such as about 50 microns to about 200 microns. In some embodiments, the electrode has a conductivity of less than about 10 mg / cm ² , such as from about 0.1 mg / cm ² to about 10 mg / cm ² , less than about 5 mg / cm ^2, less than about 4 mg / cm ² , cm ² , and a mass loading on the substrate of from about 1 mg / cm ² to about 2 mg / cm ² . In certain embodiments, a material having a high areal density, such as greater than about 0.1 mg / cm ^2, greater than about 0.5 mg / cm ² , or greater than about 1 mg / cm ² , such as greater than about 0.5 mg / cm ² to about 5 mg / cm ² , such as about 1 mg / cm ² to about 5 mg / cm ² ) is used. In certain embodiments, the electrodes and / or materials provided herein have a good capacity per electrode area. For example, in some embodiments, the electrodes and materials provided herein have a conductivity of at least 1 mAh / cm ² , such as at least about 2 mAh / cm ^{2, at} least about 3 mAh / cm ² , or from about 2 mAh / cm ² to about 5 and an area capacity of mAh / cm ² . Figure 26 shows the capacity and capacity retention of an exemplary full battery with an anode having a capacity of about 3 mAh / cm ² , which is about twice as large as that seen in a conventional lithium ion battery full battery.

In various embodiments, the current collector is any suitable material such as a metal (e.g., aluminum, copper, etc.) (e.g., metal foil) or a carbon substrate (e.g., carbon cloth, carbon paper, etc.). In certain embodiments, the carbon substrate provides improved flexibility to the combined electrode and current collector product.

In various embodiments, the electrode materials and electrodes provided herein have a high capacity (e.g., a lithium ion battery, such as a non-capacitive battery or a full capacity battery). In certain embodiments, the electrode material and / or the electrode have a specific capacity of at least about 500 mAh / g at a fill rate of about 1 A / g. In a more particular embodiment, the electrode material and / or the electrode has a specific capacity of at least about 600 mAh / g at a fill rate of about 1 A / g. In a still further particular embodiment, the electrode material and / or the electrode has a specific capacity of at least about 700 mAh / g at a fill rate of about 1 A / g. In a more particular embodiment, the electrode material and / or the electrode has a specific capacity of at least about 800 mAh / g at a fill rate of about 1 A / g. In a more particular embodiment, the electrode material and / or electrode has a specific capacity of at least about 1000 mAh / g (e.g., at least about 1100 mAh / g, or at least about 1200 mAh / g) at a fill rate of about 1 A / g . In some embodiments, the electrode material and / or the electrode have a specific capacity of at least about 500 mAh / g at a fill rate of about 2 A / g. In a more particular embodiment, the electrode material and / or the electrode has a specific capacity of at least about 600 mAh / g at a fill rate of about 2 A / g. In a more particular embodiment, the electrode material and / or the electrode has a specific capacity of at least about 700 mAh / g at a fill rate of about 2 A / g. In a more particular embodiment, the electrode material and / or electrode has a specific capacity of at least about 800 mAh / g at a fill rate of about 2 A / g. In a more specific embodiment, the electrode material and / or electrode has a specific capacity of at least about 1000 mAh / g (e.g., at least about 1100 mAh / g, or at least about 1200 mAh / g) at a fill rate of about 2 A / g . In certain embodiments, such a capacity may be used in an initial cycle (charge and / or discharge cycle), at or after the second cycle, at or after the fifth cycle, at or after the tenth cycle, At or after the 150th cycle, then at or after the 100th cycle, at or after the 150th cycle, at or after the 200th cycle, then at or after the 250th cycle, or a combination thereof. In certain embodiments, the specific capacity of the electrode material and / or electrode at or after the 200th and / or 250th cycle (e.g., a charge and / or discharge cycle) may be a first cycle, a fifth cycle, and / (For example, 85% or more) of the specific capacity of the electrode material and / or electrode in the first cycle.

In some embodiments, a battery (e. G., A lithium battery, e. G., A lithium ion battery) comprising the electrode or electrode material described herein is provided herein. In certain embodiments, the batteries provided herein comprise an anode and a cathode, of which at least one electrode is the electrode described herein. In some embodiments, batteries are provided herein that include a negative electrode comprising a direct-immersion electrode as described herein, an electrode material described herein, and / or a carbon-silicon web and / or an envelope as described herein. In a more particular embodiment, a lithium ion battery is provided herein that includes a cathode, an anode, a separator, and an electrolyte, wherein the cathode comprises an electrode as described herein (e.g., a plurality of nanostructures, (Electrode active material), which is the nanostructure.

In some embodiments, a binder-free electrode, such as a binder-free electrode that is manufacturable by the manufacturing process described herein, is provided herein. In some embodiments herein, a general method of making the electrode using any suitable materials is provided. In some instances, a general approach is provided to fabricate highly uniform electrodes in a highly efficient manner. In certain instances, the process described herein provides direct deposition of an electrode on a conductive substrate (e.g., a current collector) without the need for downstream processes such as drop casting, slurry coating, long term or high temperature drying steps, .

In various embodiments of the disclosure, inclusions and materials are described as having unique properties. It is to be understood that the disclosure includes disclosure for a plurality of enclosures having an average equivalent to that of the identified proprietary nature and vice versa.

In various embodiments, the term "electrode" as used herein to have a particular nature, functionality, and / or configuration includes the disclosure for electrode materials having the same properties, functionality, and / Also, reference to a solution herein is meant to include a liquid composition in which the inclusion portion is dissolved and / or dispersed.

Example

Example 1

Fluid stocks were prepared by combining silicon nanoparticles, graphene oxide and water in a weight ratio of Si NP (7.5%): GO (2.5%): water (90%). Thereafter, in the direction of the substrate (e.g., a metal current collector) at a flow rate of 0.2 mL / min at 2 kV / cm, the fluid reservoir is introduced into the gas stream The fluid reservoir was electrosprayed. Deposits (electrodes) with mass loading of about 1-2 mg / cm ² were collected on a substrate without the need to add binders or further processing.

(Active material) in N-methyl-2-pyrrolidone (NMP): 10 (super P (polytetrafluoroethylene) ): 10 PAA, another electrode / collector system was also prepared using silicon nanoparticles and graphene oxide. In one embodiment, the slurry is drop cast on a current collector; In another embodiment, the slurry was cast on a current collector using a doctor blade.

Figure 13 shows an image of the electrode / current collector composition made according to the process as described above, and also an image of such a composition after folding. While the electrospray composition is being dried immediately or almost instantaneously, the drop cast and doctor blade compositions require up to 6 hours or more to dry in the oven at 120 ° C. In addition, it has been observed that the electrospray composition exhibits very good uniformity and adhesion properties (i.e., good adhesion of the electrode to the current collector) upon folding. The drop cast composition, however, has very poor uniformity and has partial coverage of the current collector in the middle, but exhibits adequate adhesion of the electrode to the current collector at folding. The slurry (doctor blade) composition exhibited excellent uniformity as shown in FIG. 13, but also exhibited very poor adhesion (i. E., It exfoliates or delaminates from the current collector when folded).

In addition, these compositions utilized much higher amounts of inert (or less active) electrode material during fabrication and exhibited much less specific capacity. The 2032 coin cell Li ion battery was fabricated using the various cathode / collector systems described herein. To fabricate the half-cell, Li metal was used as a counter electrode, and polyethylene (about 25 占 퐉 thickness) was inserted as a separator between the working electrode and the counter electrode. A coin cell Li ion battery was assembled with the electrolyte in an Ar filled glove box. A homomixed 1M hexafluorophosphate (LiPF ₆ ) solution with dimethyl carbonate and fluoroethylene carbonate (50:50 wt / wt%) was used as the electrolyte. The half-cells were galvanostatically charged and discharged in a voltage window of 0.01-1.5 V vs. Li / Li +, while the full cell was operated at 2.5-4.2 V.

Figure 15 shows the specific capacity of the electrode material made using drop cast and electrospray techniques, as described above. As shown, the electrodes fabricated using the electrospray techniques described herein demonstrated significantly higher capacities than the electrodes made using the drop cast technique, even at higher charge / discharge ratios. Further, Fig. 16 shows the improved impedance characteristics of the electrode produced by electrospray.

Example 2

A complete cell was prepared using the mixed lithium cobalt oxide (LCO) cathode and anode of Example 1. FIG. 9 shows full cell data at a charging / discharging rate of 0.1 C. As shown, the initial specific capacity of the anode was about 1600 mAh / g and had excellent cycling retention.

Example 3

Electrodes were prepared according to the electrospray technique described in Example 1. (For example, to convert graphene oxide to what is referred to herein as reduced graphene oxide by at least partially reducing and / or removing defects of the graphene oxide thereof) Respectively. Figure 5 shows images of electrodes electrosprayed at various magnifications and also images of non-heat treated and heat treated electrodes. Figure 10 shows the coulombic efficiency of various loading for both heat treated and non-heat treated electrodes. As shown, for both loading, the heat-treated sample (referred to as "RGO" in the figure) demonstrated improved Coulomb efficiency compared to the non-heat treated analogue, especially in the first cycle. Figure 12 shows CV curves for both heat treated and non-heat treated electrodes.

Example 4

Using a process similar to the process described in Example 1, electrodes were prepared using nanofibers and composites comprising carbon and silicon (e.g., a carbon matrix with embedded silicon nanoparticles therein). As described in Example 3, both heat treated and non-heat treated anodes were prepared. In addition, a semi-conductive paper was produced according to a process similar to the process described in Example 1. Figure 34 shows an image of a graphene web with carbon and silicon fibers trapped in its graphene pocket as a cross-sectional (microtome) SEM image of an exemplary graphene web.

In Fig. 17, the non-capacity data for such electrodes is shown. As shown, good specific capacity and excellent retention were obtained, and the heat treated (labeled "RGO") sample demonstrated even higher specific capacity.

In addition, a full cell was prepared using an electrode using the same method as described in Example 2. Fig. 7 shows the specific capacity of the electrode, and excellent capacity and storage ratio were observed.

Example 5

Using a process similar to the process described in Example 1, the electrode was fabricated using nanofibers and a composite comprising carbon and tin material (e.g., a tin-embedded carbon matrix inside). As described in Example 3, both heat treated and non-heat treated anodes were prepared. In addition, a semi-conductive paper was produced according to a process similar to that described in Example 1.

Fig. 11 shows the non-capacity data for these electrodes. As shown, good specific capacity and excellent retention were obtained, and the heat treated (labeled "RGO") sample demonstrated even higher specific capacity.

Example 6

Using a process similar to that described in Example 1, microstructured silicon and graphene oxide were used to form deposits on the current collector to produce electrodes. The prepared deposit was used as a first electrode, and a lithium metal was used as a counter electrode to prepare a half-cell. As shown in Fig. 22, a specific capacity of about 1,400 mAh / g at 1 A / g was achieved. The capacity retention was excellent and the first cycle Coulomb efficiency was about 89%.

Example 7

Various electrodes and electrode materials were prepared using an active material (silicon or silicon oxide (SiOx)). 3.0 g of the GO aqueous suspension was diluted to 5.0 g DI water. After suspending the suspension for 1 hour, 60 mg or 120 mg of active material (1: 1 or 2: 1 weight ratio with graphene oxide) was added. In another embodiment, silicon nanoparticles (70-100 nm), SiOx microsized particles (3-10 mu m), silicon microparticles (1-3 microns, polycrystalline, 99.99% purity) were used as active materials. Thereafter, the mixture of the active material and the graphene oxide was ultrasonicated for one hour and stirred overnight and then sprayed. Air-controlled electrospray was applied to the preparation of electrode material, which involved direct deposition of the binderless electrode. Electrospray was performed under ambient conditions using a Harvard Apparatus PHD 2000 Infusion Syringe Pump with a set of coaxial needles. The solution was fed through the inner 17G needle and the gas was fed through the outer 12G needle. The operating voltage was 20 kV, the working distance was 20 cm, the solution feed rate was set at 0.05 mL min ^-1 -0.1 mL min ^-1 and the gas pressure was 28 psi. In order to obtain an active material / RGO electrode, the sprayed active / GO is annealed in an N ₂ atmosphere (tube furnace) at 400 ° C for 1 hour to reduce the GO and ramp at 5 ° C / min . A direct immersion electrode was immersed on the copper foil.

The structure and morphology of the samples were characterized by scanning electron microscopy (SEM, LEO 1550) and transmission electron microscopy (TEM, FEI T12 Spirit). The active material and carbon ratio were determined by thermogravimetric analysis (TA instruments Q500). Electrochemical measurements were performed using a CR-2032 coin cell. The prepared electrode was used directly without any further treatment. 1 M LiPF ₆ in a mixture of ethylene carbonate, diethyl carbonate and dimethyl carbonate (2: 1: 2 by vol%) together with the additive of 10 wt% fluoroethylene carbonate was used as the electrode for the silicon-related material. In a half cell, a lithium foil was used as a counter electrode. A LiCoO ₂ electrode (MTI.) Was used as the cathode in the full cell. Battery assembly was performed in an argon filled glove box. The galvanostatic charge / discharge measurements were performed in a voltage cut-off window of 0.01-1.5V for the half-cell and 2.5-4.2V for the full cell using a Land battery test system. The current density and the non-capacity were based on the total mass of the electrode material. Cyclic voltammetry was measured using a PARSTAT 4000 (Princeton Applied Research) electrochemical workstation. In some cases, the cell was stabilized to a pre-cycle of 3-10 (i.e., the cycle before the first cycle; however, the first cycle Coulomb efficiency refers to the complete first cycle, whether it is a pre-cycle or not) . Unless otherwise specified, the cycling speed is typically 1C.

Example 8

Using a process similar to that described in Example 7, a direct-immersion anode was prepared using nanofibers having a carbon matrix backbone with silicon nanoparticles embedded therein. The direct-immersed anode had a loading of 1.93 mg / cm ² , a capacity loading of 4.52 mAh / cm ² , a weight capacity of 2,338 mAh / g, a first cycle Coulomb efficiency of 80%, an electrode density of 0.46 g / cc , And a volume energy density of 1061 mAh / cc. The prepared half cell was provided with the capacity retention rate disclosed in Fig. 23 and the cycling efficiency described in Fig. As shown in the figure, despite having a weight capacity well in excess of 2,000 mAh / g, the material exhibited excellent first cycle Coulomb efficiency with very good capacity retention.

Example 9

Using the process described in Example 7, a direct-deposited anode was prepared using silicon oxide (SiOx) microparticles. A half-cell was fabricated and showed an initial capacity of about 1,200 mAh / g after three pre-cycles as shown in Figure 25 and a good capacity retention rate (about 1,000 mAh / g) after 100 cycles.

Example 10

Using the process described in Example 7, a directly deposited anode was prepared with silicon (Si) microparticles at an initial SiMP: GO weight ratio of 2: 1 and a final SiMP: rGO weight ratio of about 4: 1 . , Which showed an initial capacity of about 1,600 mAh / g (after some pre-cycles) and a good capacity retention (> 85%) after 100 cycles (at 1 A / g). In addition, an extremely high first cycle Coulomb efficiency was achieved (> 88%), which is much higher than the first cycle Coulomb efficiency achieved for similar systems using silicon nanoparticles (about 80% for Si NP, Typically> 85% is required for industry).

The complete cell was also prepared using a direct immersion anode, with very high loading of 40 mg lithium cobalt oxide (about 20 mg / cm ² ) and anode material (3.16 mg). The capacity of the anode to cathode in the prepared battery was 100: 95. As shown in Figure 26, the resultant cell exhibited an initial capacity of about 1300 mAh / g and more than 1,000 mAh / g after 65 cycles at 0.5 C. In addition, this battery exhibited a capacity of about 3 mAh / cm ^{2, which} is about twice as large as that exhibited in a conventional lithium ion battery full battery.

Example 11

Using the process described in Example 10, a directly deposited anode was prepared with silicon (Si) microparticles at an initial SiMP: GO weight ratio of 8: 1 and a final SiMP: rGO weight ratio of about 16: 1 . A half cell was fabricated and showed an initial capacity of about 1,600 mAh / g. In addition, an extremely high first cycle Coulomb efficiency was achieved (91%).

Example 12

Using the process described in Example 7, an electrode material was prepared using silicon oxide (SiOx) microparticles and graphene oxide in a weight ratio of about 1: 1. However, instead of fabricating the direct immersion anode, the anode material was removed from the substrate and the anode was prepared using a paste process (using about 5 wt% binder such as polyvinylidene fluoride (PVDF)). A half cell was prepared similar to that described in Example 7 to obtain a battery having an anode with a capacity of about 800 mAh / g and a very good capacity retention after 200 cycles at 1 A / g.

The electrode material was similarly prepared using silicon oxide (SiOx) microparticles and graphene oxide in a weight ratio of about 2: 1 and 4: 1. Following thermal treatment, these anode materials had silicon oxide (SiOx) microparticles and graphene oxide at a weight ratio of about 4: 1 and 8: 1, respectively. With an excellent cycling retention rate, an initial capacity of about 1250 mAh / g (after pre-cycle) was observed for both materials.

Example 13

Similar anode materials, such as those described in Example 12, anodes and batteries were also prepared using carbon nanofibers instead of graphene oxide. Fig. 27 shows the silicon oxide microparticles coated with carbon nanofibers according to the method. The resultant reversed cell using an anode made by processing a binder using powder comprising SiOx MP coated with carbon NF was about 500 mAh / g after 200 cycles for a MP: NF weight ratio of 1: 1, and about 4: RTI ID = 0.0 &gt; 400 mAh / g &lt; / RTI &gt; after 200 cycles for the MP: NF weight ratio of 1: 1.

Example 14

Using the process described in Example 7, the film material was coated with silicon (Si) microparticles and graphene oxide having a lateral size of about 5 microns to about 25 microns and a lateral size of about 0.5 microns to about 5 microns . Figure 28 shows the excellent coverage of silicon microparticles with larger graphene components (at various magnification levels), while Figure 29 shows the poor coverage of silicon microparticles with smaller graphene components (at various magnification levels) Respectively. As shown in Figure 29, some silicon microparticle components remain unprotected by the graphene component when smaller graphene components are used.

While both films demonstrate good capacity, an anode material with excellent silicon coverage (using a larger graphene component) has excellent capacity retention (for example, there is little capacity fade over 75 cycles) , An anode material with less ideal silicon coverage (using a smaller graphene component) proved capacity damping (e.g., about 50% capacity decay over 75 cycles).

Example 15

(Si) microparticles and graphene oxide (about 2: 1 and about 1: 1 input), without the gas being applied to the outer needle of the nozzle, using a process similar to that described in Example 7. [ Si: GO weight ratio). The resulting deposits were characterized by non-continuous co-aggregation of silicon and graphene components and had poor deposit uniformity, poor silicon coverage, and poor graffiti pocket formation. As an electrode, the deposit did not or did not generate enough capacity, and had little or no cycling capability.

For comparison, the system using graphene oxide in water (0.75 wt%) was electrosprayed with and without a high velocity gas stream. Similar conditions were used, the operating voltage was 25 kV, the distance from the nozzle to the collector was 20 cm, and the flow rate was 0.07 mL / min. After 30 seconds of gas-controlled electrospray of the stock, as shown in Figure 32 (panel A), the onset of microfilm formation of graphene oxide was observed. In contrast, large droplets and collection of graphene oxide were observed on the substrate, only 30 seconds after spraying the stock without air, as shown in Figure 32 (panel B). As shown in Figure 33 (panel B), after only one minute, the droplets started to flow together, while the good film formation, as shown in Figure 33 (panel A), caused the spray to be sprayed And was observed continuously.

Claims (177)

ai providing a fluid stock to the first inlet of the first conduit of the atomizing nozzle,
ii. Providing a voltage to the electrospray nozzle, thereby providing an electrostatically charged fluid reservoir; and
iii. Injecting an electrostatically charged fluid reservoir into a high velocity gas having a velocity of at least 0.5 m / s
Generating a electrostatically charged plume from the fluid storage by the fluid storage,
The first conduit is surrounded by a first wall having an inner surface and an outer surface along the length of the conduit, the first conduit having a first outlet,
Wherein the fluid storage comprises a plurality of inclusion particles and a liquid medium, wherein the inclusion particles comprise a plurality of silicon-containing particles and a plurality of carbon inclusions,
Wherein the plurality of silicon-containing particles comprise SiOx, wherein 0 &lt; = x &lt; = 0.5, with an average minimum dimension of less than 20 microns,
Wherein the plurality of carbon inclusions comprises a plurality of first graphene components, wherein the first graphene component is graphene oxide comprising 50 wt% to 90 wt% carbon and 10 wt% to 50 wt% oxygen ,
Wherein the weight ratio of the silicon-containing particles to the first graphene component present in the fluid reservoir is at least 1: 2,
The fluid reservoir having a viscosity of at least 200 cP; And
b. Collecting a first composition on a substrate, wherein the first composition is a first film comprising a plurality of silicon-containing particles immobilized within at least one first graphene web, wherein the at least one first graphene web is a plurality Of the first graphene component
And a second electrode. The method of claim 1, further comprising providing a pressurized gas to a second inlet of the second conduit of the nozzle, wherein the second conduit has a second inlet and a second outlet, at least a portion of the second conduit Wherein the first conduit is located around the first conduit. 3. The method of claim 2, wherein the second conduit is surrounded by a second wall having an inner surface, wherein the average distance between the outer surface of the first wall and the inner surface of the second wall is from 0.01 mm to 30 mm Way. 3. The process according to claim 2, wherein the gas velocity at the second outlet is at least 0.5 m / s. The method of claim 1, comprising collecting the first composition on a substrate having a substrate surface opposite the atomizing nozzle. The process according to claim 1, wherein the viscosity of the fluid stock is at least 1000 cP. The method of claim 1, wherein the electrostatic downward, and the charged flume comprises a plurality of flume particles, and a plurality of plumes particles in the base material d / 4 contains inclusions particles of less than a total of 50, where d is the nozzle Lt; RTI ID = 0.0 &gt; 1 &lt; / RTI &gt; The method of claim 1, wherein the substrate is attached to a conveyor system or a portion thereof. The method of claim 1, further comprising heat treating the first composition to provide a second composition, wherein the second composition comprises a plurality of heat treated silicon-containing particles anchored in the at least one second graphene web Wherein the at least one second graphene web comprises a plurality of second graphene components and wherein the plurality of second graphene components comprise 85 wt% to 99.9 wt% carbon and 0.1 wt% to 15 wt% Oxygen. &Lt; / RTI &gt; The process according to claim 9, wherein the second composition comprises 50 wt% to 95 wt% of SiOx. The process according to claim 10, wherein the second graphene component comprises from 5% to 50% by weight of the second composition. 10. The method of claim 9, further comprising compressing the first and / or second composition (s). 3. The method of claim 2, wherein the first composition has a thickness of 1 mm or less. 13. The method of claim 12, wherein the first composition has a bulk density of at least 0.5 g / cm &lt; ³ &gt;. The process according to claim 1, wherein the silicon-containing particles and the plurality of first graphene constitutes at least 80 wt.% Of the total content of incluent particles of the fluid stock. The method according to claim 1, wherein the first film and / or its component parts have a surface exposed to the outside, and the surface exposed to the outside is less than 20% SiOx on a surface area basis. The method according to claim 1, wherein the first film and / or its constituent parts have a surface exposed to the outside, and the surface exposed to the outside is graphene of 80% or more on a surface area basis. The method of claim 1, wherein the at least one first graphene web comprises a plurality of first graphene envelopes, wherein the first graphene envelope comprises an outer surface and an inner surface, And wherein at least one of the silicon-containing particles is disposed within the graphene pocket, and wherein the graphene envelope comprises at least one of the first graphene component (s). 19. The method of claim 18 wherein 1 < b & amp ; le; 5, wherein b is the average number of silicon-containing particles disposed in the graphene pocket (s). 3. The method of claim 1, wherein the average lateral dimension of the first graphene component is equal to or greater than the average of the minimum dimensions of the silicon-containing particles. The method of claim 1, wherein the electrostatically charged plume comprises a plurality of plume particles, wherein the plurality of plume particles in d / 4 of the substrate have an average dimension less than 50 times the average dimension of the silicon containing particles, wherein d Is the average distance between the first outlet of the nozzle and the substrate surface. 2. The method of claim 1, wherein the silicon-containing particles have an average dimension of from 1 micron to 10 microns. 5. The method of claim 1, wherein the silicon-containing particles have an average initial dimension of between 0.5 microns and 5 microns. An electrode produced according to the method of any one of claims 1 to 23. 10. The method of claim 9, wherein the first and / or second composition has a thickness of 1 mm or less. delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete delete

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