Separator, additive, energy storage device and electrode including the same, and method for manufacturing the

Abstract

Separators and additives (e.g., electrode additives) for use in energy storage devices are disclosed. In certain embodiments, the separator includes inorganic particles. In certain embodiments, the additive includes inorganic particles. The additive may be used in an electrode, such as a cathode or anode in a battery. The inorganic particles (whether included in a separator or used (e.g., as an additive) in an additive, such as an electrode) may be functional inorganic particles that promote battery performance and / or safety. For example, the functional inorganic particles may act to reduce or eliminate side reactions or mitigate the effects of side reactions during electrochemical cycling (e.g., battery discharge and / or charge) of energy storage devices in which they are included. As another example, the functional inorganic particles may additionally or alternatively promote ionic conductivity.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Application No. 63 / 395,748, filed on August 5, 2022, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure generally relates to separators, electrode additives, and methods of making the same, generally for use in energy storage devices. Background Art

[0004] Energy storage devices such as electrochemical cells typically include multiple components, such as electrodes, electrolytes, and separators. Each of these components can contribute to the performance of the overall energy storage device. In addition, these components generally provide a complex electrochemical environment together. Complex electrochemical environments typically lead to undesirable side reactions that act to reduce battery performance and / or safety. Therefore, it is necessary to promote separators and / or electrode compositions that promote favorable electrochemical reactions in energy storage devices (e.g., during battery charging and / or discharging). Summary of the invention

[0005] In particular, separators and additives (e.g., electrode additives) for energy storage devices are described herein. In certain embodiments, the separator includes inorganic particles. In certain embodiments, the additive includes inorganic particles. The additive can be used in an electrode, such as a cathode or an anode in a battery. The inorganic particles (whether included in the separator or used (e.g., used as) in an additive, such as an additive for an electrode) can be functional inorganic particles that promote battery performance and / or safety. For example, the functional inorganic particles can play a role in reducing or eliminating side reactions or mitigating the effects of side reactions during the electrochemical cycle (e.g., battery discharge and / or charging) of the energy storage device in which they are included. As another example, the functional inorganic particles can additionally or alternatively promote ionic conductivity. In certain embodiments, the separator and / or additive include one or more functional materials, each of which includes one or more organic ligands, one or more non-metallic oxides, or a combination thereof. In certain embodiments, the separator includes partially reduced graphene oxide, partially reduced graphite oxide, or a combination thereof.

[0006] In some aspects, the present disclosure relates to a membrane for use in an energy storage device, the membrane comprising inorganic particles and optionally one or more binders, wherein the one or more binders bind the inorganic particles (eg, of one type or different types) together.

[0007] In some embodiments, the inorganic particles are functional inorganic particles. In some embodiments, the separator is a solid layer or a semi-solid (e.g., gel or colloidal) layer (e.g., a surface layer). In some embodiments, the inorganic particles account for at least 50 wt.% of the separator (e.g., at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%).

[0008] In some embodiments, the inorganic particles include one or more elements selected from the group consisting of oxygen, hydrogen, sulfur, aluminum, silicon, and phosphorus [e.g., wherein the one or more elements account for at least 10 wt.% (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%) of the inorganic particles] [e.g., wherein the one or more elements account for no more than 80 wt.% (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 20 wt.%) of the inorganic particles]. In some embodiments, the inorganic particles include one or more metal atoms [e.g., wherein the one or more metal atoms account for at least 10 wt.% (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%) of the inorganic particles] [e.g., wherein the one or more metal atoms account for no more than 80 wt.% (e.g., no more than 50 wt.%, no more than 30 wt.%) of the inorganic particles]. In some embodiments, the one or more metal atoms are selected from the group consisting of aluminum, silicon, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

[0009] In some embodiments, the inorganic particles are porous. In some embodiments, the inorganic particles have microporosity, mesoporosity, macroporosity, or a combination thereof. In some embodiments, the inorganic particles contain one or more pores having a size (e.g., diameter) less than 2 nm (e.g., each of the inorganic particles contains one or more pores having a size less than 2 nm). In some embodiments, the inorganic particles contain one or more pores having a size (e.g., diameter) of at least 2 nm and not more than 50 nm (e.g., each of the inorganic particles contains one or more pores having a size of at least 2 nm and not more than 50 nm). In some embodiments, the inorganic particles contain one or more pores having a size (e.g., diameter) greater than 50 nm (e.g., each of the inorganic particles contains one or more pores having a size greater than 50 nm). In some embodiments, each of the inorganic particles contains one or more pores having a size (e.g., diameter) greater than 50 nm. to (For example, to to to )[For example, (For example, )to (For example, )]. In some embodiments, each of the inorganic particles comprises one or more holes connected to form at least one channel passing through the inorganic particles. In some embodiments, the at least one channel of each of the inorganic particles is connected to form a channel system. In some embodiments, the channel system is a 1-dimensional channel system, a 2-dimensional channel system, or a 3-dimensional channel system. In some embodiments, the channel system extends through the diaphragm [e.g., from a first surface of the diaphragm to a second surface of the diaphragm opposite to the first surface (e.g., from the anode side to the cathode side)].

[0010] In some embodiments, the inorganic particle comprises one or more cage structures. In some embodiments, at least one of the one or more cage structures is disposed at the intersection of the pores of the inorganic particle. In some embodiments, the size (e.g., diameter) of each of the one or more cage structures is between to (For example, to to to to to or to ). In some embodiments, at least one of the one or more cage structures is disposed in a 1-dimensional pore. In some embodiments, one or more species are disposed in (e.g., adsorbed in) the one or more cage structures.

[0011] In some embodiments, one or more species are disposed in (e.g., adsorbed on) one or more pores of the inorganic particle [e.g., on a surface (e.g., an interior surface, near an opening, or both) of the one or more pores] (e.g., wherein the one or more species are not covalently bonded to the one or more pores). In some embodiments, the one or more species comprise a member selected from the group consisting of olefins, paraffins, cycloalkanes, and aromatic hydrocarbons. In some embodiments, the one or more species comprise water. In some embodiments, the one or more species comprise one or more gaseous species. In some embodiments, the one or more gaseous species are selected from the group consisting of hydrogen, oxygen, carbon oxides, nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides, and sulfur oxides. In some embodiments, the one or more species comprise one or more cationic species. In some embodiments, the one or more cationic species are each a cationic form of an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium. In some embodiments, the one or more species comprise one or more anionic species. In some embodiments, the one or more anionic species is selected from the group consisting of hydroxide, alkoxide, peroxide, superoxide, nitrate, nitrite, sulfate, sulfite, phosphate, phosphide, fluoride, chloride, bromide, iodide, chlorate, bromate, iodate, polyoxometalate, and combinations thereof.

[0012] In some embodiments, the surface area of ​​the inorganic particles is at least 10 m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g).

[0013] In some embodiments, the inorganic particles include one or more particles having M y Al x Si 1-x O 2 ·zH 2 In some embodiments, the present invention provides particles of a composition of 1, 2 or 3 O, wherein M is a metal. In some embodiments, x is in the range of 0 to 0.5 (e.g., 0 to 0.1 or 0.01 to 0.5), and y is in the range of 0 to 0.5 (e.g., 0 to 0.1). In some embodiments, x is in the range of 0.5 to 1, and y is in the range of 0 to 1. In some embodiments, z is in the range of 0 to 10,000.

[0014] In some embodiments, the polar sites are disposed on the surface [e.g., the inner surface (e.g., porous)] of the inorganic particles. In some embodiments, the inorganic particles are crystalline or amorphous. In some embodiments, the average particle size (d 50 In some embodiments, the inorganic particles include one or more particles having a spherical shape, one or more particles having a rod shape, one or more particles having a needle shape, one or more particles having a flake shape, one or more particles having a platelet shape, one or more particles having a cubic shape, one or more particles having a disk shape, one or more particles having a tube shape, or a combination thereof.

[0015] In some embodiments, the inorganic particles have been prepared by subjecting a chemical precursor to a crystallization reaction at 30-250° C. for no more than 30 days. In some embodiments, the reaction is carried out under stirring. In some embodiments, the crystallization reaction is carried out without stirring. In some embodiments, the chemical precursor comprises a silica source and an alumina source. In some embodiments, the chemical precursor comprises a mineralizer, an acidic medium or an alkaline medium, a template, a structure directing agent (SDA) or a combination thereof.

[0016] In some embodiments, the one or more binders account for no more than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%) of the diaphragm. In some embodiments, the one or more binders are selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and styrene butadiene rubber (SBR). In some embodiments, at least one of the one or more binders comprises one or more binder additives. In some embodiments, the one or more binder additives comprise one or more members selected from the group consisting of pH adjusters, pH buffers, rheology modifiers, defoamers, antifoaming agents, adhesion promoters, and leveling agents.

[0017] In some embodiments, the separator further comprises a conductive polymer. In some embodiments, the conductive polymer accounts for no more than 80 wt.% (e.g., no more than 50 wt.%) of the separator. In some embodiments, the conductive polymer is selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), and PEDOT.

[0018] In some embodiments, the separator has been coated on an electrode (e.g., an anode, a cathode, or both) in situ or ex situ (e.g., by wet chemical reaction, physical vapor deposition, chemical vapor deposition, atomic layer deposition, sintering, pressing, hot pressing, extrusion, die casting, slot die coating, doctor blade coating, dip coating, or a combination thereof) (e.g., by a liquid coating method). In some embodiments, the separator has been further calendered (e.g., to increase bonding strength, layer uniformity, or both), annealed, or both.

[0019] In some embodiments, the thickness of the membrane is in the range of 5 μm to 500 μm. In some embodiments, the membrane is a self-supporting film.

[0020] The diaphragm can be included in an energy storage device together with two electrodes, wherein the diaphragm is disposed between the two electrodes so that the diaphragm prevents the two electrodes from direct physical contact. In some embodiments, the energy storage device further comprises a second diaphragm disclosed herein, wherein the second diaphragm is disposed between the two electrodes so that the second diaphragm prevents the two electrodes from direct physical contact.

[0021] In some embodiments, the energy storage device further comprises an electrolyte [e.g., a solid or liquid (e.g., aqueous) electrolyte] (e.g., an ion-conductive matrix) disposed between the two electrodes. In some embodiments, the electrolyte is a solid polymer electrolyte selected from the group consisting of: (i) polymers comprising repeating units of one or more of the following: ethylene oxide, propylene oxide, madder pigment, alginate, quinone, hydroxyquinone, hydroxyquinoline, silicon, silicate, and sulfone, (ii) cellulosic, natural or modified natural polymers, and (iii) synthetic fluorinated polymers (e.g., polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE)). In some embodiments, the electrolyte comprises one or more materials each having the following stoichiometry: M1 1+ x N1 p , or M1 2+ x N1 p , or M1 3+ x N1 p , or M1 4+ x N1 p , or M1 1+ x N1 p N2 q , or M1 2+ x N1 p N2 q , or M1 3+ x N1 p N2 q , or M1 4+ x N1 p N2 q , or M1 1+ x M2 2+ y N1 p , or M1 1+ x M2 3+ y N1 p , or M1 1+ x M2 4+ y N1 p , or M1 2+ x M2 3+ y N1 p , or M12+ x M2 4+ y N1 p , or M1 3+ x M2 4+ y N1 p , or M1 1+ x M2 2+ y N1 p N2 q , or M1 1+ x M2 3+ y N1 p N2 q , or M1 1+ x M2 4+ y N1 p N2 q , or M1 2+ x M2 3+ y N1 p N2 q , or M1 2+ x M24+ y N1 p N2 q , or M1 3+ x M2 4+ y N1 p N2 q , or M1 1+ x M2 2+ y M3 3+ z N1p, or M1 1+ x M2 2+ y M3 4+ z N1 p , or M1 2+ x M2 3+ y M3 4+ z N1 p , or M1 1+ x M2 2+y M3 3+ z N1 p N2 q , or M1 1 + x M2 2+ y M3 4+ z N1 p N2 q , or M1 2+ x M2 3+ y M3 4+ z N1 p N2 q , or M1 1 +x M2 2+ y M3 3+ z M4 4+ s N1 p , or M1 1 + xM2 2+ y M3 3+ z M4 4+ s N1 p N2 q, wherein each M (e.g., M1, M2, M3, M4) is a monovalent or polyvalent atom, and each N (e.g., N1, N2) is a functional group (e.g., selected from the group consisting of: hydroxide, alkoxide, peroxide, superoxide, nitrate, nitrite, sulfate, sulfite, sulfide, carbonate, phosphate, phosphate, phosphide, and halide). In some embodiments, the electrolyte comprises one or more of the following: a salt, an acid, and a base. In some embodiments, the electrolyte: (i) comprises the salt, wherein the salt is selected from the group consisting of: an oxide salt, hydroxide salt, alkoxide salt, peroxide salt, superoxide salt, nitrate, nitrite, sulfate, sulfite, sulfide salt, carbonate, carbide salt, phosphate, phosphorus, or one or more of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, and copper. (ii) comprising the acid, wherein the acid is selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, sulfurous acid, trifluoromethanesulfonic acid, hydrofluoric acid, peracetic acid, boric acid, uric acid, citric acid, hydroiodic acid, carbonic acid, oxalic acid, bromic acid, chromic acid, formic acid, ascorbic acid and acetic acid; (iii) comprising the base, wherein the base is selected from the group consisting of hydroxides of sodium, potassium, calcium, magnesium, manganese, lithium, zinc, zirconium, cerium, tin, titanium, aluminum, ammonium, iron, indium, molybdenum, nickel, platinum, palladium, ruthenium, silver, vanadium and copper; or (iv) any combination of (i), (ii) and (iii). In some embodiments, the electrolyte comprises one or more ceramics selected from the group consisting of aluminum oxide, antimony ammonium tungstate oxide, barium titanate, strontium titanate, bismuth strontium calcium copper oxide, boron oxide, boron nitride, ferrite, lead zirconate titanate, magnesium diboride, porcelain, sialon, silicon, silicate, carbide, nitride, titanium carbide, uranium oxide, yttrium barium copper oxide, zinc oxide, cesium oxide, cerium oxide, zirconium oxide, vanadium oxide, tin oxide, iron oxide, tungsten oxychloride, beryllium oxide, bismuth oxide, lithium oxide, lead oxide, manganese oxide, magnesium oxide, nickel oxide, titanium oxide, cadmium oxide, copper oxide, indium oxide, and silicon oxide. In some embodiments, the electrolyte is a self-supporting film or has been applied to the separator and / or at least one of the two electrodes.

[0022] In some embodiments, at least one of the two electrodes comprises an electroactive material comprising an oxide, suboxide, sulfide, oxysulfide, phosphate, phosphide, carbide, or elementary forms of an element, and combinations thereof, selected from the group consisting of silicon, vanadium, niobium, molybdenum, rhenium, tantalum, tungsten, bismuth, titanium, tin, antimony, manganese, nickel, aluminum, lithium, sodium, potassium, calcium, zinc, cobalt, chromium, indium, lanthanum, cerium, strontium, iron. In some embodiments, the electroactive material has been modified with (e.g., doped with) one or more elements. In some embodiments, the one or more elements include one or more members selected from the group consisting of hydrogen, lithium, boron, carbon, nitrogen, iodine, phosphorus, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, antimony, arsenic, lanthanum, cerium, neodymium, tantalum, tungsten, tellurium, rhenium, platinum, gold, lead, and bismuth. In some embodiments, the one or more elements comprise less than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%) of the electroactive material.

[0023] In some embodiments, one of the two electrodes is disposed on a substrate. In some embodiments, the substrate is a carbon structure or a metal structure. In some embodiments, the substrate is a foam, paper, aerogel, foil, fiber, nanostructure (e.g., nanoparticles), sheet, net or raw material. In some embodiments, the substrate comprises a polymer material. In some embodiments, the polymer material is selected from the group consisting of: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR), polyaniline (PANI), polypyrrole (PPyr), polystyrene (PS) and polythiophene (PT).

[0024] In some embodiments, at least one of the two electrodes comprises a binder selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyacrylic acid (PAA), polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR) and copolymers thereof. In some embodiments, at least one of the two electrodes comprises a conductive additive selected from the group consisting of carbon black, acetylene black, carbon fiber, carbon nanotubes, graphene, graphite, fullerene, carbon aerogel, metal flakes, metal fibers or metal particles, and conductive polymers. In some embodiments, the conductive additive is a conductive polymer selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), and PEDOT.

[0025] In some embodiments, at least one of the two electrodes comprises an additive material selected from the group consisting of metals, oxides, suboxides, hydroxides, oxyhydroxides, oxychlorides, sulfides, oxysulfides, oxynitrates, carbonates, nitrides, phosphates, phosphites, carbides, and polymers, containing one or more members selected from the group consisting of hydrogen, lithium, boron, carbon, nitrogen, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, lanthanum, cerium, neodymium, tantalum, tungsten, rhenium, platinum, gold, lead, and bismuth.

[0026] In some embodiments, the energy storage device is a primary battery, a secondary battery, a secondary battery, a fuel cell unit, or a capacitor. In some embodiments, the energy storage device is an aqueous battery (eg, an aqueous secondary battery or an aqueous primary battery).

[0027] In some aspects, the present disclosure relates to a method for making inorganic particles for use as a diaphragm or as an additive in an energy storage device, the method comprising subjecting a chemical precursor to a crystallization reaction at 30-250° C. for no more than 30 days. In some embodiments, the method comprises stirring the chemical precursor during the crystallization reaction. In some embodiments, the crystallization reaction is carried out without stirring. In some embodiments, the chemical precursor comprises a silica source and an alumina source. In some embodiments, the chemical precursor further comprises a mineralizer, an acidic medium or an alkaline medium, a template, a structure directing agent (SDA) or a combination thereof.

[0028] In some aspects, the present disclosure relates to a method of operating an energy storage device, the method comprising: providing an energy storage device disclosed herein; and trapping gas in pores of the inorganic particles during charging and / or discharging of the energy storage device.

[0029] In some aspects, the present disclosure relates to a method of operating and / or preparing an energy storage device, the method comprising: providing the energy storage device, wherein the energy storage device comprises inorganic particles, the inorganic particles comprising one or more members selected from the group consisting of: silicates, phosphates, sulfates, oxides, hydrides, and combinations thereof (e.g., one or more silicates and / or one or more phosphates) [e.g., in stable (e.g., salt) and / or ionic (e.g., anionic) form]; reacting the one or more members with one or more species (e.g., one or more portions thereof) in the energy storage device to form one or more reaction products; and passivating the surface of a material in the energy storage device with the one or more reaction products (e.g., thereby inhibiting one or more undesirable side reactions). In some embodiments, the reaction occurs during electrochemical cycling (e.g., during charging and / or discharging) of the energy storage device (e.g., wherein the energy storage device is a primary battery or a secondary battery). In some embodiments, the reaction occurs before assembly of the energy storage device is completed (e.g., during a preconditioning process of the energy storage device). In some embodiments, the one or more reaction products comprise polymer species (e.g., polysilicates and / or polyphosphates). In some embodiments, the method comprises reacting the one or more reaction products with the surface of the material. In some embodiments, reacting the one or more members comprises dissolving at least a portion of the inorganic particles (e.g., dissolving in the electrolyte of the energy storage device). In some embodiments, passivating the surface of the material comprises precipitating polysilicates and / or polyphosphates onto the surface. In some embodiments, at least a portion of the inorganic particles is contained in a diaphragm of the energy storage device. In some embodiments, at least a portion of the inorganic particles is contained in an additive, which is contained in an electrode of the energy storage device (e.g., wherein the electrode is an anode or a cathode, or wherein the additive is contained in both an anode and a cathode). In some embodiments, the material is metallic. In some embodiments, the material is an electroactive material.

[0030] In some aspects, the present disclosure relates to an energy storage device comprising inorganic particles comprising one or more members selected from the group consisting of silicates, phosphates, sulfates, oxides, hydrides, and combinations thereof (e.g., one or more silicates and / or one or more phosphates) [e.g., in stable (e.g., salt) and / or ionic (e.g., anionic) form], and a material comprising a passivated surface, the passivated surface being passivated with one or more species derived from one or more members (e.g., the one or more silicates and / or the one or more phosphates) (e.g., being reaction products of the one or more members) [e.g., wherein the one or more species comprise one or more polymer species (e.g., one or more polysilicates and / or one or more polyphosphates)] (e.g., wherein the inorganic particles are contained in a separator and / or an electrode).

[0031] In some aspects, the present disclosure relates to an additive (eg, an electrode additive) for use in an energy storage device, the additive comprising inorganic particles (eg, of one type or of different types).

[0032] In some embodiments, the inorganic particles are functional inorganic particles. In some embodiments, the inorganic particles include one or more elements selected from the group consisting of oxygen, hydrogen, sulfur, aluminum, silicon and phosphorus [e.g., wherein the one or more elements account for at least 10 wt.% of the inorganic particles (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%)] [e.g., wherein the one or more elements account for no more than 80 wt.% of the inorganic particles (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 20 wt.%)]. In some embodiments, the inorganic particles include one or more metal atoms [e.g., wherein the one or more elements account for at least 10 wt.% of the inorganic particles (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%)] [e.g., wherein the one or more elements account for no more than 80 wt.% of the inorganic particles (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 50 wt.%)]. In some embodiments, the one or more metal atoms are selected from the group consisting of aluminum, silicon, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

[0033] In some embodiments, the inorganic particles are porous. In some embodiments, the inorganic particles have microporosity, mesoporosity, macroporosity, or a combination thereof. In some embodiments, the inorganic particles contain one or more pores having a size (e.g., diameter) less than 2 nm (e.g., each of the inorganic particles contains one or more pores having a size less than 2 nm). In some embodiments, the inorganic particles contain one or more pores having a size (e.g., diameter) of at least 2 nm and not more than 50 nm (e.g., each of the inorganic particles contains one or more pores having a size of at least 2 nm and not more than 50 nm). In some embodiments, the inorganic particles contain one or more pores having a size (e.g., diameter) greater than 50 nm (e.g., each of the inorganic particles contains one or more pores having a size greater than 50 nm). In some embodiments, each of the inorganic particles contains one or more pores having a size (e.g., diameter) greater than 50 nm. to (For example, to to to )[For example, (For example, )to (For example, )]. In some embodiments, each of the inorganic particles comprises one or more pores connected to form at least one channel passing through the inorganic particles.

[0034] In some embodiments, the at least one channel of each inorganic particle in the inorganic particles is connected to form a channel system. In some embodiments, the channel system is a 1-dimensional channel system, a 2-dimensional channel system, or a 3-dimensional channel system. In some embodiments, the channel system extends through the diaphragm [e.g., from a first surface of the diaphragm to a second surface of the diaphragm opposite to the first surface (e.g., from an anode side to a cathode side)].

[0035] In some embodiments, the inorganic particle comprises one or more cage structures. In some embodiments, at least one of the one or more cage structures is disposed at the intersection of the pores of the inorganic particle. In some embodiments, the size (e.g., diameter) of each of the one or more cage structures is between to (For example, to to to to to or to In some embodiments, at least one of the one or more cage structures is disposed in a 1-dimensional pore.

[0036] In some embodiments, one or more species are disposed in (e.g., adsorbed in) the one or more cage structures. In some embodiments, one or more species are disposed in (e.g., adsorbed in) one or more pores of the inorganic particles [e.g., on the surface (e.g., inner surface, near the opening, or both) of the one or more pores]. In some embodiments, the one or more species comprise members selected from the group consisting of olefins, paraffins, cycloalkanes, and aromatic hydrocarbons. In some embodiments, the one or more species comprise water. In some embodiments, the one or more species comprise one or more gas species. In some embodiments, the one or more gas species are selected from the group consisting of hydrogen, oxygen, carbon oxides, nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides, and sulfur oxides. In some embodiments, the one or more species comprise one or more cationic species. In some embodiments, the one or more cationic species are each a cationic form of an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium. In some embodiments, the one or more species comprise one or more anionic species. In some embodiments, the one or more anionic species is selected from the group consisting of hydroxide, alkoxide, peroxide, superoxide, nitrate, nitrite, sulfate, sulfite, phosphate, phosphide, fluoride, chloride, bromide, iodide, chlorate, bromate, iodate, polyoxometalate, and combinations thereof.

[0037] In some embodiments, the surface area of ​​the inorganic particles is at least 10 m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g).

[0038] In some embodiments, the inorganic particles include one or more particles having My Al x Si 1-x O 2 ·zH 2 In some embodiments, the present invention provides particles of a composition of 1, 2 or 3 O, wherein M is a metal. In some embodiments, x is in the range of 0 to 0.5 (e.g., 0 to 0.1 or 0.01 to 0.5), and y is in the range of 0 to 0.5 (e.g., 0 to 0.1). In some embodiments, x is in the range of 0.5 to 1, and y is in the range of 0 to 1. In some embodiments, z is in the range of 0 to 10,000.

[0039] In some embodiments, the polar sites are disposed on the surface [e.g., the inner surface (e.g., porous)] of the inorganic particles. In some embodiments, the inorganic particles are crystalline or amorphous. In some embodiments, the average particle size (d 50 diameter) in the range of 100 nm to 30 μm.

[0040] In some embodiments, the inorganic particles include one or more particles having a spherical shape, one or more particles having a rod shape, one or more particles having a needle shape, one or more particles having a flake shape, one or more particles having a platelet shape, one or more particles having a cubic shape, one or more particles having a disk shape, one or more particles having a tube shape, or a combination thereof.

[0041] In some embodiments, the inorganic particles have been prepared by subjecting a chemical precursor to a crystallization reaction at 30-250° C. for no more than 30 days. In some embodiments, the reaction is carried out under stirring. In some embodiments, the crystallization reaction is carried out without stirring. In some embodiments, the chemical precursor comprises a silica source and an alumina source. In some embodiments, the chemical precursor comprises a mineralizer, an acidic medium or an alkaline medium, a template, a structure directing agent (SDA) or a combination thereof.

[0042] The additive may be included in an electrode further comprising an electroactive material. In some embodiments, the electrode further comprises a current collector, wherein the electroactive material and the additive are coated on the current collector.

[0043] In some embodiments, the electrode further comprises one or more binders. In some embodiments, the one or more binders account for no more than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%) of the separator. In some embodiments, the one or more binders are selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and styrene butadiene rubber (SBR).

[0044] In some embodiments, the electrode further comprises a conductive additive. In some embodiments, the conductive additive accounts for no more than 80 wt.% of the electrode (e.g., no more than 70 wt.%, no more than 60 wt.%, no more than 50 wt.%, no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, or no more than 10 wt.%). In some embodiments, the conductive additive is selected from the group consisting of carbon black, acetylene black, carbon fiber, carbon nanotube, graphene, graphite, fullerene, carbon aerogel, metal flakes, metal fibers, metal particles, and conductive polymers. In some embodiments, the conductive additive is a conductive polymer selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), and PEDOT.

[0045] In some embodiments, the inorganic particles account for 1 vol.% to 50 vol.% (eg, 5 vol.% to 30 vol.% or 10 vol.% to 20 vol.%) of the active layer (eg, coating or film) of the electrode.

[0046] In some embodiments, the inorganic particles are disposed on one or more surfaces of the electroactive material [e.g., surfaces of microstructures and / or nanostructures such as particles (e.g., rods and / or spheres), films, tubes and / or fibers]. In some embodiments, the inorganic particles and the electroactive material together form one or more core-shell structures, each of which has a core and a shell, the core comprising at least a portion of the electroactive material, and the shell comprising one of the inorganic particles. In some embodiments, the inorganic particles are disposed in a layer (e.g., a uniform or non-uniform layer), the layer being disposed on (e.g., completely surrounding) the surface of one or more particles comprising the electroactive material. In some embodiments, the thickness of the layer is no greater than 2 μm. In some embodiments, the inorganic particles are adhered to the one or more surfaces by electrostatic potential. In some embodiments, the inorganic particles and / or the electroactive material have been surface modified (e.g., to change electrostatic potential and / or hydrophobicity).

[0047] In some embodiments, the electroactive material [eg, microstructured and / or nanostructured surfaces such as particles (eg, rods and / or spheres), films, tubes and / or fibers] and the inorganic particles are dispersed throughout the electrode.

[0048] The electrode may be included in an energy storage device. In some embodiments, the energy storage device further includes a diaphragm, which is disposed between the two electrodes so that the diaphragm prevents the two electrodes from directly physically contacting each other. In some embodiments, the energy storage device further comprises an electrolyte, which is disposed between the two electrodes. In some embodiments, the energy storage device is a primary battery, a secondary battery, a secondary battery, a fuel cell unit, or a capacitor. In some embodiments, the energy storage device is an aqueous battery (e.g., an aqueous secondary battery or an aqueous primary battery).

[0049] In some aspects, the present disclosure relates to a membrane or electrode additive for an energy storage device, wherein the membrane or electrode additive comprises a functional material, wherein the functional material comprises: (i) one or more organic ligands, one or more non-metallic oxides, or a combination thereof; or (ii) partially reduced graphene oxide, partially reduced graphite oxide, or a combination thereof.

[0050] In some embodiments, the functional material comprises the one or more organic ligands. In some embodiments, the one or more organic ligands are doped. In some embodiments, the one or more organic ligands comprise one or more elements selected from the group consisting of: sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine and iodine. In some embodiments, the one or more organic ligands comprise one or more water molecules (e.g., coordinated and / or bonded to the framework ligands).

[0051] In some embodiments, the functional material comprises the one or more non-metal oxides. In some embodiments, the one or more non-metal oxides are doped. In some embodiments, the one or more non-metal oxides comprise one or more dopants selected from the group consisting of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine, and iodine.

[0052] In some embodiments, the functional material comprises the partially reduced graphene oxide. In some embodiments, the partially reduced graphene oxide is doped. In some embodiments, the partially reduced graphene oxide comprises one or more dopants selected from the group consisting of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine, and iodine. In some embodiments, the partially reduced graphene oxide is coordinated and / or bonded (e.g., hydrogen bonded) to one or more water molecules.

[0053] In some embodiments, the functional material comprises the partially reduced graphite oxide. In some embodiments, the partially reduced graphite oxide is doped. In some embodiments, the partially reduced graphite oxide comprises one or more dopants selected from the group consisting of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine, and iodine. In some embodiments, the partially reduced graphite oxide is coordinated and / or bonded (e.g., hydrogen bonded) to one or more water molecules.

[0054] In some embodiments, the functional material is crystalline or amorphous.

[0055] In some embodiments, the functional material is contained in particles. In some embodiments, the particles include one or more particles having a spherical shape, one or more particles having a rod shape, one or more particles having a needle shape, one or more particles having a flake shape, one or more particles having a platelet shape, one or more particles having a cubic shape, one or more particles having a disk shape, one or more particles having a tube shape, or a combination thereof.

[0056] In some embodiments, the functional material is porous (e.g., contained in porous particles). In some embodiments, the functional material has microporosity, mesoporosity, macroporosity, or a combination thereof. In some embodiments, the functional material comprises one or more pores having a size (e.g., diameter) of less than 2 nm. In some embodiments, the functional material comprises one or more pores having a size (e.g., diameter) of at least 2 nm and no greater than 50 nm. In some embodiments, the functional material comprises one or more pores having a size (e.g., diameter) of greater than 50 nm. In some embodiments, the functional material comprises one or more pores having a size (e.g., diameter) of less than 2 nm. to (For example, to to to )[For example, (For example, )to (For example, )]. In some embodiments, the functional material comprises one or more holes, and the one or more holes are connected by the functional material to form at least one channel. In some embodiments, the at least one channel is connected to form a channel system. In some embodiments, the channel system is a 1-dimensional channel system, a 2-dimensional channel system, or a 3-dimensional channel system. In some embodiments, the channel system extends through the functional material [e.g., from the first surface of the diaphragm to the second surface of the diaphragm opposite to the first surface (e.g., from the anode side to the cathode side)].

[0057] In some embodiments, one or more species are disposed in (e.g., adsorbed on) one or more pores of the functional material [e.g., on a surface (e.g., an interior surface, near an opening, or both) of the one or more pores]. In some embodiments, the one or more species comprise a member selected from the group consisting of olefins, paraffins, cycloalkanes, and aromatic hydrocarbons. In some embodiments, the one or more species comprise water. In some embodiments, the one or more species comprise one or more gas species. In some embodiments, the one or more gas species are selected from the group consisting of hydrogen, oxygen, carbon oxides, nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides, and sulfur oxides. In some embodiments, the one or more species comprise one or more cationic species. In some embodiments, the one or more cationic species are each a cationic form of an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium. In some embodiments, the one or more species comprise one or more anionic species. In some embodiments, the one or more anionic species is selected from the group consisting of hydroxide, alkoxide, peroxide, superoxide, nitrate, nitrite, sulfate, sulfite, phosphate, phosphide, fluoride, chloride, bromide, iodide, chlorate, bromate, iodate, polyoxometalate, and combinations thereof.

[0058] In some embodiments, the surface area of ​​the functional material is at least 10 m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2In some embodiments, the functional material is contained in particles, and the average particle size (D 50 ) is 100nm to 30μm.

[0059] The additive may be included in a diaphragm, which further includes one or more adhesives. In some embodiments, the one or more adhesives account for no more than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.% or no more than 1 wt.%) of the diaphragm. In some embodiments, the one or more adhesives are selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and styrene butadiene rubber (SBR). In some embodiments, at least one of the one or more adhesives includes one or more adhesive additives. In some embodiments, the one or more adhesive additives include one or more members selected from the group consisting of pH adjusters, pH buffers, rheology modifiers, defoamers, antifoaming agents, adhesion promoters and leveling agents. In some embodiments, the separator further comprises a conductive polymer. In some embodiments, the conductive polymer accounts for no more than 80 wt.% (e.g., no more than 70 wt.%, no more than 60 wt.%, no more than 50 wt.%, no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, or no more than 10 wt.%) of the separator. In some embodiments, the conductive polymer is selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), and PEDOT.

[0060] In some embodiments, the separator has been coated on an electrode (e.g., an anode, a cathode, or both) in situ or ex situ (e.g., by wet chemical reaction, physical vapor deposition, chemical vapor deposition, atomic layer deposition, sintering, pressing, hot pressing, extrusion, die casting, slot die coating, doctor blade coating, dip coating, or a combination thereof) (e.g., by a liquid coating method). In some embodiments, the separator has been further calendered (e.g., to increase bonding strength, layer uniformity, or both), annealed, or both.

[0061] In some embodiments, the thickness of the membrane is in the range of 5 μm to 500 μm. In some embodiments, the membrane is a self-supporting film.

[0062] The additive may be included in an electrode, the electrode further comprising an electroactive material. In some embodiments, the electrode further comprises a current collector, wherein the electroactive material and the additive are coated on the current collector. In some embodiments, the electrode further comprises one or more adhesives. In some embodiments, the one or more adhesives account for no more than 50wt.% (e.g., no more than 40wt.%, no more than 30wt.%, no more than 20wt.%, no more than 10wt.%, no more than 5wt.% or no more than 1wt.%) of the separator. In some embodiments, the one or more adhesives are selected from the group consisting of: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and styrene butadiene rubber (SBR). In some embodiments, the electrode further comprises a conductive additive. In some embodiments, the conductive additive accounts for no more than 80 wt.% of the electrode (e.g., no more than 70 wt.%, no more than 60 wt.%, no more than 50 wt.%, no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, or no more than 10 wt.%). In some embodiments, the conductive additive is selected from the group consisting of carbon black, acetylene black, carbon fiber, carbon nanotube, graphene, graphite, fullerene, carbon aerogel, metal flakes, metal fibers, metal particles, and conductive polymers. In some embodiments, the conductive additive is a conductive polymer selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), and PEDOT.

[0063] In some embodiments, the functional material comprises 1 vol.% to 50 vol.% (eg, 5 vol.% to 30 vol.% or 10 vol.% to 20 vol.%) of an active layer (eg, coating or film) of the electrode.

[0064] In some embodiments, the functional material is disposed on one or more surfaces of the electroactive material [e.g., the surface of a microstructure and / or nanostructure such as a particle (e.g., rods and / or spheres), a film, a tube and / or a fiber]. In some embodiments, the functional material and the electroactive material together form one or more core-shell structures, each of which has a core and a shell, the core comprising at least a portion of the electroactive material, and the shell comprising the functional material. In some embodiments, the functional material is disposed in a layer (e.g., a uniform or non-uniform layer), the layer being disposed on (e.g., completely surrounding) the surface of one or more particles comprising the electroactive material. In some embodiments, the thickness of the layer is no greater than 2 μm. In some embodiments, the functional material is adhered to one or more surfaces by electrostatic potential. In some embodiments, the functional material and / or the electroactive material has been surface modified (e.g., to change electrostatic potential and / or hydrophobicity).

[0065] Any two or more features described in this specification (including in this summary) may be combined to form an embodiment, such as an energy storage device embodiment not specifically and explicitly described in this specification. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] The accompanying drawings are presented herein for illustrative purposes and not limiting. The foregoing and other objects, aspects, features and advantages of the present disclosure will become more apparent and can be better understood by reference to the following description made in conjunction with the accompanying drawings, in which:

[0067] Figure 1A shows a particle having a one-dimensional channel system according to an illustrative embodiment of the present disclosure;

[0068] Figure 1B shows a particle having a two-dimensional channel system according to an illustrative embodiment of the present disclosure;

[0069] Figure 1C shows a particle having a one-dimensional channel system and a cage structure according to an illustrative embodiment of the present disclosure;

[0070] Figure 2 is a cross-section of a battery according to an illustrative embodiment of the present disclosure, the battery comprising two electrode layers and one separator layer, the two electrode layers and the one separator layer each comprising particles; and

[0071] Figure 3 is a perspective representation of a coin cell assembly according to an illustrative embodiment of the present disclosure.

[0072] The schematic diagrams are not necessarily drawn to scale. DETAILED DESCRIPTION

[0073] In this application, unless otherwise apparent from the context or otherwise explicitly stated, (i) the term "a" may be understood to mean "at least one"; (ii) the term "or" may be understood to mean "and / or"; (iii) the terms "comprising" and "including" may be understood to cover the subcomponents or steps, whether the subcomponents or steps are presented alone or together with one or more additional components or steps; (iv) the terms "about" and "approximately" may be understood to allow for standard variations understood by a person of ordinary skill in the relevant art; and (v) where a range is provided, the endpoints are included.

[0074] It is considered that the system, device, method and process of the present disclosure cover changes and adaptations developed using information from the embodiments described herein. Ordinary technicians in the relevant field can perform adaptations and / or modifications to the systems, devices, methods and processes described herein. Throughout this specification, in the case where products, devices and systems are described as having, including or containing specific components or in the case where processes and methods are described as having, including or containing specific steps, it is considered that, in addition, there are products, devices and systems according to certain embodiments of the present disclosure that are generally composed of the listed components or composed of the listed components, and there are processes and methods according to certain embodiments of the present disclosure that are generally composed of the listed processing steps or composed of the listed processing steps. It should be understood that the order of steps or the order in which certain actions are performed is irrelevant, as long as operability is not lost. In addition, two or more steps or actions can be performed simultaneously. As understood by those skilled in the art, the terms "above", "below", "above", "below", "below" and "on" are relative terms and can be interchanged with respect to different orientations of layers, elements and substrates included in the present disclosure. For example, in some embodiments, a first layer is located on a second layer means that the first layer is directly located on the second layer and is in contact with the second layer. In other embodiments, a first layer is located on a second layer can include another layer located therebetween. Headings are provided for the convenience of the reader and are not intended to limit the claimed subject matter.

[0075] In particular, separators and additives (e.g., electrode additives) for energy storage devices are described herein. In certain embodiments, the separator includes inorganic particles. In certain embodiments, the additive includes inorganic particles. The additive can be used in an electrode, such as a cathode or an anode in a battery. The inorganic particles (whether included in the separator or used (e.g., used as) in an additive, such as an additive for an electrode) can be functional inorganic particles that promote battery performance and / or safety. For example, the functional inorganic particles can play a role in reducing or eliminating side reactions or mitigating the effects of side reactions during the electrochemical cycle (e.g., battery discharge and / or charging) of the energy storage device in which they are included. As another example, the functional inorganic particles can additionally or alternatively promote ionic conductivity. In certain embodiments, the separator and / or additive include one or more functional materials, each of which includes one or more organic ligands, one or more non-metallic oxides, or a combination thereof. In certain embodiments, the separator includes partially reduced graphene oxide, partially reduced graphite oxide, or a combination thereof.

[0076] The energy storage device may include a separator disclosed herein, an additive disclosed herein (e.g., included in an electrode), or both. The energy storage device may be, for example, a battery, a fuel cell unit, or a capacitor. The battery may be a primary battery or a secondary battery. Whether the battery is primary or secondary, the battery may be an aqueous battery or a non-aqueous battery (e.g., including a solid electrolyte). For example, the battery may be an ion battery, such as an aluminum ion battery, a sodium ion battery, a potassium ion battery, a proton battery, a calcium ion battery, a manganese ion battery, a lithium ion battery, an air battery, or a combination of one or more thereof. The energy storage device does not need to have a specific battery cell configuration, cathode composition, anode composition, electrolyte composition, or any other electrode composition.

[0077] Diaphragm

[0078] In some embodiments, a separator for an energy storage device (e.g., an electrochemical cell) includes inorganic particles. The separator may also include one or more adhesives, which are used to bind the inorganic particles together. The inorganic particles may be functional inorganic particles. The separator is a solid or semisolid (e.g., gel or colloidal) layer. For example, the semisolid layer may be a surface layer, such as a surface layer formed in situ or ex situ (e.g., by coating when in contact with a mixture (e.g., a solution)). This surface layer may act as a separator when placed between two electrodes of an electrochemical cell. A solid separator may be, for example, a self-supporting film, for example, a self-supporting film formed ex situ and then placed between two electrodes. The following description provides, in particular, different types of inorganic particles (e.g., different compositions, sizes, morphologies, porosities, or combinations thereof). The separator may include only one type or different types of inorganic particles mixed together.

[0079] In some embodiments, the inorganic particles comprise at least 50 wt.% (e.g., at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%) of the separator. The inorganic particles may include oxygen, hydrogen, aluminum, silicon, phosphorus, metal atoms, or combinations thereof. Useful metal atoms include aluminum, silicon, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium. The one or more elements contained in the inorganic particles may account for at least 10 wt.% (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%) of the inorganic particles. Alternatively or in addition, the one or more metal atoms contained in the inorganic particles may account for no more than 80 wt.% (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 20 wt.%) of the inorganic particles. The inorganic particles may have M y Al x Si 1-x O 2 ·zH 2 O, wherein M is a metal. x may be in the range of 0 to 0.5 (e.g., 0 to 0.1 or 0.01 to 0.5), and y may be in the range of 0 to 0.5 (e.g., 0 to 0.1). x may be in the range of 0.5 to 1, and y may be in the range of 0 to 1. z may be in the range of 0 to 10,000. The inorganic particles may be crystalline, amorphous, or a combination thereof. The average particle size (D 50) can be in the range of 100 nm to 30 μm. The inorganic particles can have the shape of spheres, rods, needles, flakes, platelets, cubes, disks or tubes.

[0080] The inorganic particles may be porous. The porosity may be microporosity, mesoporosity, macroporosity, or a combination thereof. The inorganic particles may include one or more pores having a size (e.g., diameter) of less than 2 nm. The inorganic particles may include one or more pores having a size (e.g., diameter) of at least 2 nm and not greater than 50 nm. The inorganic particles may include one or more pores having a size (e.g., diameter) of greater than 50 nm. In some embodiments, the inorganic particles include one or more pores having a size (e.g., diameter) of less than 2 nm. to (For example, to to to )[For example, (For example, )to (For example, The surface area of ​​the inorganic particles can be at least 10m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g), for example due to its porosity.

[0081] One or more holes of inorganic particles can be connected to form one or more channels. One or more channels of one or more inorganic particles can intersect to form one or more channel systems, such as extending through particles or in some embodiments through the channel system of barrier film (for example, through multiple particles). The channel system can be 1-dimensional channel system, 2-dimensional channel system or 3-dimensional channel system. Figure 1A An example of a one-dimensional pore forming a one-dimensional channel system through a particle is shown. Figure 1B An example of a two-dimensional hole forming a two-dimensional channel system is shown. Figure 1A-1B , but this is not necessarily the case; the pores may follow complex (non-linear) paths into and / or through the particle. Figure 1A-1B A three-dimensional channel system is not shown, which would include holes in the third dimension (e.g., see Figure 1B , enter and leave the page. ) In some embodiments, one or more cage structures exist at the intersection of two or more holes. The cage structure can be located at the intersection of holes. The cage structure can be located within one or more 1-dimensional holes. Figure 1C Examples of cage-like structures located within one or more 1-dimensional pores are shown.

[0082] In certain embodiments, one or more holes and / or one or more cage structures have one or more species placed therein. For example, one or more species can be absorbed into one or more holes and / or one or more cage structures, and are not covalently bound to inorganic particles. One or more species placed in holes and / or cage structures can be, for example, adsorbed onto the surface (for example, inner surface or opening) of holes and / or cage structures, absorbed into holes and / or cage structures, or both. The size, shape, dimension and hydrophobicity / hydrophilicity environment of holes and / or cage structures can determine which one or more species can be applied to such holes, can be accommodated in such holes and / or can be absorbed in such holes. For example, larger holes can be used to accommodate larger species, and smaller holes are used for smaller species. Similarly, the membrane can include inorganic particles of the first type and inorganic particles of the second type, the inorganic particles of the first type include hydrophobic holes, can have hydrophobic species adsorbed thereon, and the inorganic particles of the second type include hydrophilic (or not too hydrophobic) holes, can have hydrophilic (or not too hydrophobic) species adsorbed thereon. The hydrophobicity / hydrophilicity environment of inorganic particles can be tuned, for example, by modifying the chemical composition of the particles and / or by surface treatment. Incorporation of different species (e.g., different atomic species and / or ionic species) can change the overall polarity of the surface and thereby change the hydrophobicity / hydrophilicity.

[0083] One or more species placed in one or more holes and / or one or more cage structures can be or include water, olefins, paraffins, cycloalkanes and aromatic hydrocarbons or their combinations. One or more gas species can be included in one or more holes and / or one or more cage structures (e.g., on the surface). The one or more gas species can include hydrogen, oxygen, carbon oxides (e.g., carbon dioxide), nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides (e.g., nitrogen dioxide), sulfur oxides (e.g., sulfur dioxide) or their combinations. One or more cationic species can be included in one or more holes and / or one or more cage structures (e.g., on the surface). The one or more cationic species can include the following cationic forms: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium or a combination thereof. The one or more anionic species can be located in one or more cage structures and / or one or more holes (e.g., disposed on the surface thereof). The one or more anionic species can include polyatomic anions. The one or more anionic species can include hydroxides, alkoxides, peroxides, superoxides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphides, fluorides, chlorides, bromides, iodides, chlorates, bromates, iodates, polyoxometalates or combinations thereof. The method suitable for inserting species into the holes and / or cage structures of inorganic particles and replacing the species is known to those of ordinary skill in the art.

[0084] An example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1-x O 2 ·zH 2O structure, wherein x is in the range of 0 to 0.1, y is in the range of 0 to 0.1, and z is in the range of 0 to 10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have a three-dimensional interconnected pore structure that defines a three-dimensional channel system. These pores have openings, the sizes of which range from Preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to , preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 100m 2 / g, and more preferably at least 300m 2 A plurality of these inorganic particles may be included in the separator, for example, combined with one or more binders.

[0085] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1- x O 2·zH 2 O structure, wherein x is in the range of 0 to 0.5, y is in the range of 0 to 0.5, and z is in the range of 0 to 10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have three-dimensionally interconnected pores that define a three-dimensional channel system. These pores have openings, the sizes of which range from , preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to Preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 250m 2 / g, and more preferably at least 700m 2 A plurality of these inorganic particles may be included in the separator, for example, combined with one or more binders.

[0086] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1- x O2 ·zH 2 O structure, wherein x is in the range of 0.5-1, y is in the range of 0-1, and z is in the range of 0-10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have a three-dimensional interconnected pore structure that defines a three-dimensional channel system. These pores have openings, the sizes of which range from Preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to , preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 250m 2 / g, and more preferably at least 500m 2 A plurality of these inorganic particles may be included in the separator, for example, combined with one or more binders.

[0087] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1-x O 2 ·zH 2 O structure, wherein x is in the range of 0.01 to 0.5, y is in the range of 0-0.5, and z is in the range of 0-10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have a three-dimensional interconnected pore structure that defines a three-dimensional channel system. These pores have openings, the sizes of which range from , preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to Preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 250m 2 / g, and more preferably at least 500m 2 A plurality of these inorganic particles may be included in the separator, for example, combined with one or more binders.

[0088] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M yAl x Si 1- x O 2 ·zH 2 O structure, wherein x is in the range of 0.01 to 0.5, y is in the range of 0 to 0.5, and z is in the range of 0-10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). This inorganic particle contains one-dimensional pores. These pores have openings, and the size of the openings ranges from Preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 150m 2 / g, and more preferably at least 300m 2 A plurality of these inorganic particles may be included in the separator, for example, combined with one or more binders.

[0089] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1- x O 2 ·zH 2O structure, wherein x is in the range of 0.01 to 0.5, y is in the range of 0 to 0.5, and z is in the range of 0 to 10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium) and Pu (plutonium). Such inorganic particles have a two-dimensional interconnected pore structure. These pores have openings, and the size of the openings ranges from Preferably between and and more preferably between and These two-dimensional holes intersect to produce cage-like structures with diameters ranging from to , preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 150m 2 / g, and more preferably at least 300m 2 A plurality of these inorganic particles may be included in the separator, for example, combined with one or more binders.

[0090] Another example of an inorganic particle (e.g., a functional inorganic particle) is a structure having a general chemical composition of MxOy, where x is in the range of 0 to 2 and y is in the range of 0 to 5. M can be any one or more of the following: Mg (magnesium), Al (aluminum), Si (silicon), Ti (titanium), Mn (manganese), Ca (calcium), Zn (zinc), Sr (strontium), Y (yttrium), Zr (zirconium), Nb (niobium), Sn (tin), Sb (antimony), Ba (barium), La (lanthanum), Ce (cerium), Ta (tantalum), Bi (bismuth). In some embodiments, such inorganic particles may include secondary particles. In some embodiments, the inorganic particles are non-porous. In some embodiments, the inorganic particles are amorphous. In other embodiments, the inorganic particles are partially or completely crystalline. The surface area of ​​these inorganic particles is typically at least 0.1 m 2 / g and less than 1000m 2 / g. The inorganic particles can be prepared by a chemical precursor at 30-250°C for 0-30 days under static or stirring conditions to undergo a crystallization reaction. The chemical precursor may include one or more of the following: a silica source, an alumina source, a mineralizer, an acid medium or an alkaline medium, one or more templates or structure directing agents (SDA). The inorganic particles can also be synthesized by mineral extraction, flame pyrolysis or other methods known to those skilled in the art.

[0091] In some embodiments, in addition to inorganic particles, the diaphragm includes one or more adhesives. One or more adhesives can account for no more than 50wt.%, preferably no more than 20wt.% of the diaphragm. In some embodiments, the one or more adhesives account for no more than 50wt.% (e.g., no more than 40wt.%, no more than 30wt.%, no more than 20wt.%, no more than 10wt.%, no more than 5wt.% or no more than 1wt.%) of the diaphragm. One or more adhesives can include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR) or a combination thereof. Optionally, adhesives can include one or more additives. pH regulators, pH buffers, rheology modifiers, defoamers, antifoaming agents, adhesion promoters and leveling agents can be used as additives. In some embodiments, the separator may further include a conductive polymer. In some embodiments, the conductive polymer accounts for no more than 80 wt.%, preferably no more than 50 wt.% of the separator. The separator may include one or more of the following conductive polymers: polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), PEDOT.

[0092] The separator can be directly coated on one or more electrodes (e.g., anode or cathode or both anode and cathode) in non-situ. The coating technique may include, but is not limited to, one or more or a combination of the following: wet chemical reaction, physical vapor deposition, chemical vapor deposition, atomic layer deposition, sintering, pressing, hot pressing, extrusion, die casting, slot die coating and blade coating. When one or more liquid coating methods are used to coat the separator, any mixing method known to those familiar with the art can be used to prepare the coating. The coating can be aqueous or solvent-based, including inorganic particles and one or more adhesives. The wet-coated layer can be placed on an electrode with a thickness in the range of 5 μm to 500 μm. The coated layer can be dried in air at any temperature ranging from 25 ° C to 200 ° C. The coated layer can be further subjected to calendaring to increase bonding strength or layer uniformity or both. Temperature treatments such as annealing can also be used. Further, the separator may or may not be used in combination with a liquid electrolyte (e.g., it may be used with a solid electrolyte).

[0093] The membrane containing inorganic particles can also be prepared by dip coating the electrode into a coating formulation containing inorganic particles. When the membrane is coated using a dip coating method, any mixing method known to those familiar with the art can be used to prepare the coating. The coating can be aqueous or solvent-based and include inorganic particles and one or more binders.

[0094] In certain embodiments, a diaphragm comprising inorganic particles can be placed on the surface of an electrode by in situ synthesis. In one example, this can be accomplished by crystallizing a mixture of chemical precursors on the surface of an electrode (e.g., an anode). A crystallization reaction of a chemical precursor can be performed at 30-250° C., statically or under stirring conditions for 0-30 days. The chemical precursor can include one or more of the following: a silica source, an alumina source, a mineralizer, an acid medium or an alkaline medium, one or more templates or structure directing agents (SDAs).

[0095] In some embodiments, the diaphragm can be prepared with a self-supporting film. The self-supporting film can be prepared in any way. In an example, the self-supporting film can be prepared by coating the inorganic particle diaphragm on the release layer, and the release layer is then dissolved. The release layer can then be dissolved in a suitable solvent. The self-supporting film can also be produced by extruding a film containing inorganic particles and one or more adhesives (for example, a binding polymer). One or more adhesives can include a binding polymer, such as polyethylene, polyvinyl chloride, polycarbonate, acrylonitrile butadiene styrene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) or styrene butadiene rubber (SBR) or a combination thereof.

[0096] In some embodiments, the separator comprising inorganic particles and optionally one or more binders can be combined with a second separator (e.g., a second separator comprising inorganic particles and one or more binders) for use in, for example, an energy storage device (e.g., a battery). The second separator can be placed between two electrodes (e.g., anodes or cathodes), for example, on the anode side of the first separator or the cathode side of the first separator, or both. Alternatively, the first separator can be placed on one or both sides of the second separator; the second separator can then be placed between the two electrodes.

[0097] In some embodiments, the inorganic particle separator can be applied to (e.g., coated on) a current collector substrate or can be a part of a current collector substrate. The inorganic particle mixture can also include one, more, or a combination of polymers as binders, polymers as conductive additives, carbon as conductive additives, other conductive additives such as metals and metal oxides, and other additives necessary to stabilize the coating in an electrochemical environment.

[0098] Without wishing to be bound by any particular theory, the inorganic particles in the separator can provide one or more of several functions. The particles can provide ionic conductivity, thereby allowing ionic charge carriers to be transferred to the electrode (e.g., anode and cathode) and transferred from the electrode (e.g., through an electrolyte), such as thereby promoting the insertion and deintercalation of ions in one or more electroactive materials in the electrode. The conductivity of the ions can be promoted by the presence of holes and polar sites on the surface (e.g., inner surface) of the inorganic particles. Additionally or alternatively, the inorganic particles can act as an absorbent. Species from undesirable side reactions can be collected in the inorganic particles, such as in the holes and cage structures of the inorganic particles. Inorganic particles can additionally or alternatively provide protection from the effects of undesirable side reactions, including but not limited to irreversible surface reactions, active material mass loss, corrosion, embrittlement and crushing. For example, these reactions can occur in the electrode, at the surface of the electrode, at the surface of the current collector, or in the entirety of the current collector. The reactants of one or more side reactions can be present in the electrolyte, such as by migrating from the electrode formed therefrom.

[0099] In one such example, according to some embodiments, a silicate, phosphate, sulfate, oxide, hydride, or combination thereof that forms part of the structure of the inorganic particle can dissolve and precipitate as one or more polymer species (e.g., polysilicate and / or polyphosphate) onto the surface of one or more materials in the energy storage device, thereby passivating it due to undesirable side reactions (e.g., additional undesirable side reactions). The energy storage device may include inorganic particles, such as in an electrode additive and / or a separator, comprising a silicate, phosphate, sulfate, oxide, hydride, or combination thereof (e.g., one or more silicates and / or one or more phosphates). The silicate, phosphate, sulfate, oxide, hydride, or combination thereof (e.g., silicate and / or phosphate) may be in a stable (e.g., salt) form and / or an ionic (e.g., anionic) form. Silicates, phosphates, sulfates, oxides, hydrides, or combinations thereof (e.g., silicates and / or phosphates) can react with one or more species (e.g., in an electrolyte and / or an electrode) (e.g., one or more portions of a species); one or more species can be reactants in one or more undesirable side reactions of an energy storage device. In some embodiments, the reaction includes dissolving at least a portion of the inorganic particles. After the reaction, one or more reaction products can passivate the surface of a material in the energy storage device (e.g., a metal surface and / or a surface of an electroactive material). The surface can be passivated by forming one or more polymer species (e.g., including polysilicates and / or polyphosphates) on the surface or by depositing one or more polymer species onto the surface. Thus, the passivated surface can prevent one or more undesirable side reactions from occurring or further occurring. The reaction and / or passivation can occur during the electrochemical cycle of the energy storage device (e.g., during battery charging and / or discharging) or before the assembly of the energy storage device is completed (e.g., during the preconditioning process of the electrodes of the energy storage device).

[0100] Various embodiments of these inorganic particles may be included in the separator, for example, with a surface area less than 10 m 2 / g is dispersed over a surface area greater than 100m 2 / g of inorganic particles between particles. In one embodiment, the separator containing these inorganic particles can resist the puncture of dendrites formed on adjacent electrodes. In another embodiment, before the first electrode is assembled into a battery cell relative to a second electrode containing a metal, a protective separator layer is formed on the surface of the first electrode. In an even further embodiment, the separator physically compresses the second electrode, thereby minimizing the growth of dendrites and preventing the dendrites from penetrating the separator to the first electrode.

[0101] additive

[0102] In some embodiments, additives for energy storage devices (e.g., electrochemical cells) include inorganic particles. The additives can be used for electrodes (e.g., anodes and / or cathodes of electrochemical cells). The electrode includes an electroactive material, and optionally, in addition to the electroactive material and the inorganic particles, one or more adhesives can also be included, the one or more adhesives being used to bind the inorganic particles together, one or more conductive additives together, or both together. The inorganic particles can be functional inorganic particles. One or more additives can be included in the electrode during the electrode manufacturing process. In some embodiments, an electrode can be prepared by coating a mixture (e.g., a solution) including one or more additives and one or more electroactive materials onto, for example, a substrate (e.g., a current collector). The following description provides, among other things, different types of inorganic particles (e.g., different compositions, sizes, morphologies, porosities, or combinations thereof). The additive can include only one type or different types of inorganic particles mixed together.

[0103] In some embodiments, the inorganic particles comprise at least 50 wt.% (e.g., at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%) of the additive. The inorganic particles may include oxygen, hydrogen, aluminum, silicon, phosphorus, metal atoms, or combinations thereof. Useful metal atoms include aluminum, silicon, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium. The one or more elements contained in the inorganic particles may account for at least 10 wt.% (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%) of the inorganic particles. Alternatively or in addition, the one or more metal atoms contained in the inorganic particles may account for no more than 80 wt.% (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 20 wt.%) of the inorganic particles. The inorganic particles may have M y Al x Si 1-x O 2 ·zH 2 O, wherein M is a metal. x can be in the range of 0 to 0.5 (e.g., 0 to 0.1 or 0.01 to 0.5), and y is in the range of 0 to 0.5 (e.g., 0 to 0.1). x can be in the range of 0.5 to 1, and y is in the range of 0 to 1. z can be in the range of 0 to 10,000.

[0104] The inorganic particles may be crystalline, amorphous or a combination thereof. The average particle size (D 50 ) can be in the range of 100nm-30μm. The inorganic particles can have the shape of a sphere, a rod, a needle, a flake, a platelet, a cube, a disk or a tube. In some embodiments, the inorganic particles of the electrode additive account for 1vol.% to 50vol.% (e.g., 5vol.% to 30vol.% or 10vol.% to 20vol.%) of the electrode active layer (e.g., coating or film) of the electrode (e.g., excluding any current collector), preferably 5vol.% to 30vol.%, more preferably 10vol.% to 20vol.%.

[0105] The inorganic particles may be porous. The porosity may be microporosity, mesoporosity, macroporosity, or a combination thereof. The inorganic particles may include one or more pores having a size (e.g., diameter) of less than 2 nm. The inorganic particles may include one or more pores having a size (e.g., diameter) of at least 2 nm and not greater than 50 nm. The inorganic particles may include one or more pores having a size (e.g., diameter) of greater than 50 nm. In some embodiments, the inorganic particles include one or more pores having a size (e.g., diameter) of less than 2 nm. to (For example, to to to )[For example, (For example, )to (For example, The surface area of ​​the inorganic particles can be at least 10m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g), for example due to its porosity.

[0106] One or more holes of inorganic particles can be connected to form one or more channels. One or more channels of one or more inorganic particles can intersect to form one or more channel systems, such as extending through particles or in some embodiments through the channel system of electrodes (e.g., through multiple particles). The channel system can be 1-dimensional channel system, 2-dimensional channel system or 3-dimensional channel system. Figure 1A An example of a one-dimensional pore forming a one-dimensional channel system through a particle is shown. Figure 1A An example of a two-dimensional hole forming a two-dimensional channel system is shown. Figure 1A-1B , but this is not necessarily the case; the pores may follow complex (non-linear) paths into and / or through the particle. Figure 1A-1B A three-dimensional channel system is not shown, which would include holes in the third dimension (e.g., see Figure 1B , enter and leave the page. ) In some embodiments, one or more cage structures exist at the intersection of two or more holes. The cage structure can be located at the intersection of holes. The cage structure can be located within one or more 1-dimensional holes. Figure 1C Examples of cage-like structures located within one or more 1-dimensional pores are shown.

[0107] In certain embodiments, one or more holes and / or one or more cage structures have one or more species placed therein. For example, one or more species can be absorbed into one or more holes and / or one or more cage structures, and are not covalently bound to inorganic particles. One or more species placed in holes and / or cage structures can be, for example, adsorbed onto the surface (for example, inner surface or opening) of holes and / or cage structures, absorbed into holes and / or cage structures, or both. The size, shape, dimension and hydrophobicity / hydrophilicity environment of holes and / or cage structures can determine which one or more species can be applied to such holes, can be accommodated in such holes and / or can be absorbed in such holes. For example, larger holes can be used to accommodate larger species, and smaller holes are used for smaller species. Similarly, additives can include inorganic particles of the first type and inorganic particles of the second type, the inorganic particles of the first type include hydrophobic holes, can have hydrophobic species adsorbed thereon, and the inorganic particles of the second type include hydrophilic (or not too hydrophobic) holes, can have hydrophilic (or not too hydrophobic) species adsorbed thereon. The hydrophobicity / hydrophilicity environment of inorganic particles can be tuned, for example, by modifying the chemical composition of the particles and / or by surface treatment. Incorporation of different species (e.g., different atomic species and / or ionic species) can change the overall polarity of the surface and thereby change the hydrophobicity / hydrophilicity.

[0108] One or more species placed in one or more holes and / or one or more cage structures can be or include water, olefins, paraffins, cycloalkanes and aromatic hydrocarbons or their combinations. One or more gas species can be included in one or more holes and / or one or more cage structures (e.g., on the surface). The one or more gas species can include hydrogen, oxygen, carbon oxides (e.g., carbon dioxide), nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides (e.g., nitrogen dioxide), sulfur oxides (e.g., sulfur dioxide) or their combinations. One or more cationic species can be included in one or more holes and / or one or more cage structures (e.g., on the surface). The one or more cationic species can include the following cationic forms: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium or a combination thereof. The one or more anionic species can be located in one or more cage structures and / or one or more holes (e.g., disposed on the surface thereof). The one or more anionic species can include polyatomic anions. The one or more anionic species can include hydroxides, alkoxides, peroxides, superoxides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphides, fluorides, chlorides, bromides, iodides, chlorates, bromates, iodates, polyoxometalates or combinations thereof. The method suitable for inserting species into the holes and / or cage structures of inorganic particles and replacing the species is known to those of ordinary skill in the art.

[0109] An example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1-x O 2 ·zH 2O structure, wherein x is in the range of 0 to 0.1, y is in the range of 0 to 0.1, and z is in the range of 0 to 10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have a three-dimensional interconnected pore structure that defines a three-dimensional channel system. These pores have openings, the sizes of which range from Preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to , preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 100m 2 / g, and more preferably at least 300m 2 A plurality of these inorganic particles may be included in an additive or electrode, for example, combined with one or more binders in an electrode.

[0110] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1- x O2 ·zH 2 O structure, wherein x is in the range of 0 to 0.5, y is in the range of 0 to 0.5, and z is in the range of 0 to 10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have three-dimensionally interconnected pores that define a three-dimensional channel system. These pores have openings, the sizes of which range from Preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to , preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 250m 2 / g, and more preferably at least 700m 2 A plurality of these inorganic particles may be included in an additive, such as added to an electrode, such as combined with one or more binders.

[0111] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si1- x O 2 ·zH 2 O structure, wherein x is in the range of 0.5-1, y is in the range of 0-1, and z is in the range of 0-10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have a three-dimensional interconnected pore structure, and the three-dimensional interconnected pore structure defines a three-dimensional channel system. These holes have openings whose sizes range from 1- , preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to , preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 250m 2 / g, and more preferably at least 500m 2 A plurality of these inorganic particles may be included in an additive, such as added to an electrode, such as combined with one or more binders.

[0112] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition My Al x Si 1- x O 2 ·zH 2 O structure, wherein x is in the range of 0.01 to 0.5, y is in the range of 0-0.5, and z is in the range of 0-10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). Such inorganic particles have a three-dimensional interconnected pore structure that defines a three-dimensional channel system. These pores have openings, the sizes of which range from , preferably between and and more preferably between and These three-dimensional holes intersect to create cage-like structures with diameters ranging from to Preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 250m 2 / g, and more preferably at least 500m 2 A plurality of these inorganic particles may be included in an additive, such as added to an electrode, such as combined with one or more binders.

[0113] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1- x O 2 ·zH 2 O structure, wherein x is in the range of 0.01 to 0.5, y is in the range of 0 to 0.5, and z is in the range of 0-10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium), Pu (plutonium). This inorganic particle contains one-dimensional pores. These pores have openings, and the size of the openings ranges from Preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 150m 2 / g, and more preferably at least 300m 2 A plurality of these inorganic particles may be included in an additive, such as added to an electrode, such as combined with one or more binders.

[0114] Another example of an inorganic particle (eg, a functional inorganic particle) is a particle having a general chemical composition M y Al x Si 1- x O 2 ·zH2 O structure, wherein x is in the range of 0.01 to 0.5, y is in the range of 0 to 0.5, and z is in the range of 0 to 10,000. M can be any one or more of the following: Li (lithium), Na (sodium), K (potassium), Rb (rubidium), Cs (cesium), Be (beryllium), Mg (magnesium), Ca (calcium), Sr (strontium), Ba (barium), B (boron), Ga (gallium), In (indium), Tl (thallium), C (carbon), Ge (germanium), Sn (tin), Pb (lead), N (nitrogen), P (phosphorus), As (arsenic), Sb (antimony), Bi (bismuth), Sc (scandium), Ti (titanium), V (vanadium), Cr (chromium), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Cu (copper), Zn (zinc), Y (yttrium), Zr (zirconium), ), Nb (niobium), Mo (molybdenum), Ru (ruthenium), Rh (rhodium), Pd (palladium), Ag (silver), Cd (cadmium), Hf (hafnium), Ta (tantalum), W (tungsten), Re (rhenium), Os (osmium), Ir (iridium), Pt (platinum), Au (gold), Hg (mercury), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Th (thulium), Yb (ytterbium), Lu (lutetium), Ac (actinium), Th (thorium), Pa (protactinium), U (uranium), Np (neptunium) and Pu (plutonium). Such inorganic particles have a two-dimensional interconnected pore structure. These pores have openings, and the size of the openings ranges from Preferably between and and more preferably between and These two-dimensional holes intersect to produce cage-like structures with diameters ranging from to Preferably between and and more preferably between and The surface area of ​​these inorganic particles is typically at least 10 m 2 / g, preferably at least 150m 2 / g, and more preferably at least 300m 2 A plurality of these inorganic particles may be included in an additive, such as added to an electrode, such as combined with one or more binders.

[0115] Inorganic particles can be prepared by crystallization of chemical precursors at 30-250° C. for 0-30 days either statically or under stirring conditions. The chemical precursors may include one or more of the following: a silica source, an alumina source, a mineralizer, an acid medium or an alkaline medium, one or more templates or structure directing agents (SDA).

[0116] One or more inorganic particles of electrode additives can be added directly to a mixture (e.g., solution and / or coating formulation) for placing an electrode active layer on a current collector to form an electrode. The mixture can contain any combination of one or more electroactive materials, one or more conductive additives, one or more binders, and one or more additives. Examples of electroactive materials that can be used for electrodes include the following: oxides, suboxides, sulfides, oxysulfides, phosphates, phosphides, and carbides, as well as silicon, vanadium, niobium, molybdenum, rhenium, tantalum, tungsten, bismuth, titanium, tin, antimony, manganese, nickel, aluminum, lithium, sodium, potassium, calcium, zinc, cobalt, chromium, indium, lanthanum, cerium, strontium, and iron in their basic forms and combinations thereof. The electroactive material of the electrode can be modified (e.g., doped) using one or more elements. The one or more elements may be any of the following: hydrogen, lithium, boron, carbon, nitrogen, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, antimony, lanthanum, cerium, neodymium, tantalum, tungsten, rhenium, platinum, gold, lead, bismuth. The electrode active layer comprising one or more electroactive materials and one or more additives may be a self-supporting film, or may be present (e.g., coated) on a substrate such as a current collector. The substrate may include a carbon material such as foam, paper, aerogel, foil, fiber or nanostructure (e.g., nanoparticles), or a metal foil, foam, sheet, mesh or raw material.

[0117] In some embodiments, the electrode of the energy storage device includes one or more binders. Each of the one or more binders can be, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyacrylic acid (PAA), polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR) or its copolymer. In some embodiments, in addition to one or more additives containing inorganic particles, the electrode of the energy storage device also includes one or more conductive additives. Each of the one or more conductive additives can be selected from the following: carbon black, acetylene black, carbon fiber, carbon nanotubes, graphene, graphite, fullerene, carbon aerogel, metal flakes, metal fibers, metal particles and conductive polymers. The conductive polymer used for the electrode in the energy storage device can be, for example, polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide) or PEDOT.

[0118] The inorganic particles of the electrode additive can be placed on the surface of the electroactive material. For example, the inorganic particles can be placed on one or more surfaces of microstructures and / or nanostructures (such as particles (having any shape, such as spheres or rods), films, tubes and / or fibers) formed by the electroactive material. The inorganic particles of the electrode additive can be placed on the surface of the conductive additive. For example, the inorganic particles can be placed on one or more surfaces of microstructures and / or nanostructures (such as particles (having any shape, such as spheres or rods), films, tubes and / or fibers) formed by the conductive additive.

[0119] In some embodiments, the inorganic particles of the additive in the electrode can form a core-shell structure with the electroactive material, for example, when the electroactive material is in the form of particles (e.g., microparticles and / or nanoparticles) and the inorganic particles are disposed on the electroactive material particles. The inorganic particles can form a layer of uniform thickness or non-uniform thickness on (e.g., completely surrounding) the electroactive material (e.g., electroactive material particles). Figure 2 is a cross-section of a battery having an arrangement in which both the electrode layers (anode and cathode) and the separator layer include particles (e.g., additives) disclosed herein. In some embodiments, an energy storage device according to the present disclosure can be a battery, for example, having Figure 3 In some embodiments, the battery may include a first electrode, a second electrode, and a separator as disclosed herein disposed between the first electrode and the second electrode. Figure 3In the embodiment, the battery 300 includes a top 310, a spring 320, a first separator 330, a cathode 340, a separator 350 (e.g., as disclosed herein), an anode 360, a second separator 370, an electrolyte (not labeled), and a base 380. Other form factors of batteries having the same or similar components may also be used, as discussed further below. In some embodiments, the thickness of the inorganic material layer of the additive is no greater than 2 μm.

[0120] Inorganic particles can adhere to the surface of the electroactive material through electrostatic potential. This electrostatic potential can be generated when the inorganic particles and the electroactive material have opposite charges. Inorganic particles and electroactive materials (e.g., electroactive particles) can be dry blended or combined in an aqueous slurry. One or more surfactants and one or more surface modifiers known to those skilled in the art can be used to change the surface chemistry of the electroactive material or inorganic particles to achieve the desired electrostatic potential. Alternatively or in addition, inorganic particles can be deposited on the surface of the electroactive material by chemical reaction. Sol-gel synthesis is an example of a method that can be used to deposit inorganic particles on the surface of the electroactive material. In some embodiments, the inorganic particles can be evenly distributed throughout the active layer of the electrode, that is, for example, deposited on the collector. For example, additive inorganic particles and electroactive material particles can be dispersed throughout the electrode (e.g., its active layer).

[0121] Without wishing to be bound by any particular theory, the inorganic particles in the additive in the electrode can provide one or more of several functions. The inorganic particles can provide ionic conductivity, thereby allowing non-electronic charge carriers to be transferred to or from one or more electroactive materials, for example, thereby promoting the insertion and extraction of ions in the electroactive materials. Ionic conductivity can be promoted by the presence of holes and polar sites on one or more surfaces of the inorganic particles in the additive. This increase in conductivity can improve the performance of the cell by reducing the resistance of the electrochemical cell and / or improving the quantum efficiency of the electrochemical cell. Alternatively or in addition, the inorganic particles in the additive can act as an absorbent. One or more species from one or more undesirable side reactions can be collected in the inorganic particles (e.g., in their pores). Isolating these byproducts maintains the integrity of the energy storage device, for example, by preventing one or more electrodes to which the additive is added from being poisoned. This improves the overall cycle life of the energy storage device. The inorganic particles can also provide protection from the effects of undesirable side reactions, including but not limited to irreversible surface reactions, loss of active material mass, corrosion, embrittlement, and crushing. These reactions can occur within one or more electrodes, at one or more surfaces of one or more electrodes, at one or more surfaces of one or more current collectors, or in the bulk of the current collector. Preventing one or more undesirable side reactions can help maintain the quantum efficiency and overall performance of the energy storage device.

[0122] In one such example, according to some embodiments, a silicate, phosphate, sulfate, oxide, hydride, or combination thereof that forms part of the structure of the inorganic particle can dissolve and precipitate as one or more polymer species (e.g., polysilicate and / or polyphosphate) onto the surface of one or more materials in the energy storage device, thereby passivating it due to undesirable side reactions (e.g., additional undesirable side reactions). The energy storage device may include inorganic particles, such as in an electrode additive and / or a separator, comprising a silicate, phosphate, sulfate, oxide, hydride, or combination thereof (e.g., one or more silicates and / or one or more phosphates). The silicate, phosphate, sulfate, oxide, hydride, or combination thereof (e.g., silicate and / or phosphate) may be in a stable (e.g., salt) form and / or an ionic (e.g., anionic) form. Silicates, phosphates, sulfates, oxides, hydrides, or combinations thereof (e.g., silicates and / or phosphates) can react with one or more species (e.g., in an electrolyte and / or an electrode) (e.g., one or more portions of a species); one or more species can be reactants in one or more undesirable side reactions of an energy storage device. In some embodiments, the reaction includes dissolving at least a portion of the inorganic particles. After the reaction, one or more reaction products can passivate the surface of a material in the energy storage device (e.g., a metal surface and / or a surface of an electroactive material). The surface can be passivated by forming one or more polymer species (e.g., including polysilicates and / or polyphosphates) on the surface or by depositing one or more polymer species onto the surface. Thus, the passivated surface can prevent one or more undesirable side reactions from occurring or further occurring. The reaction and / or passivation can occur during the electrochemical cycle of the energy storage device (e.g., during battery charging and / or discharging) or before the assembly of the energy storage device is completed (e.g., during the preconditioning process of the electrodes of the energy storage device).

[0123] Additional separator and additive materials: organic ligands, non-metal oxides and partially reduced carbon (graphite and graphene)

[0124] The separator may include a functional material. The functional material may be used as an additive in an energy storage device, such as an electrode of a battery (such as a secondary battery). The functional material may include one or more organic ligands. Additionally or alternatively, the functional material may include one or more non-metallic oxides. Additionally or alternatively, the functional material may include partially reduced carbon, such as partially reduced graphene, partially reduced graphite, or both.

[0125] Functional materials can be modified (e.g., doped) with one or more elements. One or more elements can be one or more of the following: sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine and iodine. Functional materials can additionally include one or more water molecules. For example, one or more water molecules can coordinate and / or bond with functional materials (e.g., framework ligands in the case of one or more ligands included in the functional material or partially reduced carbon in the case of partially reduced carbon included in the functional material), such as hydrogen bonding.

[0126] In some embodiments, the functional material is porous. The porosity can be microporosity, mesoporosity, macroporosity, or a combination thereof. The functional material can include one or more pores having a size (e.g., diameter) of less than 2 nm. The functional material can include one or more pores having a size (e.g., diameter) of at least 2 nm and no greater than 50 nm. The functional material can include one or more pores having a size (e.g., diameter) of greater than 50 nm. In some embodiments, the functional material includes one or more pores having a size (e.g., diameter) of less than 2 nm. to (For example, to to to )[For example, (For example, )to (For example, The surface area of ​​the functional material can be at least 10m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g), for example due to its porosity and / or structure (for example, in the form of particles).

[0127] One or more holes of the functional material can be connected to form one or more channels. One or more channels of one or more parts of the functional material can intersect to form one or more channel systems, such as a channel system extending through the diaphragm. The channel system can be a 1-dimensional channel system, a 2-dimensional channel system, or a 3-dimensional channel system.

[0128] In certain embodiments, one or more holes have one or more species arranged therein. For example, one or more species can be absorbed into one or more holes, and are not covalently bound to inorganic particles. One or more species arranged in holes and / or cage structures can be, for example, adsorbed onto the surface (for example, inner surface or opening) of holes and / or cage structures, absorbed into holes and / or cage structures, or both. The size, shape, dimension and hydrophobicity / hydrophilicity environment of holes and / or cage structures can determine which one or more species can be applied to such holes, can be accommodated in such holes and / or can be absorbed in such holes. For example, larger holes can be used to accommodate larger species, and smaller holes are used for smaller species. Similarly, barrier film can include inorganic particles of the first type and inorganic particles of the second type, the inorganic particles of the first type include hydrophobic holes, can have hydrophobic species adsorbed thereon, and the inorganic particles of the second type include hydrophilic (or not too hydrophobic) holes, can have hydrophilic (or not too hydrophobic) species adsorbed thereon. The hydrophobicity / hydrophilicity environment of inorganic particles can be tuned, for example, by modifying the chemical composition of the particles and / or by surface treatment. Incorporation of different species (e.g., different atomic species and / or ionic species) can change the overall polarity of the surface and thereby change the hydrophobicity / hydrophilicity.

[0129] The one or more species disposed in the one or more holes may be or include water, olefins, paraffins, cycloalkanes, aromatic hydrocarbons or a combination thereof. One or more gas species may be included in the one or more holes (e.g., on the surface). One or more gas species may include hydrogen, oxygen, carbon dioxide gas, nitrogen, argon, hydrogen disulfide gas, ammonia, nitric oxide, nitrogen dioxide, sulfur dioxide or a combination thereof. One or more cationic species may be included in the one or more holes (e.g., on the surface). The one or more cationic species can include the following cationic forms: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, plutonium or a combination thereof. The one or more anionic species can be located in one or more cage structures and / or one or more holes (e.g., disposed on the surface thereof). The one or more anionic species can include polyatomic anions. The one or more anionic species can include hydroxides, alkoxides, peroxides, superoxides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphides, fluorides, chlorides, bromides, iodides, chlorates, bromates, iodates, polyoxometalates or combinations thereof. The method suitable for inserting species into the holes and / or cage structures of inorganic particles and replacing the species is known to those of ordinary skill in the art.

[0130] In some embodiments, the functional material comprises at least 50 wt.% of the membrane (e.g., at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.%) of the membrane. The functional material can be crystalline, amorphous, or a combination thereof. The functional material can be disposed in a plurality of discrete structures (e.g., particles). Thus, the average size (D 50 ) (eg, particle size) may be in the range of 100 nm-30 μm. Also therefore, the functional material may additionally or alternatively have the shape of a sphere, a rod, a needle, a flake, a platelet, a cube, a disk or a tube.

[0131] In some embodiments, in addition to functional materials, the diaphragm includes one or more adhesives. One or more adhesives can account for no more than 50wt.%, preferably no more than 20wt.% of the diaphragm. In some embodiments, the one or more adhesives account for no more than 50wt.% (e.g., no more than 40wt.%, no more than 30wt.%, no more than 20wt.%, no more than 10wt.%, no more than 5wt.% or no more than 1wt.%) of the diaphragm. One or more adhesives can include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR) or a combination thereof. Optionally, adhesives can include one or more additives. pH regulators, pH buffers, rheology modifiers, defoamers, antifoaming agents, adhesion promoters and leveling agents can be used as additives. In some embodiments, for example, in addition to one or more binders (and functional materials), the separator may also include a conductive polymer. In some embodiments, the conductive polymer accounts for no more than 80 wt.%, preferably no more than 50 wt.% of the separator. The separator may include one or more of the following conductive polymers: polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), PEDOT.

[0132] The diaphragm including the functional material can be directly coated on one or more electrodes (e.g., anode or cathode or both anode and cathode) in non-situ. The coating technique may include, but is not limited to, one or more or a combination of the following: wet chemical reaction, physical vapor deposition, chemical vapor deposition, atomic layer deposition, sintering, pressing, hot pressing, extrusion, die casting, slot die coating and blade coating. When the diaphragm is coated with one or more liquid coating methods, any mixing method known to those familiar with the art can be used to prepare the coating. The coating can be aqueous or solvent-based, including functional materials and one or more adhesives. The wet-coated layer can be placed on an electrode with a thickness in the range of 5 μm to 500 μm. The coated layer can be dried in air at any temperature ranging from 25° C. to 200° C. The coated layer can be further subjected to calendering to increase bonding strength or layer uniformity or both. Temperature treatments such as annealing can also be used. Further, the diaphragm may or may not be used in combination with a liquid electrolyte (e.g., it may be used with a solid electrolyte).

[0133] The membrane containing the functional material can also be prepared by dip coating the electrode into a coating formulation (e.g., in particulate form) containing the functional material. When the membrane is coated using a dip coating method, any mixing method known to those familiar with the art can be used to prepare the coating. The coating can be aqueous or solvent-based and include the functional material and one or more binders.

[0134] In certain embodiments, a membrane comprising a functional material can be placed on the surface of an electrode by in situ synthesis. In one example, this can be accomplished by crystallizing a mixture of chemical precursors on the surface of an electrode (e.g., an anode). A crystallization reaction of a chemical precursor can be performed at 30-250° C., statically or under stirring conditions for 0-30 days. The chemical precursor can include one or more of the following: a silica source, an alumina source, a mineralizer, an acid medium or an alkaline medium, one or more templates or structure directing agents (SDAs).

[0135] In some embodiments, the diaphragm can be prepared with a self-supporting film. The self-supporting film can be prepared in any way. In an example, the self-supporting film can be prepared by coating the inorganic particle diaphragm on the release layer, and the release layer is then dissolved. The release layer can then be dissolved in a suitable solvent. The self-supporting film can also be produced by extruding a film containing a functional material and one or more adhesives (for example, a binding polymer). One or more adhesives can include a binding polymer, such as polyethylene, polyvinyl chloride, polycarbonate, acrylonitrile butadiene styrene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) or styrene butadiene rubber (SBR) or a combination thereof.

[0136] In some embodiments, the separator comprising the functional material and one or more binders can be combined with a second separator (e.g., a second separator comprising the functional material and one or more binders) for use in, for example, an energy storage device (e.g., a battery). The second separator can be placed between two electrodes (e.g., an anode or a cathode), for example, on the anode side of the first separator or the cathode side of the first separator, or both. Alternatively, the first separator can be placed on one or both sides of the second separator; the second separator can then be placed between the two electrodes.

[0137] Energy storage devices comprising the materials, membranes and / or additives disclosed herein

[0138] The energy storage device may include a membrane disclosed herein, an additive disclosed herein (e.g., included in an electrode), or both. The energy storage device may be or include an electrochemical cell (e.g., a half-cell). The energy storage device may be, for example, a battery, a fuel cell cell, or a capacitor. The battery may be a primary battery or a secondary battery. Whether the battery is primary or secondary, the battery may be an aqueous battery or a non-aqueous battery (e.g., including a solid electrolyte). For example, the battery may be an ion battery, such as an aluminum ion battery, a sodium ion battery, a potassium ion battery, a proton battery, a calcium ion battery, a manganese ion battery, a lithium ion battery, an air battery, or a combination of one or more thereof. The energy storage device does not need to have a specific cell configuration, cathode composition, anode composition, electrolyte composition, or any other electrode composition. The following is an illustrative but non-limiting example of an energy storage device contemplated for use with the materials, membranes, additives, or combinations thereof disclosed herein.

[0139] In some embodiments, a separator disclosed herein (e.g., comprising inorganic particles, one or more organic ligands, and / or partially reduced carbon (e.g., graphite or graphene)) is used in an electrochemical cell (e.g., a battery). This separator may include inorganic particles disclosed herein. In some embodiments, the separator disclosed herein is used in an electrochemical cell as an ion conductive material disposed between two electrodes (e.g., an anode and a cathode). In some embodiments, the use of the separator disclosed herein in an electrochemical cell increases the wettability of the electrolyte. In some embodiments, the separator disclosed herein is used in a capacitor, for example as an ion conductive material disposed between two electrodes and / or to increase the wettability of the electrolyte. In some embodiments, the separator disclosed herein is used in a fuel cell unit.

[0140] In some embodiments, the energy storage device includes a cathode, an anode, an electrolyte, and a separator disclosed herein. The separator is placed between the anode and the cathode, thereby preventing the cathode from directly physically contacting the anode. The cathode, the anode, or both may include additives disclosed herein (e.g., different additives in the anode and the cathode). In some embodiments, the energy storage device includes a cathode, an anode, an electrolyte, and a separator, wherein the anode, the cathode, or both include additives disclosed herein. High energy density, extended battery cell life, and stability are achieved using the separator disclosed herein, and one or more of these can be achieved in an energy storage device including this separator. The separator disclosed herein can be made very thin, for example, less than 100 microns, less than 50 microns, or less than 25 microns.

[0141] The inorganic particles described herein may have ion conductive properties. In some embodiments, the inorganic particle membrane is capable of trapping gases produced by one or more undesirable side reactions in holes and / or cage structures produced by the inorganic particles. In some embodiments, the inorganic particle membrane provides protection from the effects of one or more undesirable side reactions, including but not limited to irreversible surface reactions, loss of active material mass, corrosion, embrittlement, crushing, and electrode surface passivation. In some embodiments, the inorganic particles may also provide a support for the byproducts of one or more electrochemical reactions present in an energy storage device (e.g., an electrochemical cell), thereby extending the useful device life (e.g., cell life).

[0142] The separators disclosed herein can be used with an electrode (e.g., a cathode or an anode) comprising an electroactive material that is an oxide, suboxide, sulfide, oxysulfide, phosphate, phosphide, and carbide or a base form and combinations thereof of silicon, vanadium, niobium, molybdenum, rhenium, tantalum, tungsten, bismuth, titanium, tin, antimony, manganese, nickel, aluminum, lithium, sodium, potassium, calcium, zinc, cobalt, chromium, indium, lanthanum, cerium, strontium, iron. The electroactive material can be modified (e.g., doped) with one or more elements including hydrogen, lithium, boron, carbon, nitrogen, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, antimony, lanthanum, cerium, neodymium, tantalum, tungsten, rhenium, platinum, gold, lead, bismuth, and combinations thereof. Electrodes comprising electroactive materials may be self-supporting or may be present on a substrate (e.g., a current collector). (An electrode may be said to be disposed on a current collector or the electrode may be considered to include a current collector.) The substrate may include, but is not limited to, a carbon material such as a foam, paper, aerogel, foil, fiber, or nanostructure (e.g., nanoparticles, nanorods, nanopillars), or a metal foil, foam, sheet, mesh, or stock.

[0143] The electroactive materials used in the electrodes in combination with the separators disclosed herein may be further modified with one or more elements (e.g., doped with the one or more elements). Without wishing to be bound by any particular theory, further modification (e.g., doping) may change the conductivity, chemical reactivity, and / or electrochemical reactivity of the electroactive materials. In some embodiments, upon doping, the elemental dopant replaces less than 50 wt.% of the metal of the electroactive material, preferably less than 20 wt.% of the metal of the electroactive material. In some embodiments, the one or more elements account for less than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%) of the electroactive material. The one or more elements (e.g., dopants) may be selected from: carbon, boron, nitrogen, iodine, phosphorus, antimony, indium, arsenic, gallium, tungsten, cadmium, and tellurium.

[0144] The energy storage device may include an anode. The anode may be modified by a grinding process. The grinding process may be used to reduce or expand the particle size distribution (e.g., the particle size distribution of the additive particles in an electrode (such as an anode)). Additionally or alternatively, the grinding process may be used to alloy one or more conductive additives or chemically implant the one or more conductive additives. Examples of such additives include carbon, metal grit, and metal flakes. Carbon may be in the form of carbon black, acetylene black, carbon fiber, carbon nanotubes, graphene, graphite, fullerene, or carbon aerogel. Available grinding processes include, but are not limited to, horizontal ball milling, vertical stirring mixer mill, planetary ball milling, and jet milling.

[0145] In some embodiments, the electrode of the energy storage device includes one or more binders. Each of the one or more binders can be, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyacrylic acid (PAA), polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR) or its copolymer. In some embodiments, the electrode of the energy storage device includes one or more conductive additives. Each of the one or more conductive additives can be selected from the following: carbon black, acetylene black, carbon fiber, carbon nanotubes, graphene, graphite, fullerene, carbon aerogel, metal flakes, metal fibers, metal particles and conductive polymers. The conductive polymer used for the electrode in the energy storage device can be, for example, polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide) or PEDOT.

[0146] In some embodiments, the diaphragm can be used with an electrode including a conductive substrate. The substrate can include one or more carbon materials, such as foam, paper, aerogel, foil, fiber, particle, conductive polymer, nanostructure, or metal foil, foam, sheet, net or raw material or a combination thereof. The substrate can include a conductive film applied to a physical carrier. The physical carrier can include one or more carbon materials, such as foam, paper, aerogel, foil, fiber, or nanostructure, or metal foil, foam, sheet, net or raw material. The physical carrier can alternatively or additionally include one or more polymer materials, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR), polyaniline (PANI), polypyrrole (PPyr), polystyrene (PS), polythiophene (PT) or its copolymer.

[0147] The polymer used in an electrode (eg, anode or cathode) can be incorporated into the electrode during electrode synthesis or assembly, it can be chemically or electrochemically deposited onto the electrode during cycling, or it can be incorporated by some combination.

[0148] Electrode substrate (for example, collector) can include active material or inert material.These potential materials include metal, oxide, suboxide, hydroxide, oxyhydroxide, oxychloride, sulfide, oxysulfide, oxynitrate, carbonate, nitride, phosphate, phosphite, carbide and polymer, containing one or more of the following: hydrogen, lithium, boron, carbon, nitrogen, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, lanthanum, cerium, neodymium, tantalum, tungsten, rhenium, platinum, gold, lead and bismuth.In addition, material can also include inorganic particles described herein.The physical form of these materials can include but is not limited to thin slice, granule, powder, particle, tube, cube or fiber.

[0149] In certain embodiments, an energy storage device includes a membrane disclosed herein immersed or otherwise surrounded by an electrolyte (eg, an electrolytic solution).

[0150] In certain embodiments, the electrolyte is a solid electrolyte. In certain embodiments, the electrolyte is a solid polymer electrolyte. In certain embodiments, the solid polymer electrolyte comprises one or more polymers selected from the group consisting of: (i) polymers comprising repeating units of one or more of: ethylene oxide, propylene oxide, madder pigment, alginate, quinone, hydroxyquinone, hydroxyquinoline, silicon, silicate, and sulfone, (ii) cellulosic, natural or modified natural polymers, and (iii) synthetic fluorinated polymers (e.g., polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE)).

[0151] In certain embodiments, the electrolyte comprises one or more materials each having the following stoichiometry: M1 1+ x N1 p , or M1 2+ x N1 p , or M1 3+ x N1 p , or M1 4+ x N1 p , or M1 1+ x N1 p N2 q , or M1 2+ x N1 p N2 q , or M1 3+ x N1 p N2 q , or M1 4+ x N1 p N2 q , or M1 1+ x M2 2+ y N1 p , or M1 1+ x M2 3+ y N1 p , or M1 1+ x M2 4+ y N1 p , or M1 2+ x M2 3+ y N1 p , or M1 2+ xM2 4+ y N1 p , or M1 3+ x M2 4+ y N1 p , or M1 1+ x M2 2+ y N1 p N2 q , or M1 1+ x M2 3+ y N1 p N2 q , or M1 1+ x M2 4+ y N1 p N2 q , or M1 2+ x M2 3+ y N1 p N2 q , or M1 2+ x M24+ y N1 p N2 q , or M1 3+ x M2 4+ y N1 p N2 q , or M1 1+ x M2 2+ y M3 3+ z N1p, or M1 1+ x M2 2+ y M3 4+ z N1 p , or M1 2+ x M2 3+ y M3 4+ z N1 p , or M1 1+ x M2 2+ y M3 3+z N1 p N2 q , or M1 1+ x M2 2+ y M3 4+ z N1 p N2 q , or M1 2+ x M2 3+ y M3 4+ z N1 p N2 q , or M1 1 +x M2 2+ y M3 3+ z M4 4+ s N1 p , or M1 1 + xM2 2+ y M3 3+ z M4 4+ s N1 p N2 q , wherein each M (e.g., M1, M2, M3, M4) is a monovalent or polyvalent atom, and each N (e.g., N1, N2) is a functional group (e.g., selected from the group consisting of hydroxide, alkoxide, peroxide, superoxide, nitrate, nitrite, sulfate, sulfite, sulfide, carbonate, phosphate, phosphate, phosphide, and halide). In certain embodiments, one or more materials included in the electrolyte form an ionically conductive matrix.

[0152] In certain embodiments, the electrolyte comprises (e.g., further comprises) one or more of the following: a salt, an acid, and a base. In certain embodiments, the electrolyte: (i) comprises the salt, wherein the salt is selected from the group consisting of: an oxide salt, a hydroxide salt, an alkoxide salt, a peroxide salt, a superoxide salt, a nitrate salt, a nitrite salt, a sulfate salt, a sulfite salt, a sulfide salt, a carbonate salt, a carbide salt, a phosphate salt, a phosphorus salt, a nitrite salt, a nitrite salt, a sulfide salt, a sulfide salt, a nitrate salt, a nitrite salt, a nitrite salt, a nitrite salt, a nitrite salt, a nitride salt, a nitrate salt, a nitrite salt, a nitride salt, a nitrate salt, a nitrate salt, a nitrate salt, a nitrate salt, a nitride ... (ii) comprising the acid, wherein the acid is selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, sulfurous acid, trifluoromethanesulfonic acid, hydrofluoric acid, peracetic acid, boric acid, uric acid, citric acid, hydroiodic acid, carbonic acid, oxalic acid, bromic acid, chromic acid, formic acid, ascorbic acid and acetic acid; (iii) comprising the base, wherein the base is selected from the group consisting of hydroxides of sodium, potassium, calcium, magnesium, manganese, lithium, zinc, zirconium, cerium, tin, titanium, aluminum, ammonium, iron, indium, molybdenum, nickel, platinum, palladium, ruthenium, silver, vanadium and copper; or (iv) any combination of (i), (ii) and (iii).

[0153] In certain embodiments, the electrolyte comprises one or more ceramics selected from the group consisting of aluminum oxide, antimony ammonium tungstate oxide, barium titanate, strontium titanate, bismuth strontium calcium copper oxide, boron oxide, boron nitride, ferrite, lead zirconate titanate, magnesium diboride, porcelain, sialon, silicon, silicate, carbide, nitride, titanium carbide, uranium oxide, yttrium barium copper oxide, zinc oxide, cesium oxide, cerium oxide, zirconium oxide, vanadium oxide, tin oxide, iron oxide, tungsten oxychloride, beryllium oxide, bismuth oxide, lithium oxide, lead oxide, manganese oxide, magnesium oxide, nickel oxide, titanium oxide, cadmium oxide, copper oxide, indium oxide, and silicon oxide. In certain embodiments, the electrolyte further comprises water molecules (e.g., hydrated water) disposed in a crystal structure.

[0154] In certain embodiments, the electrolyte is a self-supporting film, or has been applied to the separator, anode, cathode, or a combination thereof.

[0155] An energy storage device including a separator disclosed herein, an additive disclosed herein, or both can be an electrochemical cell such as a battery having any one or more of a variety of form factors. For example, the electrochemical cell can be a pouch cell, a coin cell, a cylindrical cell, or a prismatic cell.

[0156] Certain embodiments of the present disclosure are described above. However, it is expressly pointed out that the present disclosure is not limited to these embodiments, but it is intended that additions and modifications to the contents explicitly described in the present disclosure are also included in the scope of the present disclosure. In addition, it should be understood that the features of the various embodiments described in the present disclosure are not necessarily mutually exclusive, and may exist in various combinations and arrangements without departing from the spirit and scope of the present disclosure, even if such combinations or arrangements are not expressly stated herein. The present disclosure has been described in detail with specific reference to certain embodiments, but it should be understood that changes and modifications may be implemented within the spirit and scope of the claimed invention.

Claims

1. A separator for an energy storage device, the separator comprising inorganic particles. 2 . The separator according to claim 1 , comprising one or more binders, wherein the one or more binders bind the inorganic particles (eg, of one type or different types) together. 3 . The separator according to claim 1 , wherein the inorganic particles are functional inorganic particles.

4. The membrane according to any one of the preceding claims, wherein the membrane is a solid layer or a semi-solid (eg gel or jelly-like) layer (eg a surface layer).

5. The membrane of any one of the preceding claims, wherein the inorganic particles comprise at least 50 wt.% of the membrane (e.g., at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, or at least 95 wt.% of the membrane).

6. A membrane according to any of the preceding claims, wherein the inorganic particles comprise one or more elements selected from the group consisting of: oxygen, hydrogen, sulfur, aluminum, silicon and phosphorus [e.g., wherein the one or more elements account for at least 10 wt.% of the inorganic particles (e.g., at least 20 wt.%, at least 30 wt.% or at least 50 wt.%)] [e.g., wherein the one or more elements account for no more than 80 wt.% of the inorganic particles (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 20 wt.%)].

7. A membrane according to any of the preceding claims, wherein the inorganic particles contain one or more metal atoms [for example, wherein the one or more metal atoms account for at least 10 wt.% of the inorganic particles (for example, at least 20 wt.%, at least 30 wt.% or at least 50 wt.%)] [for example, wherein the one or more metal atoms account for no more than 80 wt.% of the inorganic particles (for example, no more than 50 wt.%, no more than 30 wt.%)].

8. The membrane of claim 7, wherein the one or more metal atoms are selected from the group consisting of aluminum, silicon, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

9. The membrane of any one of the preceding claims, wherein the inorganic particles are porous. 10 . The separator according to claim 9 , wherein the inorganic particles have microporosity, mesoporosity, macroporosity, or a combination thereof.

11. A membrane according to claim 9 or claim 10, wherein the inorganic particles contain one or more pores having a size (e.g., diameter) less than 2 nm (e.g., wherein each of the inorganic particles contains one or more pores having a size less than 2 nm).

12. A membrane according to any one of claims 9 to 11, wherein the inorganic particles contain one or more pores having a size (e.g., diameter) of at least 2 nm and not more than 50 nm (e.g., wherein each of the inorganic particles contains one or more pores having a size of at least 2 nm and not more than 50 nm).

13. The membrane of any one of claims 9 to 12, wherein the inorganic particles comprise one or more pores having a size (e.g., diameter) greater than 50 nm (e.g., wherein each of the inorganic particles comprises one or more pores having a size greater than 50 nm).

14. The separator according to any one of claims 9 to 13, wherein each of the inorganic particles comprises one or more particles having a size (e.g., diameter) between to (For example, to to to )[For example, (For example, )to (For example, )] within the range of the hole. 15 . The membrane of claim 9 , wherein each of the inorganic particles comprises one or more pores connected to form at least one channel passing through the inorganic particles. 16 . The separator according to claim 9 , wherein the at least one channel of each of the inorganic particles is connected to form a channel system.

17. The membrane according to claim 16, wherein the channel system is a 1-dimensional channel system, a 2-dimensional channel system or a 3-dimensional channel system.

18. A membrane according to claim 16 or claim 17, wherein the channel system extends through the membrane [e.g., from a first surface of the membrane to a second surface of the membrane opposite the first surface (e.g., from the anode side to the cathode side)].

19. The separator according to any one of claims 9 to 18, wherein the inorganic particles comprise one or more cage structures.

20. The membrane of claim 19, wherein at least one of the one or more cage structures is disposed at an intersection of pores of the inorganic particles.

21. The membrane of claim 19 or claim 20, wherein the size (e.g., diameter) of each of the one or more cage structures is between to (For example, to to to to to or to ) within the range of .

22. The membrane of any one of claims 19 to 21, wherein at least one of the one or more cage structures is disposed in a 1-dimensional pore.

23. The membrane of any one of claims 19 to 22, wherein one or more species are disposed in (eg, adsorbed in) the one or more cage structures.

24. A membrane according to any one of claims 9 to 23, wherein one or more species are disposed in (e.g., adsorbed on) one or more pores of the inorganic particles [e.g., on a surface (e.g., an interior surface, near an opening, or both) of the one or more pores] (e.g., wherein the one or more species are not covalently bonded to the one or more pores).

25. The membrane of claim 23 or claim 24, wherein the one or more species comprises a member selected from the group consisting of olefins, paraffins, cycloalkanes, and aromatic hydrocarbons.

26. The membrane of any one of claims 23 to 25, wherein the one or more species comprises water.

27. The membrane of any one of claims 23 to 26, wherein the one or more species comprises one or more gas species.

28. The membrane of claim 27, wherein the one or more gas species are selected from the group consisting of hydrogen, oxygen, carbon oxides, nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides, and sulfur oxides.

29. The membrane of any one of claims 23 to 28, wherein the one or more species comprises one or more cationic species.

30. The membrane of claim 29, wherein the one or more cationic species are each a cationic form of an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

31. The membrane of any one of claims 23 to 30, wherein the one or more species comprises one or more anionic species.

32. The membrane of claim 31 , wherein the one or more anionic species is selected from the group consisting of hydroxides, alkoxides, peroxides, superoxides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphides, fluorides, chlorides, bromides, iodides, chlorates, bromates, iodates, polyoxometalates, and combinations thereof.

33. The membrane of any one of the preceding claims, wherein the surface area of ​​the inorganic particles is at least 10 m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g).

34. The membrane according to any one of the preceding claims, wherein the inorganic particles comprise one or more particles having M y Al x Si 1-x Particles composed of O2·zH2O, wherein M is a metal.

35. The membrane of claim 34, wherein x is in the range of 0 to 0.5 (eg, 0 to 0.1 or 0.01 to 0.5), and y is in the range of 0 to 0.5 (eg, 0 to 0.1).

36. The membrane of claim 34, wherein x is in the range of 0.5 to 1, and y is in the range of 0 to 1.

37. The membrane of any one of claims 34 to 36, wherein z is in the range of 0 to 10,000.

38. The membrane of any one of the preceding claims, wherein polar sites are disposed on a surface [eg, an inner surface (eg, having pores)] of the inorganic particles.

39. The membrane of any one of the preceding claims, wherein the inorganic particles are crystalline or amorphous.

40. The membrane according to any one of the preceding claims, wherein the average particle size (d 50 diameter) in the range of 100 nm to 30 μm.

41. A diaphragm according to any of the preceding claims, wherein the inorganic particles comprise one or more particles having a spherical shape, one or more particles having a rod shape, one or more particles having a needle shape, one or more particles having a flake shape, one or more particles having a platelet shape, one or more particles having a cubic shape, one or more particles having a disk shape, one or more particles having a tubular shape, or a combination thereof.

42. The membrane of any one of the preceding claims, wherein the inorganic particles have been prepared by subjecting chemical precursors to a crystallization reaction at 30-250°C for no more than 30 days.

43. The membrane of claim 42, wherein the reaction is carried out under stirring.

44. A membrane according to claim 42 or claim 43, wherein the crystallization reaction is carried out without stirring.

45. The membrane of any one of claims 42 to 44, wherein the chemical precursor comprises a silicon dioxide source and an aluminum oxide source.

46. ​​The membrane of any one of claims 42 to 45, wherein the chemical precursor comprises a mineralizer, an acidic or alkaline medium, a templating agent, a structure directing agent (SDA), or a combination thereof.

47. The membrane of any of the preceding claims, wherein the one or more binders comprise no more than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%) of the membrane.

48. The membrane of any of the preceding claims, wherein the one or more binders are selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), and styrene butadiene rubber (SBR).

49. The membrane of any one of the preceding claims, wherein at least one of the one or more binders comprises one or more binder additives.

50. The membrane of claim 49, wherein the one or more adhesive additives comprise one or more members selected from the group consisting of pH adjusters, pH buffers, rheology modifiers, defoamers, anti-foaming agents, adhesion promoters, and leveling agents.

51. The membrane of any preceding claim further comprising a conductive polymer.

52. The membrane of claim 51, wherein the conductive polymer comprises no more than 80 wt. % (eg, no more than 50 wt. %) of the membrane.

53. The membrane of claim 51 or claim 52, wherein the conductive polymer is selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide), and PEDOT.

54. A membrane according to any of the preceding claims, wherein the membrane has been coated on an electrode (e.g., an anode, a cathode, or both) in situ or ex situ (e.g., by wet chemical reaction, physical vapor deposition, chemical vapor deposition, atomic layer deposition, sintering, pressing, hot pressing, extrusion, die casting, slot die coating, doctor blade coating, dip coating, or a combination thereof) (e.g., by liquid coating).

55. The membrane of claim 54, wherein the membrane has been further calendered (e.g., to increase bond strength, layer uniformity, or both), annealed, or both.

56. The membrane according to any one of the preceding claims, wherein the membrane has a thickness in the range of 5 μm to 500 μm.

57. The membrane of any one of the preceding claims, wherein the membrane is a self-supporting film.

58. An energy storage device comprising a membrane according to any one of the preceding claims and two electrodes, wherein the membrane is disposed between the two electrodes such that the membrane prevents the two electrodes from being in direct physical contact.

59. The energy storage device of claim 58, further comprising a second diaphragm of any one of claims 1 to 57, wherein the second diaphragm is disposed between the two electrodes such that the second diaphragm prevents the two electrodes from making direct physical contact.

60. The energy storage device of claim 58 or claim 59, further comprising an electrolyte [e.g., a solid or liquid (e.g., aqueous) electrolyte] (e.g., an ion-conductive matrix) disposed between the two electrodes.

61. An energy storage device according to claim 60, wherein the electrolyte is a solid polymer electrolyte selected from the group consisting of: (i) polymers comprising repeating units of one or more of the following: ethylene oxide, propylene oxide, madder pigment, alginate, quinone, hydroxyquinone, hydroxyquinoline, silicon, silicate and sulfone, (ii) cellulosic, natural or modified natural polymers, and (iii) synthetic fluorinated polymers (e.g., polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE)).

62. An energy storage device according to claim 60 or claim 61, wherein the electrolyte comprises one or more materials each having the following stoichiometry: M1 1+ x N1 p , or M1 2+ x N1 p , or M1 3+ x N1 p , or M1 4+ x N1 p , or M1 1+ x N1 p N2 q , or M1 2+ x N1 p N2 q , or M1 3+ x N1 p N2 q , or M1 4+ x N1 p N2 q , or M1 1+ x M2 2+ y N1 p , or M1 1+ x M2 3+ y N1 p , or M1 1+ x M2 4+ y N1 p , or M1 2+ x M2 3+ y N1 p , or M1 2+ x M2 4+ y N1 p , or M1 3+ x M2 4+ y N1 p , or M1 1+ x M2 2+ y N1 p N2 q , or M1 1+ x M2 3+ y N1 p N2 q , or M1 1+ x M2 4+ y N1 p N2 q , or M1 2+ x M2 3+ y N1 p N2 q , or M1 2+ x M24+ y N1 p N2 q , or M1 3+ x M2 4+ y N1 p N2 q , or M1 1+ x M2 2+ y M3 3+ z N1p, or M1 1+ x M2 2+ y M3 4+ z N1 p , or M1 2+ x M2 3+ y M3 4+ z N1 p , or M1 1+ x M2 2+ y M3 3+ z N1 p N2 q , or M1 1 + x M2 2+ y M3 4+ z N1 p N2 q , or M1 2+ x M2 3+ y M3 4+ z N1 p N2 q , or M1 1 +x M2 2+ y M3 3+ z M4 4+ s N1 p , or M1 1 + xM2 2+ y M3 3+ z M4 4+ s N1 p N2 q , wherein each M (e.g., M1, M2, M3, M4) is a monovalent or polyvalent atom, and each N (e.g., N1, N2) is a functional group (e.g., selected from the group consisting of hydroxide, alkoxide, peroxide, superoxide, nitrate, nitrite, sulfate, sulfite, sulfide, carbonate, phosphate, phosphate, phosphide, and halide).

63. The energy storage device of any one of claims 60-62, wherein the electrolyte comprises one or more of: a salt, an acid, and a base.

64. The energy storage device of claim 63, wherein the electrolyte: (i) comprises the salt, wherein the salt is selected from the group consisting of an oxide salt, hydroxide salt, alkoxide salt, peroxide salt, superoxide salt, nitrate, nitrite, sulfate, sulfite of one or more of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, and copper. (ii) comprising said acid, wherein said acid is selected from the group consisting of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, sulfurous acid, trifluoromethanesulfonic acid, hydrofluoric acid, peracetic acid, boric acid, uric acid, citric acid, hydroiodic acid, carbonic acid, oxalic acid, bromic acid, chromic acid, formic acid, ascorbic acid and acetic acid; (iii) comprising said base, wherein said base is selected from the group consisting of hydroxides of sodium, potassium, calcium, magnesium, manganese, lithium, zinc, zirconium, cerium, tin, titanium, aluminum, ammonium, iron, indium, molybdenum, nickel, platinum, palladium, ruthenium, silver, vanadium and copper; or (iv) any combination of (i), (ii) and (iii).

65. An energy storage device according to any one of claims 60 to 64, wherein the electrolyte comprises one or more ceramics selected from the group consisting of aluminum oxide, antimony ammonium tungsten oxide, barium titanate, strontium titanate, bismuth strontium calcium copper oxide, boron oxide, boron nitride, ferrite, lead zirconate titanate, magnesium diboride, porcelain, sialon, silicon, silicates, carbides, nitrides, titanium carbide, uranium oxide, yttrium barium copper oxide, zinc oxide, cesium oxide, cerium oxide, zirconium oxide, vanadium oxide, tin oxide, iron oxide, tungsten oxychloride, beryllium oxide, bismuth oxide, lithium oxide, lead oxide, manganese oxide, magnesium oxide, nickel oxide, titanium oxide, cadmium oxide, copper oxide, indium oxide, and silicon oxide.

66. An energy storage device according to any one of claims 60 to 65, wherein the electrolyte is a self-supporting film or has been applied to the separator and / or at least one of the two electrodes.

67. An energy storage device according to any one of claims 58 to 66, wherein at least one of the two electrodes comprises an electroactive material comprising oxides, suboxides, sulfides, oxysulfides, phosphates, phosphides, carbides, or elementary forms of elements and combinations thereof, the elements being selected from the group consisting of silicon, magnesium, vanadium, niobium, molybdenum, rhenium, tantalum, tungsten, bismuth, titanium, tin, antimony, manganese, nickel, aluminum, lithium, sodium, potassium, calcium, zinc, cobalt, chromium, indium, lanthanum, cerium, strontium, and iron.

68. The energy storage device of claim 67, wherein the electroactive material has been modified with (eg, doped with) one or more elements.

69. The energy storage device of claim 68, wherein the one or more elements comprise one or more members selected from the group consisting of hydrogen, lithium, boron, carbon, nitrogen, iodine, phosphorus, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, antimony, arsenic, lanthanum, cerium, neodymium, tantalum, tungsten, tellurium, rhenium, platinum, gold, lead, and bismuth.

70. An energy storage device according to claim 68 or claim 69, wherein the one or more elements constitute less than 50 wt.% of the electroactive material (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%).

71. The energy storage device of any one of claims 58-70, further comprising a substrate (e.g., a current collector), wherein one of the two electrodes is disposed on the substrate.

72. The energy storage device of claim 71, wherein the substrate is a carbon structure or a metal structure.

73. An energy storage device according to claim 71 or claim 72, wherein the substrate is a foam, paper, aerogel, foil, fiber, nanostructure (e.g., nanoparticles), sheet, mesh or raw material.

74. The energy storage device of any one of claims 71-73, wherein the substrate comprises a polymer material.

75. An energy storage device according to claim 74, wherein the polymer material is selected from the group consisting of: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR), polyaniline (PANI), polypyrrole (PPyr), polystyrene (PS) and polythiophene (PT).

76. An energy storage device according to any one of claims 58 to 75, wherein at least one of the two electrodes comprises a binder selected from the group consisting of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyvinyl acetate, polyacrylic acid (PAA), polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), styrene butadiene rubber (SBR), and copolymers thereof.

77. An energy storage device according to any one of claims 58 to 76, wherein at least one of the two electrodes comprises a conductive additive selected from the group consisting of carbon black, acetylene black, carbon fibers, carbon nanotubes, graphene, graphite, fullerenes, carbon aerogels, metal flakes, metal fibers or metal particles, and conductive polymers.

78. An energy storage device according to claim 77, wherein the conductive additive is a conductive polymer, and the conductive polymer is selected from the group consisting of: polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide) and PEDOT.

79. An energy storage device according to any one of claims 58 to 78, wherein at least one of the two electrodes comprises an additive material selected from the group consisting of metals, oxides, suboxides, hydroxides, oxyhydroxides, oxychlorides, sulfides, oxysulfides, oxynitrates, carbonates, nitrides, phosphates, phosphites, carbides, and polymers, containing one or more members selected from the group consisting of hydrogen, lithium, boron, carbon, nitrogen, oxygen, sulfur, sodium, magnesium, aluminum, silicon, potassium, calcium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, zirconium, niobium, molybdenum, ruthenium, silver, cadmium, indium, tin, lanthanum, cerium, neodymium, tantalum, tungsten, rhenium, platinum, gold, lead, and bismuth.

80. The membrane or energy storage device of any preceding claim, wherein the energy storage device is a primary battery, a secondary battery, a secondary battery, a fuel cell unit, or a capacitor.

81. The membrane or energy storage device of any preceding claim, wherein the energy storage device is an aqueous battery.

82. The membrane or energy storage device of claim 81, wherein the aqueous battery is an aqueous secondary battery.

83. A method of making inorganic particles for use as a separator or as an additive in an energy storage device, the method comprising subjecting a chemical precursor to a crystallization reaction at 30-250°C for no more than 30 days.

84. The method of claim 83, comprising stirring the chemical precursor during the crystallization reaction.

85. The method of claim 83, wherein the crystallization reaction is carried out without stirring.

86. The method of any one of claims 83 to 85, wherein the chemical precursor comprises a silica source and an alumina source.

87. The method of claim 86, wherein the chemical precursor further comprises a mineralizer, an acidic or alkaline medium, a templating agent, a structure directing agent (SDA), or a combination thereof.

88. A method of operating an energy storage device, the method comprising: Providing an energy storage device according to any one of claims 58 to 79; and Gases are trapped in the pores of the inorganic particles during charging and / or discharging of the energy storage device.

89. A method of operating and / or preparing an energy storage device, the method comprising: Providing the energy storage device, wherein the energy storage device comprises inorganic particles comprising one or more members selected from the group consisting of silicates, phosphates, sulfates, oxides, hydrides, and combinations thereof (e.g., one or more silicates and / or one or more phosphates) [e.g., in stable (e.g., salt) and / or ionic (e.g., anionic) form]; reacting the one or more members with one or more species (e.g., one or more portions thereof) in the energy storage device to form one or more reaction products; and The one or more reaction products are used to passivate the surface of a material in the energy storage device (eg, thereby inhibiting one or more undesirable side reactions).

90. The method of claim 89, wherein the reaction occurs during an electrochemical cycle (e.g., during charging and / or discharging) of the energy storage device (e.g., wherein the energy storage device is a primary battery or a secondary battery).

91. The method of claim 89, wherein the reaction occurs prior to completing assembly of the energy storage device (e.g., during a preconditioning process of the energy storage device).

92. The method of any one of claims 89-91, wherein the one or more reaction products comprise a polymer species (e.g., a polysilicate and / or a polyphosphate).

93. The method of any one of claims 89-92, comprising reacting the one or more reaction products with the surface of the material.

94. The method of any one of claims 89-93, wherein reacting the one or more members comprises dissolving at least a portion of the inorganic particles (e.g., dissolving in an electrolyte of the energy storage device).

95. The method of any one of claims 89-94, wherein passivating the surface of the material comprises precipitating a polymer species (e.g., polysilicate and / or polyphosphate) onto the surface.

96. The method of any one of claims 89-95, wherein at least a portion of the inorganic particles are contained in a membrane of the energy storage device.

97. The method of any one of claims 89 to 96, wherein at least a portion of the inorganic particles are contained in an additive, and the additive is contained in an electrode of the energy storage device (e.g., wherein the electrode is an anode or a cathode, or wherein the additive is contained in both the anode and the cathode).

98. The method of any one of claims 89 to 97, wherein the material is metallic.

99. The method of any one of claims 89 to 97, wherein the material is an electroactive material.

100. An energy storage device comprising inorganic particles comprising one or more members selected from the group consisting of silicates, phosphates, sulfates, oxides, hydrides, and combinations thereof (e.g., one or more silicates and / or one or more phosphates) [e.g., in stable (e.g., salt) and / or ionic (e.g., anionic) form], and a material comprising a passivated surface, wherein the passivated surface is passivated with one or more species derived from one or more members (e.g., the one or more silicates and / or the one or more phosphates) (e.g., being reaction products of the one or more members) [e.g., wherein the one or more species comprise one or more polymer species (e.g., one or more polysilicates and / or one or more polyphosphates)] (e.g., wherein the inorganic particles are contained in a separator and / or an electrode).

101. An additive (eg, an electrode additive) for an energy storage device, the additive comprising inorganic particles (eg, of one type or of different types).

102. The additive of claim 101, wherein the inorganic particles are functional inorganic particles.

103. An additive according to any one of claims 101 to 102, wherein the inorganic particles comprise one or more elements selected from the group consisting of: oxygen, sulfur, hydrogen, aluminum, silicon and phosphorus [for example, wherein the one or more elements account for at least 10 wt.% of the inorganic particles (for example, at least 20 wt.%, at least 30 wt.% or at least 50 wt.%)] [for example, wherein the one or more elements account for no more than 80 wt.% of the inorganic particles (for example, no more than 50 wt.%, no more than 30 wt.%, no more than 20 wt.%)].

104. An additive according to any one of claims 101 to 103, wherein the inorganic particles comprise one or more metal atoms [e.g., wherein the one or more elements account for at least 10 wt.% of the inorganic particles (e.g., at least 20 wt.%, at least 30 wt.%, or at least 50 wt.%)] [e.g., wherein the one or more elements account for no more than 80 wt.% of the inorganic particles (e.g., no more than 50 wt.%, no more than 30 wt.%, no more than 50 wt.%)].

105. The additive of claim 104, wherein the one or more metal atoms are selected from the group consisting of aluminum, silicon, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

106. The additive of any one of claims 101 to 105, wherein the inorganic particles are porous.

107. The additive of claim 106, wherein the inorganic particles have microporosity, mesoporosity, macroporosity, or a combination thereof.

108. An additive according to claim 106 or claim 107, wherein the inorganic particles contain one or more pores having a size (e.g., diameter) less than 2 nm (e.g., wherein each of the inorganic particles contains one or more pores having a size less than 2 nm).

109. An additive according to any one of claims 106 to 108, wherein the inorganic particles comprise one or more pores having a size (e.g., diameter) of at least 2 nm and no greater than 50 nm (e.g., wherein each of the inorganic particles comprises one or more pores having a size of at least 2 nm and no greater than 50 nm).

110. The additive of any one of claims 106 to 109, wherein the inorganic particles comprise one or more pores having a size (e.g., diameter) greater than 50 nm (e.g., wherein each of the inorganic particles comprises one or more pores having a size greater than 50 nm).

111. The additive of any one of claims 106 to 110, wherein each of the inorganic particles comprises one or more particles having a size (e.g., diameter) between to (For example, to to to )[For example, (For example, )to (For example, )] within the range of the hole.

112. The additive of any one of claims 106 to 111, wherein each of the inorganic particles comprises one or more pores connected to form at least one channel through the inorganic particle.

113. The additive of any one of claims 106 to 112, wherein the at least one channel of each of the inorganic particles is connected to form a channel system.

114. The additive of claim 113, wherein the channel system is a 1-dimensional channel system, a 2-dimensional channel system or a 3-dimensional channel system.

115. An additive according to claim 113 or claim 114, wherein the channel system extends through the membrane [e.g., from a first surface of the membrane to a second surface of the membrane opposite to the first surface (e.g., from the anode side to the cathode side)].

116. The additive of any one of claims 106 to 115, comprising one or more cage structures.

117. The additive of claim 116, wherein at least one of the one or more cage structures is disposed at an intersection of a pore of the inorganic particle.

118. The additive of claim 116 or claim 117, wherein the size (e.g., diameter) of each of the one or more cage structures is between to (For example, to to to to to or to ) within the range of .

119. The additive of any one of claims 116 to 118, wherein at least one of the one or more cage structures is disposed in a 1-dimensional pore.

120. The additive of any one of claims 116 to 119, wherein one or more species are disposed in (eg, adsorbed in) the one or more cage structures.

121. An additive according to any one of claims 106 to 120, wherein one or more species are disposed in (e.g., adsorbed on) one or more pores of the inorganic particle [e.g., on a surface (e.g., an interior surface, near an opening, or both) of the one or more pores].

122. The additive of claim 120 or claim 121, wherein the one or more species comprises a member selected from the group consisting of olefins, paraffins, cycloalkanes, and aromatic hydrocarbons.

123. The additive of any one of claims 120-122, wherein the one or more species comprises water.

124. The additive of any one of claims 120-123, wherein the one or more species comprises one or more gaseous species.

125. The additive of claim 124, wherein the one or more gas species is selected from the group consisting of: hydrogen, oxygen, carbon oxides, nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides, and sulfur oxides.

126. The additive of any one of claims 120-125, wherein the one or more species comprises one or more cationic species.

127. The additive of claim 126, wherein each of the one or more cationic species is a cationic form of an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

128. The additive of any one of claims 120-127, wherein the one or more species comprises one or more anionic species.

129. The additive of claim 128, wherein the one or more anionic species is selected from the group consisting of hydroxides, alkoxides, peroxides, superoxides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphides, fluorides, chlorides, bromides, iodides, chlorates, bromates, iodates, polyoxometalates, and combinations thereof.

130. The additive of any one of claims 101 to 129, wherein the surface area of ​​the inorganic particles is at least 10 m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g).

131. An additive according to any one of the preceding claims, wherein the inorganic particles comprise one or more particles having M y Al x Si 1-x Particles composed of O2·zH2O, wherein M is a metal.

132. The additive of claim 131, wherein x is in the range of 0 to 0.5 (e.g., 0 to 0.1 or 0.01 to 0.5), and y is in the range of 0 to 0.5 (e.g., 0 to 0.1).

133. The additive of claim 131, wherein x is in the range of 0.5 to 1 and y is in the range of 0 to 1.

134. The additive of any one of claims 131 to 133, wherein z is in the range of 0 to 10,000.

135. The additive of any one of claims 131 to 134, wherein the polar sites are disposed on a surface [eg, an interior surface (eg, having pores)] of the inorganic particle.

136. The additive of any one of claims 101 to 135, wherein the inorganic particles are crystalline or amorphous.

137. The additive of any one of claims 101 to 136, wherein the average particle size (d 50 diameter) in the range of 100 nm to 30 μm.

138. The additive of any one of claims 101 to 137, wherein the inorganic particles comprise one or more particles having a spherical shape, one or more particles having a rod shape, one or more particles having a needle shape, one or more particles having a flake shape, one or more particles having a platelet shape, one or more particles having a cubic shape, one or more particles having a disk shape, one or more particles having a tube shape, or a combination thereof.

139. The additive of any one of claims 101 to 138, wherein the inorganic particles have been prepared by subjecting chemical precursors to a crystallization reaction at 30-250°C for no more than 30 days.

140. The additive of claim 139, wherein the reaction is carried out under stirring.

141. An additive according to claim 139 or claim 140, wherein the crystallization reaction is carried out without stirring.

142. The additive of any one of claims 139 to 141, wherein the chemical precursor comprises a silica source and an alumina source.

143. The additive of any one of claims 139 to 142, wherein the chemical precursor comprises a mineralizer, an acidic or alkaline medium, a templating agent, a structure directing agent (SDA), or a combination thereof.

144. An electrode comprising an electroactive material and an additive according to any one of claims 101 to 143 (eg comprising a plurality of electroactive materials and / or a plurality of additives).

145. The electrode of claim 144, further comprising a current collector, wherein the electroactive material and the additive are coated on the current collector.

146. The electrode of claim 144 or claim 145, further comprising one or more binders.

147. An electrode according to claim 146, wherein the one or more binders constitute no more than 50 wt.% of the separator (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%).

148. An electrode according to claim 146 or claim 147, wherein the one or more binders are selected from the group consisting of: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and styrene butadiene rubber (SBR).

149. The electrode of any one of claims 144-148, further comprising a conductive additive.

150. An electrode according to claim 149, wherein the conductive additive constitutes no more than 80 wt.% of the electrode (e.g., no more than 70 wt.%, no more than 60 wt.%, no more than 50 wt.%, no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, or no more than 10 wt.%).

151. An electrode according to claim 149 or claim 150, wherein the conductive additive is selected from the group consisting of: carbon black, acetylene black, carbon fibers, carbon nanotubes, graphene, graphite, fullerenes, carbon aerogels, metal flakes, metal fibers, metal particles and conductive polymers.

152. An electrode according to claim 153, wherein the conductive additive is a conductive polymer selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide) and PEDOT.

153. An electrode according to any one of claims 144 to 152, wherein the inorganic particles comprise 1 to 50 vol.% (e.g., 5 to 30 vol.% or 10 to 20 vol.%) of an active layer (e.g., a coating or film) of the electrode.

154. An electrode according to any one of claims 144 to 153, wherein the inorganic particles are disposed on one or more surfaces of the electroactive material [e.g., the surface of a microstructure and / or nanostructure such as a particle (e.g., rods and / or spheres), a film, a tube and / or a fiber].

155. An electrode according to any one of claims 144 to 154, wherein the inorganic particles and the electroactive material together form one or more core-shell structures, each of the one or more core-shell structures having a core and a shell, the core comprising at least a portion of the electroactive material, and the shell comprising one of the inorganic particles.

156. An electrode according to claim 154 or claim 155, wherein the inorganic particles are disposed in a layer (e.g., a uniform or non-uniform layer) disposed on (e.g., completely surrounding) the surface of one or more particles comprising the electroactive material.

157. The electrode of claim 156, wherein the thickness of the layer is no greater than 2 μm.

158. The electrode of any one of claims 154-157, wherein the inorganic particles are adhered to the one or more surfaces by electrostatic potential.

159. An electrode according to any one of claims 154 to 158, wherein the inorganic particles and / or the electroactive material have been surface modified (e.g., to alter electrostatic potential and / or hydrophobicity).

160. An electrode according to any one of claims 144 to 159, wherein the electroactive material [e.g., the surface of a microstructure and / or nanostructure such as particles (e.g., rods and / or spheres), films, tubes and / or fibers] and the inorganic particles are dispersed throughout the electrode.

161. An energy storage device comprising two electrodes, wherein at least one of the two electrodes is an electrode according to any one of claims 144 to 160.

162. The energy storage device of claim 161, further comprising a diaphragm (e.g., a diaphragm according to any of the preceding claims), the diaphragm being disposed between the two electrodes such that the diaphragm prevents the two electrodes from being in direct physical contact.

163. The energy storage device of claim 161 or claim 162, further comprising an electrolyte disposed between the two electrodes.

164. An additive or electrode or energy storage device according to any one of claims 101 to 163, wherein the energy storage device is a primary battery, a secondary battery, a secondary battery, a fuel cell unit or a capacitor.

165. The additive or electrode or energy storage device of any one of claims 101 to 164, wherein the energy storage device is an aqueous battery (eg, an aqueous secondary battery or an aqueous primary battery).

166. A separator or electrode additive for an energy storage device, the separator or electrode additive comprising a functional material, the functional material comprising: (i) one or more organic ligands, one or more non-metal oxides, or a combination thereof; or (ii) partially reduced graphene oxide, partially reduced graphite oxide, or a combination thereof.

167. The membrane or electrode additive of claim 166, wherein the functional material comprises the one or more organic ligands.

168. The separator or electrode additive of claim 167, wherein the one or more organic ligands are doped.

169. A membrane or electrode additive according to claim 167 or claim 168, wherein the one or more organic ligands comprise one or more elements selected from the group consisting of: sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine and iodine.

170. The membrane or electrode additive of any one of claims 167 to 169, wherein the one or more organic ligands comprise one or more water molecules (e.g., coordinated and / or bonded to a framework ligand).

171. The separator or electrode additive of any of the preceding claims, wherein the functional material comprises the one or more non-metal oxides.

172. The separator or electrode additive of claim 171, wherein the one or more non-metal oxides are doped.

173. The membrane or electrode additive of claim 172, wherein the one or more non-metal oxides comprise one or more dopants selected from the group consisting of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine, and iodine.

174. The separator or electrode additive of claim 166, wherein the functional material comprises the partially reduced graphene oxide.

175. The separator or electrode additive of claim 174, wherein the partially reduced graphene oxide is doped.

176. The membrane or electrode additive of claim 175, wherein the partially reduced graphene oxide comprises one or more dopants selected from the group consisting of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine, and iodine.

177. The membrane or electrode additive of any one of claims 174-176, wherein the partially reduced graphene oxide is coordinated and / or bonded (e.g., hydrogen bonded) to one or more water molecules.

178. The separator or electrode additive of any one of claims 166 and claims 174 to 177, wherein the functional material comprises the partially reduced graphite oxide.

179. The separator or electrode additive of claim 178, wherein the partially reduced graphite oxide is doped.

180. The membrane or electrode additive of claim 179, wherein the partially reduced graphite oxide comprises one or more dopants selected from the group consisting of sodium, potassium, calcium, barium, cesium, scandium, cadmium, magnesium, iron, manganese, lithium, zinc, zirconium, niobium, yttrium, molybdenum, hafnium, osmium, nickel, cobalt, germanium, beryllium, mercury, tungsten, platinum, rubidium, ruthenium, rhodium, palladium, antimony, tellurium, bismuth, arsenic, lead, lanthanum, europium, gadolinium, cerium, tin, chromium, vanadium, titanium, aluminum, tantalum, gallium, indium, silver, gold, copper, carbon, hydrogen, boron, oxygen, nitrogen, fluorine, chlorine, bromine, and iodine.

181. The membrane or electrode additive of any one of claims 178 to 180, wherein the partially reduced graphite oxide is coordinated and / or bonded (e.g., hydrogen bonded) to one or more water molecules.

182. The separator or electrode additive of any one of claims 166 to 181, wherein the functional material is crystalline or amorphous.

183. The separator or electrode additive of any one of claims 166 to 182, wherein the functional material is contained in particles.

184. A membrane or electrode additive according to claim 183, wherein the particles comprise one or more particles having a spherical shape, one or more particles having a rod shape, one or more particles having a needle shape, one or more particles having a flake shape, one or more particles having a platelet shape, one or more particles having a cubic shape, one or more particles having a disk shape, one or more particles having a tubular shape, or a combination thereof.

185. The separator or electrode additive of any one of claims 166 to 184, wherein the functional material is porous (eg, contained in porous particles).

186. The membrane or electrode additive of claim 185, wherein the functional material has microporosity, mesoporosity, macroporosity, or a combination thereof.

187. A membrane or electrode additive according to claim 185 or claim 186, wherein the functional material comprises one or more pores having a size (e.g., diameter) less than 2 nm.

188. The membrane or electrode additive of any one of claims 185 to 187, wherein the functional material comprises one or more pores having a size (e.g., diameter) of at least 2 nm and no greater than 50 nm.

189. The membrane or electrode additive of any one of claims 185 to 188, wherein the functional material comprises one or more pores having a size (e.g., diameter) greater than 50 nm.

190. The membrane or electrode additive of any one of claims 185 to 189, wherein the functional material comprises one or more particles having a size (e.g., diameter) between to (For example, to to to )[For example, (For example, )to (For example, )] within the range of the hole.

191. The membrane or electrode additive of any one of claims 185 to 190, wherein the functional material comprises one or more pores connected to form at least one channel through the functional material.

192. The membrane or electrode additive of any one of claims 185 to 191, wherein the at least one channel is connected to form a channel system.

193. The membrane or electrode additive of claim 192, wherein the channel system is a 1-dimensional channel system, a 2-dimensional channel system or a 3-dimensional channel system.

194. A membrane or electrode additive according to claim 192 or claim 193, wherein the channel system extends through the functional material [e.g., from a first surface of the membrane to a second surface of the membrane opposite to the first surface (e.g., from the anode side to the cathode side)].

195. A membrane or electrode additive according to any one of claims 185 to 194, wherein one or more species are disposed in (e.g., adsorbed on) one or more pores of the functional material [e.g., on a surface (e.g., an inner surface, near an opening, or both) of the one or more pores].

196. The membrane or electrode additive of claim 195, wherein the one or more species comprises a member selected from the group consisting of olefins, paraffins, cycloalkanes, and aromatic hydrocarbons.

197. A membrane or electrode additive according to claim 195 or claim 196, wherein the one or more species comprises water.

198. The membrane or electrode additive of any one of claims 195 to 197, wherein the one or more species comprises one or more gas species.

199. The membrane or electrode additive of claim 198, wherein the one or more gas species is selected from the group consisting of hydrogen, oxygen, carbon oxides, nitrogen, argon, hydrogen disulfide, ammonia, nitrogen oxides, nitrogen oxides, and sulfur oxides.

200. The separator or electrode additive of any one of claims 194 to 199, wherein the one or more species comprises one or more cationic species.

201. The membrane or electrode additive of claim 200, wherein each of the one or more cationic species is a cationic form of an element selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, thallium, carbon, germanium, tin, lead, nitrogen, phosphorus, arsenic, antimony, bismuth, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, neptunium, and plutonium.

202. The separator or electrode additive of any one of claims 194 to 201, wherein the one or more species comprises one or more anionic species.

203. The membrane or electrode additive of claim 202, wherein the one or more anionic species is selected from the group consisting of hydroxides, alkoxides, peroxides, superoxides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphides, fluorides, chlorides, bromides, iodides, chlorates, bromates, iodates, polyoxometalates, and combinations thereof.

204. The membrane or electrode additive of any one of claims 166 to 203, wherein the surface area of ​​the functional material is at least 10 m 2 / g (e.g., at least 100m 2 / g, at least 250m 2 / g, at least 300m 2 / g, at least 500m 2 / g or at least 700m 2 / g).

205. The separator or electrode additive of any one of claims 166 to 204, wherein the functional material is contained in particles and the average particle size (D 50 ) is 100nm to 30μm.

206. A separator comprising a separator or electrode additive according to any one of the preceding claims and one or more binders.

207. The membrane of claim 206, wherein the one or more adhesives comprise no more than 50 wt.% (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%) of the membrane.

208. A membrane according to claim 206 or claim 207, wherein the one or more binders are selected from the group consisting of: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and styrene butadiene rubber (SBR).

209. The membrane of any one of claims 206 to 208, wherein at least one of the one or more binders comprises one or more binder additives.

210. The membrane of claim 209, wherein the one or more adhesive additives comprise one or more members selected from the group consisting of: pH adjusters, pH buffers, rheology modifiers, defoamers, anti-foaming agents, adhesion promoters, and leveling agents.

211. The membrane of any one of claims 206-210, further comprising a conductive polymer.

212. A membrane according to claim 211, wherein the conductive polymer accounts for no more than 80 wt.% of the membrane (e.g., no more than 70 wt.%, no more than 60 wt.%, no more than 50 wt.%, no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, or no more than 10 wt.%).

213. A membrane according to claim 211 or claim 212, wherein the conductive polymer is selected from the group consisting of: polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide) and PEDOT.

214. A membrane according to any one of claims 206 to 213, wherein the membrane has been coated on an electrode (e.g., an anode, a cathode, or both) in situ or ex situ (e.g., by wet chemical reaction, physical vapor deposition, chemical vapor deposition, atomic layer deposition, sintering, pressing, hot pressing, extrusion, die casting, slot die coating, doctor blade coating, dip coating, or a combination thereof) (e.g., by liquid coating).

215. The membrane of claim 214, wherein the membrane has been further calendered (e.g., to increase bond strength, layer uniformity, or both), annealed, or both.

216. The membrane of any one of claims 206 to 215, wherein the membrane has a thickness in the range of 5 μm to 500 μm.

217. The diaphragm of any one of claims 206 to 216, wherein the diaphragm is a self-supporting film.

218. An electrode comprising one or more electrode additives according to any one of claims 166 to 205 and an electroactive material.

219. The electrode of claim 218, further comprising a current collector, wherein the electroactive material and the additive are coated on the current collector.

220. The electrode of claim 218 or claim 219, further comprising one or more binders.

221. An electrode according to claim 220, wherein the one or more binders constitute no more than 50 wt.% of the separator (e.g., no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, no more than 10 wt.%, no more than 5 wt.%, or no more than 1 wt.%).

222. An electrode according to claim 220 or claim 221, wherein the one or more binders are selected from the group consisting of: polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol, polyvinyl pyrrolidone (PVP), polyacrylic acid (PAA), polyurethane (PU), polyvinyl acetate, polyvinyl chloride (PVC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC) and styrene butadiene rubber (SBR).

223. The electrode of any one of claims 218-222, further comprising a conductive additive.

224. An electrode according to claim 223, wherein the conductive additive constitutes no more than 80 wt.% of the electrode (e.g., no more than 70 wt.%, no more than 60 wt.%, no more than 50 wt.%, no more than 40 wt.%, no more than 30 wt.%, no more than 20 wt.%, or no more than 10 wt.%).

225. An electrode according to claim 223 or claim 224, wherein the conductive additive is selected from the group consisting of: carbon black, acetylene black, carbon fibers, carbon nanotubes, graphene, graphite, fullerenes, carbon aerogels, metal flakes, metal fibers, metal particles and conductive polymers.

226. An electrode according to claim 225, wherein the conductive additive is a conductive polymer selected from the group consisting of polyaniline, polyacetylene, polyphenylene vinylene, polypyrrole, polythiophene, polyphenylene sulfide, polyfluorene, polypyrene, polyazulene, polynaphthalene, poly(p-phenylene vinylene), poly(p-phenylene sulfide) and PEDOT.

227. An electrode according to any one of claims 218 to 226, wherein the functional material comprises 1 vol.% to 50 vol.% (e.g., 5 vol.% to 30 vol.% or 10 vol.% to 20 vol.%) of an active layer (e.g., a coating or film) of the electrode.

228. An electrode according to any one of claims 218 to 227, wherein the functional material is disposed on one or more surfaces of the electroactive material [e.g., the surface of a microstructure and / or nanostructure such as a particle (e.g., rods and / or spheres), a film, a tube and / or a fiber].

229. An electrode according to any one of claims 218 to 228, wherein the functional material and the electroactive material together form one or more core-shell structures, each of the one or more core-shell structures having a core and a shell, the core comprising at least a portion of the electroactive material, and the shell comprising the functional material.

230. An electrode according to any one of claims 218 to 229, wherein the functional material is disposed in a layer (e.g., a uniform or non-uniform layer) disposed on (e.g., completely surrounding) the surface of one or more particles comprising the electroactive material.

231. An electrode according to claim 230, wherein the thickness of the layer is no greater than 2 μm.

232. The electrode of any one of claims 228-231, wherein the functional material adheres to one or more surfaces via electrostatic potential.

233. An electrode according to any one of claims 228 to 232, wherein the functional material and / or the electroactive material has been surface modified (e.g., to change electrostatic potential and / or hydrophobicity).

234. An energy storage device comprising a membrane and two electrodes, wherein the membrane is disposed between the two electrodes such that the membrane prevents the two electrodes from being in direct physical contact, wherein: (i) the diaphragm is a diaphragm according to any one of claims 206 to 217, (ii) at least one of the two electrodes is an electrode according to any one of claims 218 to 233, or (iii) Both (i) and (ii).

235. The energy storage device of claim 234, further comprising a second diaphragm of any one of claims 206 to 217, wherein the second diaphragm is disposed between the two electrodes such that the second diaphragm prevents the two electrodes from making direct physical contact.

236. An energy storage device according to claim 234 or claim 235, further comprising an electrolyte [e.g., a solid or liquid (e.g., aqueous) electrolyte] (e.g., an ion-conductive matrix) disposed between the two electrodes.

237. An energy storage device according to any one of claims 234 to 236, wherein the energy storage device is a primary battery, a secondary battery, a secondary battery, a fuel cell unit or a capacitor.

238. The membrane or electrode or energy storage device of any one of claims 206 to 237, wherein The energy storage device is a primary battery, a secondary battery, a secondary battery, a fuel cell unit or a capacitor.

239. The membrane or electrode or energy storage device of any one of claims 206 to 238, wherein The energy storage device is an aqueous battery (eg, an aqueous secondary battery or an aqueous primary battery).

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