Compositions and methods for energy storage devices including salts and / or foams

Abstract

To provide a dry electrode film of an energy storage device, a solid state energy storage device, a method of fabricating the dry electrode film, an electrode of the energy storage device, and a dry composite solid polymer electrolyte (SPE) film.SOLUTION: An energy storage device can include a cathode, an anode, and a separator between the cathode and the anode. At least one of the electrodes can include an electrode film prepared by a dry process. The electrode film, the electrode and / or the separator can include a salt, improved porosity and increased density, be prelithiated, and / or include a foam. Processes and apparatuses used for fabricating the electrode and / or electrode film are also described.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] Incorporation by reference of priority applications This application claims the benefit of priority to U.S. Provisional Application No. 62 / 757,620, filed Nov. 8, 2018, which is hereby incorporated by reference in its entirety.

[0002] The present invention relates to energy storage devices, and more particularly, to compositions for electrodes of energy storage devices and methods for manufacturing the same.

Background Art

[0003] Description of Related Art To power an electronic device, various types of energy storage devices can be used, including, for example, capacitors, batteries, capacitor-battery hybrids, and / or fuel cells. Energy storage devices, such as conventional or solid-state lithium-ion capacitors or batteries, comprising electrodes prepared using improved electrode formulations and / or manufacturing processes can enhance the electrical performance of the capacitor. Lithium-ion capacitors or batteries comprising electrodes manufactured using improved electrode formulations and / or manufacturing processes can exhibit improved cycle performance, reduced equivalent series resistance (ESR) values, increased power density performance, and / or increased energy density performance. Improved electrode formulations and / or manufacturing processes can also help reduce the manufacturing cost of energy storage devices.

Summary of the Invention

[0004] For the purpose of summarizing the advantages achieved over the present disclosure and the prior art, certain objects and advantages of the present disclosure are set forth herein. Not all such objects or advantages will be achieved in every particular embodiment. Thus, for example, those skilled in the art will recognize that the present invention may be embodied or practiced in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages that are taught or suggested.

[0005] In a first aspect, a dry electrode film of an energy storage device is provided. The dry electrode film includes a dry active material; a dry binder; and a dry electrolyte salt. The dry electrode film is free-standing.

[0006] In some embodiments, the dry electrolyte salt is LiPF6, LiBF4, LiBOB, LiN(SO2CF3)2, LiOSO2CF3, LiNO3, lithium acetate, lithium halide, tetraalkylammonium tetrafluoroborate, tetraalkylammonium hexafluorophosphate, garnet ion conductor, sulfur-based ion conductor, Li 0.5 La 0.5 TiO3 (LLTO), Li7La3Zr2O 12 (LLZO), lithium superionic conductor (LISCON), lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium perchlorate, lithium bis(trifluoromethanesulfonimide) (LiTFSI), lithium bis(oxalato)borate, Li 6.4 La3Zr 1.4 Ta 0.6 O 12 、Li 10 SnP2S 12 、Li 3x La 2 / 3-x TiO3、Li 0.8 La 0.6 Zr2(PO4)3、Li 1+x Ti 2-x Al x (PO4)3、Li 1+x+y Ti 2-x Al x Si y (PO4) 3-y and LiTi x Zr 2-x (PO4)3 or a combination thereof.

[0007] In some embodiments, the dry electrolyte salt constitutes 1 to 10% by weight of the dry electrode film. In some embodiments, the dry electrode film has a thickness of at least 110 μm is carried out. In some embodiments, the dry electrode film has an electrode film density of at least 0.8 g / cm 3 .

[0008] In some aspects, a dry gradient electrode film of an energy storage device is provided. The dry gradient electrode film has a first dry electrode film of a dry electrode film of the energy storage device containing an electrolyte salt at a first concentration and a second dry electrode film of a dry electrode film of the energy storage device containing an electrolyte salt at a second concentration, where the electrolyte salt at the first concentration is less than the electrolyte salt at the second concentration.

[0009] In some aspects, a solid energy storage device is provided that includes a dry electrode film of a dry electrode film of an energy storage device, where the solid energy storage device does not contain a liquid solvent.

[0010] In some aspects, an energy storage device is provided that includes a dry electrode film of a dry electrode film of an energy storage device and a solvent contained within a device housing. In some embodiments, the solvent is a highly volatile solvent.

[0011] In some aspects, a battery is provided that includes a dry electrode film of a dry electrode film of an energy storage device.

[0012] In a second aspect, a method for manufacturing a dry electrode film of an energy storage device is provided. The method includes preparing a dry active material, a dry binder, and a dry electrolyte salt. The method further includes forming a free standing dry electrode film from the dry active material, the dry binder, and the dry electrolyte salt.

[0013] In some embodiments, the method further includes exposing a dry electrode film to a solvent, thereby dissolving an electrolyte salt. In some embodiments, the method further includes disposing the dry electrode film within an energy storage device housing, where exposing the dry electrode film to the solvent is performed within the energy storage device housing. In some embodiments, the method further includes disposing the dry electrode film within an energy storage device housing, where exposing the dry electrode film to the solvent is performed prior to disposing the dry electrode within the energy storage device housing. In some embodiments, the method further includes performing prelithiation of the dry electrode film during the step of exposing the dry electrode film to the solvent. In some embodiments, the method further includes rolling the lithiated dry electrode.

[0014] In a third aspect, a foam-active material composite of an energy storage device is provided. The composite includes a dry active material, a dry binder, and a foam.

[0015] In a fourth aspect, a foam-active material composite of an energy storage device is provided. The composite includes a dry active material and a foam.

[0016] In some embodiments, the foam is a metal foam, a ceramic foam, or a combination thereof. In some embodiments, the dry active material is encapsulated by the foam. In some embodiments, the dry active material and the dry binder are encapsulated by the foam.

[0017] In some aspects, an electrode of an energy storage device includes a foam-active material composite and does not include a separate current collector.

[0018] In some aspects, an electrode of an energy storage device includes a foam-active material composite and further includes a current collector.

[0019] In a fifth aspect, a dried composite solid polymer electrolyte (SPE) film of an energy storage device is provided. This SPE film includes a dried ion-conductive polymer; a dried lithium source; a dried binder; an ion-conductive medium; and a dried filler.

[0020] In some aspects, the dried ion-conductive polymer is selected from polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly(methylene oxide), polyoxymethylene, poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), poly(methyl methacrylate), poly(vinyl acetate), poly(vinyl chloride), poly(vinyl acetate), poly(oxyethylene)9 methacrylate, poly(ethylene oxide) methyl ether methacrylate, and poly(propylene imine) or combinations thereof. In some embodiments, the dried lithium source is lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (Li(C2F5SO2)2N), lithium bis(oxalato)borate (LiB(C2O4)2), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(pentafluoroethanesulfonyl)imide (C4F 10 LiNO4S2), lithium bis(fluorosulfonyl)imide (F2LiNO4S2), lithium difluoro(oxalato)borate (LiBF2(C2O4), lithium difluorophosphate (F2LiO2P), lithium oxalyldifluoroborate, lithium trifluorochloroborate (LiBF3Cl), lithium hexafluoroarsenate (LiAsF6), Li 6.4 La3Zr 1.4 Ta 0.6 O 12 、Li7La3Zr2O 12 、Li 10 SnP2S 12 、Li3xLa 2 / 3-x TiO3、Li 0.8 La 0.6 Zr2(PO4)3、Li 1+x Ti 2-x Alx (PO4)3, Li 1+x+y Ti 2-x Al x Si y (PO4) 3-y and LiTi x Zr 2-x (PO4)3 or a combination thereof. In some embodiments, the dry filler is titanium oxide (TiO2), silica (SiO2), silicon monoxide (SiO), copper oxide (CuO), montmorillonite ((Na,Ca) 0.33 (Al,Mg)2(Si4O 10 ), bentonite (Al2O 34 SiO2H2O), kaolinite (Al2Si2O5(OH)4), hectorite (Na 0.3 (Mg,Li)3Si4O 10 (OH)2), halloysite (Al2Si2O5(OH)4)), 4'-amino-2,3'-dimethylazobenzene (CH3C6H4N=NC6H3(CH3)NH2), yttrium aluminum oxide (Y3Al5O 12 ), yttrium iron oxide (Y3Fe5O 12 ), and nanoclay, or a combination thereof. In some embodiments, the ion-conductive medium is selected from nanoclay and garnet, or a combination thereof.

[0021] In some aspects, an energy storage device is provided. The energy storage device includes a dry cathode electrode including a dry electrode film, a dry composite SPE film, and a lithium metal anode.

[0022] In some embodiments, the energy storage device is a solid energy storage device that does not contain a liquid solvent.

[0023] All of these embodiments are intended to be within the scope of the invention disclosed herein. These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of the preferred embodiments with reference to the accompanying drawings, and the invention is not limited to the specific preferred embodiments disclosed.

Brief Description of the Drawings

[0024] These and other features, aspects, and advantages of the present disclosure will be described with reference to the drawings of specific embodiments. The drawings are intended to illustrate specific embodiments and are not intended to limit the present invention.

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Mode for Carrying Out the Invention

[0025] Detailed Description Definitions As used herein, the terms "battery" and "capacitor" should be given their ordinary and customary meaning to one of ordinary skill in the art. The terms "battery" and "capacitor" are not mutually exclusive. The term capacitor or battery may refer to a single electrochemical cell that can operate alone or as a component of a multi-cell system.

[0026] As used herein, the voltage of an energy storage device is the operating voltage of a single battery or capacitor cell. The voltage may exceed or be less than the rated voltage depending on the load applied or manufacturing tolerances.

[0027] As provided herein, a "self-supporting" electrode film is an electrode film that incorporates a binder matrix structure sufficient to support the film or layer and maintain its shape so that the electrode film or layer can stand on its own. When incorporated into an energy storage device, the self-supporting electrode film or active layer incorporates such a binder matrix structure. Support elements are used to facilitate the manufacturing process of the energy storage device, but generally, depending on the method employed, such electrode films or active layers have sufficient strength to be used in the energy storage device manufacturing process without external support elements such as current collectors, support webs, or other structures. For example, a "self-supporting" electrode film can have sufficient strength to be wound, handled, and unrolled within the electrode manufacturing process without other support elements. Dry electrode films such as cathode electrode films or anode electrode films can be self-supporting.

[0028] As provided herein, a "solvent-free" electrode film is an electrode film that does not contain detectable processing solvents, processing solvent residues, or processing solvent impurities. Dry electrode films such as cathode electrode films or anode electrode films can be solvent-free.

[0029] A "wet" electrode, "wet process" electrode, or slurry electrode is an electrode prepared by at least one step involving a slurry of an active material, a binder, and optionally an additive. The wet electrode may contain a processing solvent, processing solvent residues, and / or processing solvent impurities.

[0030] Description Specific embodiments and examples are described below, but those skilled in the art will understand that the present invention extends beyond the specifically disclosed embodiments and / or uses and their obvious modifications and equivalents. Accordingly, it is intended that the scope of the invention disclosed herein should not be limited by any specific embodiment described below.

[0031] Electrode film packing density or electrode film porosity is an important property in energy storage device components for achieving improved electrochemical performance. Therefore, it is necessary to determine and manufacture an appropriate electrode film density. An appropriate electrode film density provides both high ionic conductivity and high electronic conductivity. In the wet electrode coating process, the packing weight of the electrode material and the electrode film density are generated in separate steps, and the electrode film density after solvent removal is usually smaller than that of the desired target electrode film density.

[0032] In the dry electrode process, the control of the electrode film density and the packing weight of the target electrode material is measured by controlling the thickness of the free-standing film and the magnitude of the applied compression pressure, and is generally achieved by successive calendar passes. Thus, different from the wet coating technique the independent control of the packing weight of the electrode material and the electrode film thickness is limited. The porosity of the electrode film in dry electrode film manufacturing is mainly controlled by the powder formulation used in the manufacture of the free-standing film. Particle size, surface chemistry, and morphology are common properties that affect the electrode film density of the supplied dry free-standing electrode film.

[0033] In some cases, a pore-forming material can be added to a powder formulation and then removed, leaving pore volume in the self-supporting film. The pore-forming materials used are materials that may require liquid extraction such as salts and subsequent rinsing steps, or thermal decomposition to gaseous by-products. In some embodiments, the present disclosure provides materials and processes for manufacturing a dried electrode film that has a high porosity (low density) without such post-treatment steps that increase manufacturing costs.

[0034] Furthermore, in some embodiments, these materials and processes can also be used to pre-lithiate the dried electrode film. Conventional processes for lithiating an anode utilize lithium metal as a counter electrode for lithiating the electrodes in a reel-to-reel fashion. Low-cost salt approaches avoid the use of lithium metal, but conventionally require real-time monitoring and metering of the salt into the electrolyte chamber to maintain sufficient lithium ions for the reduction process in continuous reel-to-reel lithiation using a galvanic cell. The present disclosure describes, in some embodiments, the use of electrode salt materials in a dried electrode film that can be used to pre-lithiate the electrode film. In some embodiments, the level of pre-lithiation can be adjusted by adjusting the amount of electrode salt in the dried electrode film. In some embodiments, pre-lithiation of the electrode film also provides an increase in the porosity of the electrode film.

[0035] In other examples, these materials and processes can be used to manufacture solid electrodes. Typical commercially available lithium-ion batteries contain a flammable electrolyte and thus have the potential to catch fire or explode upon overcharging. Electrodes of typical lithium-ion batteries are manufactured from a wet process where the slurry is composed of an active material and a solvent. The solvent not only adds cost to the procedure and can degrade components of the solid energy storage device, but commonly used solvents such as N-methyl-2-pyrrolidone can have an adverse health effect upon repeated exposure.

[0036] Solid batteries improve safety by using nonflammable components. Further, since the formation of dendrites is not as severe in solid batteries as in typical liquid-based lithium-ion batteries, elemental lithium metal can be safely utilized as an electrode. Lithium metal provides a significantly higher theoretical specific capacity compared to graphite, enabling an improvement in energy density over typical lithium-ion batteries. Additionally, dry electrode processing methods are expected to be less expensive and safer than conventional methods. Typically, solid lithium batteries have an ionic and / or electron-conductive cathode, a solid electrolyte, and a lithium metal anode. In some embodiments, the solid electrode includes a dry solid electrolyte salt. In some embodiments, the solid electrolyte is an ion-conductive inorganic solid electrolyte. In some embodiments, the solid electrolyte is a polymer-based film. In some embodiments, it is a dried composite solid polymer electrolyte (SPE).

[0037] In some examples, embodiments include dry electrode formulations and manufacturing processes that achieve electrode films having a higher density of active material, a greater electrode film thickness, a greater electrode film density, and / or a greater electron density (e.g., energy density, specific energy density, areal energy density, areal capacity, and / or specific capacity, etc.). Higher density electrode films will generally contain more active material in a smaller volume. Specifically, smaller particle size and closer contact of the active material, binder, and additives are realized in the dry process It can be presented. Conventional drying treatment methods use high shear and / or high pressure treatment steps to break and mix electrode film materials, which can contribute to structural advantages. The present disclosure teaches that in some embodiments, the electrode density and porosity can be modified by changing the electrode material composition, for example, by changing the active material, polymer binder, and additives. Further, it has been found that improved high electrode film density at high fillings can also be produced by controlling the calendering parameters of the electrodes, such as the calendering temperature, gap size, roll speed, sequence, and number of passes. Embodiments utilizing such processes and compositions exhibit significantly improved electrode film density at high fillings. In some embodiments, the calendering can be performed at ambient temperature. In some embodiments, high fillings and high electrode film density are achieved without problems such as cracking and / or delamination of the electrode film.

[0038] Although many embodiments and examples are described throughout the present disclosure, those skilled in the art will understand that the disclosed embodiments may be used alone or in combination. For example, high-density electrode films can be utilized in solid systems and / or thick electrode films. In other examples, thick electrode films can be utilized in electrode films containing electrode salts, solid systems, porous electrode films, and / or electrodes or electrode films containing foams. In other examples, electrodes or electrode films containing foams can be utilized in solid systems, electrode films containing electrode salts, and / or porous electrode films. Although many non-limiting examples of combinations are given herein, other combinations are also possible.

[0039] In some embodiments, an energy storage device such as a lithium-ion capacitor (LiC) or a lithium-ion battery with improved electrical and / or mechanical performance characteristics is provided. In some embodiments, the device may comprise an electrode comprising an improved electrode film composition, which can provide improved electrical and / or mechanical performance. In some embodiments, the electrode can be an anode or a cathode.

[0040] Embodiments of the present specification may include a mixture of materials for related methods having an electrode film, an energy storage device, and an electrode salt. By utilizing the electrode salt, many electrical, mechanical properties, and / or processing advantages can be realized.

[0041] For example, the dry electrode film may contain an electrode salt. Here, when the dry electrode film is exposed to a solvent, the electrode salt dissolves in the solvent, thereby achieving a dry electrode film with increased porosity. In some embodiments, the solvent is arranged to contact the dry electrode film when introduced into the housing or container of the energy storage device. For example, here, the electrode salt remains in the device to act as an electrolyte. In other examples, the solvent containing the dissolved electrode salt is removed from and / or washed out of the container of the energy storage device. In some embodiments, the solvent is introduced onto the dry electrode film outside the container of the energy storage device, thereby removing the electrode salt before the dry electrode film is laminated to the current collector as a dry electrode and / or before being placed inside the container of the energy storage device. In some embodiments, the dry electrode film is washed with a solvent and pre-lithiated simultaneously when exposed to an electric current outside the container of the energy storage device. In some embodiments, the dry electrode film is pre-lithiated after being washed with a solvent outside the container of the energy storage device. For example, the pre-lithiation can be performed in a separate pre-lithiation device or inside the container of the energy storage device.

[0042] In other examples, the dry electrode may contain an electrode salt, and the dry electrode is utilized as a solid electrode in an energy storage device. In some embodiments, the solid electrode is a dry electrode that remains solvent-free when fully assembled and operating inside the container of the energy storage device. In some embodiments, the electrode salt has high conductivity. Salts with high conductivity usually have relatively low lattice energy, so the salt dissolves in the solvent to generate a sufficient number of ions. For example, some highly conductive Li salts include LiPF6, LiClO4, and LiN(SO2CF3)2. Since the energy is relatively low, the salt dissolves in the solvent to produce a sufficient number of ions. For example, some highly conductive Li salts include LiPF6, LiClO4, and LiN(SO2CF3)2.

[0043] In some embodiments, the electrode salt can be an ionic compound. In some embodiments, the electrode salt can be a solid electrolyte additive. In some embodiments, the electrode salt can be a compound having a high ionic conductivity. In some embodiments, the electrode salt can be a ceramic compound having a high ionic conductivity. In some embodiments, the electrode salt is LiPF6, LiBF4, LiBOB, LiN(SO2CF3)2, LiOSO2CF3, LiNO3, lithium acetate, lithium halide, tetraalkylammonium tetrafluoroborate, tetraalkylammonium hexafluorophosphate, lithium fluoride, garnet ion conductor, such as Li5La3Ta2O 12 and Li3N, sulfur-based ion conductors, such as Li2S-P2S5 and Li2S-P2S5-Li3PO4, other compounds having a high ionic conductivity, such as Li 0.5 La 0.5 TiO3 (LLTO), Li7La3Zr2O 12 (LLZO), lithium superionic conductor (LISCON), such as LISCON has the chemical formula Li (2+2x) Zn (l-x)It can be of GeO4 and can be selected from at least one of them. In some embodiments, the electrode salt is selected from at least one of LiPF6, LiBF4, LiBOB, LiN(SO2CF3)2, LiOSO2CF3, LiNO3, lithium acetate, lithium halide, tetraalkylammonium tetrafluoroborate, and tetraalkylammonium hexafluorophosphate. In some embodiments, the electrode salt is a lithium salt. In some embodiments, the electrode salt is selected from at least one of lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium perchlorate, and lithium fluoride. In some embodiments, the phosphate is lithium perchlorate (LiClO4), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (Li(C2F5SO2)2N), lithium bis(oxalato)borate (LiB(C2O4)2), lithium trifluoromethanesulfonate (LiCF3SO3), Li 6.4 La3Zr 1.4 Ta 0.6 O 12 , Li7La3Zr2O 12 , Li 10 SnP2S 12 , Li 3x La 2 / 3-x TiO3, Li 0.8 La 0.6 Zr2(PO4)3, Li 1+x Ti 2-x Al x (PO4)3, Li 1+x+y Ti 2-x Al x Si y (PO4) 3-y and at least one of LiTi x Zr 2-x (PO4)3 is selected. In some embodiments, the electrode salt is lithium fluoride. In some embodiments, the electrode salt is a garnet ion conductor, for example, Li5La3Ta2O 12and Li3N. In some embodiments, the electrode salt is a sulfur-based ionic conductor, such as Li2S-P2S5 and Li2S-P2S5-Li3PO4. In some embodiments, the electrode salt is another compound having high ionic conductivity, such as Li 0.5 La 0.5 TiO3 (LLTO) and / or Li7La3Zr2O 12 (lithium lanthanum zirconate or LLZO). In some embodiments, the electrode salt is a lithium superionic conductor (LISCON), for example, the LISCON may have the chemical formula of Li (2+2x) Zn (1-x) GeO4. In some embodiments, the electrode salt does not deteriorate under the operation of a normal energy storage device.

[0044] In some embodiments, the electrode salt constitutes 0.5 wt% or about 0.5 wt%, 1 wt% or about 1 wt%, 2 wt% or about 2 wt%, 3 wt% or about 3 wt%, 4 wt% or about 4 wt%, 5 wt% or about 5 wt%, 6 wt% or about 6 wt%, 7 wt% or about 7 wt%, 8 wt% or about 8 wt%, 9 wt% or about 9 wt%, 10 wt% or about 10 wt% or 11 wt% or about 11 wt% of the dry electrode mixture, or any value between those values. For example, in some embodiments, the electrode salt constitutes 1-10 wt% of the dry electrode mixture.

[0045] In some embodiments, the solvent for use as an electrolyte in the device or for use as a cleaning outside the device is selected from at least one of carbonate, ester, amide, ether, alcohol, sulfone, and water. In some embodiments, the solvent is dimethyl carbonate. In some embodiments, the solvent is a highly volatile solvent and the solvent is a gas at ambient temperature and pressure. In some embodiments, the highly volatile solvent is a liquid at a pressure exceeding 1 atmosphere. In some embodiments, the highly volatile solvent is a liquid at a temperature below 20°C. In some embodiments, the highly volatile solvent has a boiling point under atmospheric pressure of about 10°C or up to about 10°C, about 20°C or up to about 20°C, about 30°C or up to about 30°C, about 40°C or up to about 40°C, about 50°C or up to about 50°C, about 57°C or up to about 57°C, about 60°C or up to about 60°C, about 66°C or up to about 66°C, about 70°C or up to about 70°C, about 80°C or up to about 80°C, about 90°C or up to about 90°C, about 91°C or up to about 91°C, about 95°C or up to about 95°C, or any range therebetween. In some embodiments, the highly volatile solvent can be dimethyl carbonate, tetrahydrofuran (THF), methyl acetate, or a mixture thereof.

[0046] FIG. 1 is a schematic side cross-sectional view showing an example of an energy storage device 100 according to one or more embodiments of the present disclosure. The energy storage device 100 can be classified, for example, as a battery, a capacitor, a capacitor-battery hybrid, or a fuel cell. In some embodiments, the device 100 is a lithium-ion battery. The device 100 includes a first electrode 102, a second electrode 104, and a separator 106 disposed between the first electrode 102 and the second electrode 104. The first electrode 102 and the second electrode 104 are adjacent to opposite surfaces of the separator 106. In some embodiments, the first electrode 102 can be an anode (“negative electrode”), and the second electrode 104 can be a cathode (“positive electrode”). The energy storage device 100 includes an electrolyte 122 for facilitating ion transport between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 122 can be in contact with the first electrode 102, the second electrode 104, and the separator 106. The electrolyte 122, the first electrode 102, the second electrode 104, and the separator 106 are housed within a housing 120 of the energy storage device. For example, the housing 120 of the energy storage device can be sealed following the insertion of the first electrode 102, the second electrode 104, and the separator 106, and the impregnation of the electrolyte 122 into the energy storage device 100, such that the first electrode 102, the second electrode 104, the separator 106, and the electrolyte 122 are physically sealed from the environment outside the housing. Although the energy storage device 100 is shown as a dual-electrode, double-layer device, it will be understood that other types, such as single-layer electrodes, can be implemented.

[0047] Energy storage device 100 may comprise any number of different types of electrolytes 122. For example, device 100 may comprise a lithium-ion battery electrolyte that includes a lithium source such as a lithium salt and a solvent such as an organic solvent. In some embodiments, device 100 may further include additives such as a solid electrolyte interphase (SEI)-forming additive, an electrode wetting additive, or a separator wetting additive. In some embodiments, the lithium salt may be lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2), lithium trifluoromethanesulfonate (LiSO3CF3), lithium bis(pentafluoroethanesulfonyl)imide (C4F 10 LiNO4S2), lithium bis(fluorosulfonyl)imide (F2LiNO4S2), lithium bis(oxalato)borate (LiB(C2O4)2), lithium difluoro(oxalato)borate (LiBF2(C2O4), lithium difluorophosphate (F2LiO2P), lithium oxalyldifluoroborate, lithium trifluorochloroborate (LiBF3Cl), lithium hexafluoroarsenate (LiAsF6), combinations thereof and / or equivalents thereof. In some embodiments, the lithium-ion electrolyte solvent may include one or more ethers and / or esters. For example, the lithium-ion electrolyte solvent may include ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), vinyl carbonate (VC), propylene carbonate (PC), combinations thereof and / or equivalents thereof. For example, the electrolyte may include LiPF6, ethylene carbonate, propylene carbonate, and diethyl carbonate.

[0048] In some embodiments, the electrolyte 122 of the energy storage device 100 includes at least one of a solvent and the electrode salt described above. In some embodiments, the energy storage device 100 is a solid energy storage device, and thus, the electrolyte 122 does not include a solvent.

[0049] The separator 106 can be configured to electrically insulate two adjacent electrodes, for example, the first electrode 102 and the second electrode 104, adjacent to opposite sides of the separator 106, while enabling ion transport between the two adjacent electrodes. The separator 106 can include a suitable porous electrical insulating material. In some embodiments, the separator 106 can include a polymer material. For example, the separator 106 can include a cellulose material (e.g., paper), a polyethylene (PE) material, a polypropylene (PP) material, and / or a polyethylene and polypropylene material. In some embodiments, the separator can be a multilayer material such as, for example, PP / PE or PP / PE / PP. In some embodiments, the separator can be a ceramic-coated one, such as, for example, a ceramic-coated PE, PP, or multilayer material.

[0050] In some embodiments, particularly when the energy storage device 100 is a solid energy storage device, the separator 106 can be a solid electrolyte layer. In some embodiments, the solid electrolyte layer can include a solid polymer electrolyte (SPE).

[0051] As shown in FIG. 1, the first electrode 102 and the second electrode 104 each include a first current collector 108 in contact with the first electrode film 112 and the second electrode film 114, and a second current collector 110 in contact with the third electrode film 116 and the fourth electrode film 118. The first current collector 108 and the second current collector 110 can facilitate the electrical coupling between the corresponding electrode films and an external circuit (not shown). The first current collector 108 and / or the second current collector 110 include one or more conductive materials and have any suitable shape and size selected to facilitate the movement of charge between the corresponding electrode and the external electrical circuit. For example, the current collector can include metal materials such as aluminum, nickel, copper, rhenium, niobium, tantalum, etc., noble metals such as silver, gold, platinum, palladium, rhodium, osmium, iridium, and alloys, and combinations thereof. For example, the first current collector 108 and / or the second current collector 110 can include, for example, aluminum foil or copper foil. The first current collector 108 and / or the second current collector 110 can have a rectangular or substantially rectangular shape of a size that provides for the movement of charge between the corresponding electrode and the external circuit. In some embodiments, the current collector can include a foam as described herein. In some embodiments, one or more electrode films are sealed by the current collector.

[0052] The first electrode 102 can have a first electrode film 112 (e.g., an upper electrode film) on a first surface of the first current collector 108 (e.g., the upper surface of the first current collector 108) and a second electrode film 114 (e.g., a lower electrode film) on a second opposite surface of the first current collector 108 (e.g., the bottom surface of the first current collector 108). Similarly, the second electrode 104 can have a third electrode film 116 (e.g., an upper electrode film) on a first surface of the second current collector 110 (e.g., the upper surface of the second current collector 110) and a fourth electrode film 118 on a second opposite surface of the second current collector 110 (e.g., the bottom surface of the second current collector 110). For example, the first surface of the second current collector 110 is such that the separator 106 is the third electrode film of the second electrode film 114 of the first electrode 102 and the second electrode 104 It can face the second surface of the first current collector 108 so as to be adjacent to the μ116. In some embodiments, the electrode may include two or more electrode films, such as the first electrode film 112 and the second electrode film 114 in the first current collector 108 of the first electrode 102 shown in FIG. 1. In some embodiments, the electrode may include only one electrode film, for example, the first electrode 102 shown in FIG. 1 may be composed of the first electrode film 112 and the first current collector 108.

[0053] The electrode film 112 and / or 114 can be the dry and / or self-supporting electrode films provided herein, and as provided herein, have advantageous properties such as increased thickness, increased electrode film density, increased porosity of the electrode film, increased energy density, increased specific energy density, increased areal energy, and / or increased areal capacity.

[0054] The electrode film can have a selected thickness suitable for a particular application. The thickness of the electrode film provided herein may be greater than the thickness of an electrode film prepared by a conventional process. In some embodiments, the electrode film is about 30 microns or more, about 50 microns or more, about 100 microns or more, about 110 microns or more, about 115 microns or more, about 120 microns or more, about 130 microns or more, about 135 microns or more, about 150 microns or more, about 155 microns or more, about 160 microns or more, about 170 microns or more, about 200 microns or more, about 250 microns or more, about 260 microns or more, about 265 microns or more, about 270 microns or more, about 280 microns or more, about 290 microns or more, about 300 microns or more, about 350 microns or more, about 400 microns or more, about 450 microns or more, about 500 microns or more, about 750 microns or more, about 1 mm or more or about 2 mm or more, or any range of values therebetween. The electrode film thickness can be selected to correspond to a desired areal capacity, specific capacity, areal energy density, energy density or specific energy density. In some embodiments, the electrode film thickness corresponds to the thickness of a single electrode film. In some embodiments, the electrode film thickness corresponds to the thicknesses of a plurality of single electrode films that are formed together to form the electrode film.

[0055] In some embodiments, the electrode film porosity of the electrode films provided herein may be greater than the porosity of electrode films prepared by conventional processes. In some embodiments, the electrode film porosity of the electrode films provided herein may be less than the porosity of electrode films prepared by conventional processes. In some embodiments, the electrode film may have an electrode film porosity of about 5%, about 8%, about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about 25%, about 30%, about 35% or about 40%, or any range of values therebetween (which can be expressed as a percentage of the volume of the electrode film occupied by pores). In some embodiments, the electrode film may have an electrode film porosity of at least about 5%, at least about 8%, at least about 10%, at least about 12%, at least about 14%, at least about 16%, at least about 18%, at least about 20%, at least about 25%, at least about 30%, at least about 35% or at least about 40%, or any range of values therebetween (which can be expressed as a percentage of the volume of the electrode film occupied by pores). In some embodiments, the electrode film may have an electrode film porosity of up to about 5%, at least about 8%, at least up to about 10%, up to about 12%, up to about 14%, up to about 16%, up to about 18%, up to about 20%, up to about 25%, up to about 30%, up to about 35% or up to about 40%, or any range of values therebetween (which can be expressed as a percentage of the volume of the electrode film occupied by pores).

[0056] In some embodiments, the electrode film density of the electrode films provided herein is may be less than the density of electrode films prepared by conventional processes. In some embodiments, the electrode film density of the electrode films provided herein may be greater than the electrode film density of electrode films prepared by conventional processes. In some embodiments, the electrode film has a density of about 0.8 g / cm 3 , about 1.0 g / cm 3, about 1.4 g / cm 3 , about 1.5 g / cm 3 , about 1.6 g / cm 3 , about 1.7 g / cm 3 , about 1.8 g / cm 3 , about 1.9 g / cm 3 , about 2.0 g / cm 3 , about 2.5 g / cm 3 , about 3.0 g / cm 3 , about 3.3 g / cm 3 , about 3.4 g / cm 3 , about 3.5 g / cm 3 , about 3.6 g / cm 3 , about 3.7 g / cm 3 , about 3.8 g / cm 3 , about 3.9 g / cm 3 , about 4.0 g / cm 3 , about 4.1 g / cm 3 or about 4.2 g / cm 3 , or may have an electrode film density within any range of values therebetween. In some embodiments, the electrode film is at most about 0.8 g / cm 3 , about 1.0 g / cm 3 , 1.4 g / cm 3 , at most about 1.5 g / cm 3 , at most about 1.6 g / cm 3 , at most about 1.7 g / cm 3 , at most about 1.8 g / cm 3 , at most about 1.9 g / cm 3 or at most about 2.0 g / cm 3 , or may have an electrode film density within any range of values therebetween. In some embodiments, the electrode film is at least about 0.8 g / cm 3 , about 1.0 g / cm 3 , about 1.4 g / cm 3 , at least about 1.5 g / cm 3 , at least about 1.6 g / cm 3 , at least about 1.7 g / cm 3 , at least about 1.8 g / cm 3 , at least about 1.9 g / cm 3 , at least about 2.0 g / cm 3 , at least about 2.5 g / cm3 , at least about 3.0 g / cm 3 , at least about 3.3 g / cm 3 , at least about 3.4 g / cm 3 , at least about 3.5 g / cm 3 , at least about 3.6 g / cm 3 , at least about 3.7 g / cm 3 , at least about 3.8 g / cm 3 , at least about 3.9 g / cm 3 , at least about 4.0 g / cm 3 , at least about 4.1 g / cm 3 or at least about 4.2 g / cm 3 , or may have an electrode film density in any range of values therebetween.

[0057] In some embodiments, the electrode formulation may be calendared at a temperature of about 5 °C, about 10 °C, about 15 °C, about 20 °C, about 23 °C, about 25 °C, about 30 °C, about 35 °C, about 40 °C, about 50 °C, about 60 °C, about 65 °C, about 90 °C, about 120 °C, about 150 °C, about 170 °C, about 200 °C, about 220 °C or about 250 °C or any range of values therebetween. In some embodiments, the electrode formulation may be calendared at approximately ambient temperature or room temperature.

[0058] The electrode film generally includes one or more active materials, such as an anode active material or a cathode active material as provided herein. The first electrode film 112 and / or the second electrode film 114 may also include one or more binders as provided herein. The electrode films 112 and / or 114 can be prepared by the processes described herein. The electrode films 112 and / or 114 can be wet or self-supporting dry electrodes as described herein.

[0059] In some embodiments, electrode films such as one or more electrode films 112 and / or 114 include at least one electrode salt, as described herein. In some embodiments, the electrode film also includes at least one active material and at least one binder. The at least one active material can be any active material known in the art. The at least one active material can be a material suitable for use in the anode or cathode of a battery.

[0060] The at least one active material can include one or more carbon materials. The carbon material can be selected from, for example, graphitic materials, graphite, graphene-containing materials, hard carbon, soft carbon, carbon nanotubes, porous carbon, conductive carbon, or combinations thereof. Activated carbon is obtained from a vapor process or an acid / etching process. In some embodiments, the graphitic material can be a surface-treated material. In some embodiments, the porous carbon can include activated carbon. In some embodiments the porous carbon can include hierarchically structured carbon. In some embodiments, the porous carbon can include structured carbon nanotubes, structured carbon nanowires, and / or structured carbon nanosheets. In some embodiments, the porous carbon can include graphene sheets. In some embodiments, the porous carbon can be surface-treated carbon.

[0061] The anode active material may include, for example, insertion materials (such as carbon, graphite (natural, synthetic, blend, etc.), hard carbon or amorphous carbon and / or graphene, etc.), alloying / dealloying materials (such as silicon, silicon oxide, tin and / or tin oxide, etc.), metal elements, metal alloys or compounds (such as Si-Al and / or Si-Sn, etc.), and / or modified materials (such as manganese oxide, molybdenum oxide, nickel oxide, etc. and / or copper oxide, etc.). The anode active material may be used alone or mixed to form a multiphase material (such as Si-C, Sn-C, SiOx-C, SnOx-C, Si-Sn, Si-SiOx, Sn-SnOx, Si-SiOx-C, Sn-SnOx-C, Si-Sn-C, SiOx-SnOx-C, Si-SiOx-Sn or Sn-SiOx-SnOx, etc.).

[0062] In some embodiments, the anode electrode film may include at least one active material, a binder, and an optional conductive additive. In some embodiments, the conductive additive may include a conductive carbon additive such as carbon black. In some embodiments, at least one active material of the anode may include synthetic graphite, natural graphite, hard carbon, soft carbon, graphene, mesoporous carbon, silicon, silicon oxide, tin, tin oxide, germanium, lithium titanate, a mixture, or a composite material of the foregoing materials. In some embodiments, the anode electrode film may include from about 80 to about 98 wt% or from about 94 to about 97 wt% of at least one active material. In some embodiments, the anode electrode film may include at least one active material at about 80 wt%, about 85 wt%, about 90 wt%, about 92 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 98 wt% or about 99 wt%, or any range of values therebetween. In some embodiments, the anode electrode film includes a conductive additive of up to about 5 wt%, including from about 1 to about 3 wt%. In some embodiments, the anode electrode film may include a conductive additive at about 5 wt% or up to about 5 wt%, about 3 wt% or up to about 3 wt%, about 1 wt% or up to about 1 wt%, or about 0.5 wt% or up to about 0.5 wt%, or any range of values therebetween. In some embodiments, the anode electrode film includes a binder of up to about 20 wt%, including from about 1.5 to about 10 wt%, from about 1.5 to about 5 wt%, or from about 3 to about 5 wt%. In some embodiments, the anode electrode film includes about 4 wt% of the binder. In some embodiments, the anode electrode film may include a binder at about 20 wt% or up to about 20 wt%, about 15 wt% or up to about 15 wt%, about 10 wt% or up to about 10 wt%, about 5 wt% or up to about 5 wt%, about 3 wt% or up to about 3 wt%, about 1.5 wt% or up to about 1.5 wt%, or about 1 wt% or up to about 1 wt%, or any range of values therebetween. In some embodiments, the anode film may not include a conductive additive.

[0063] The cathode active material may include, for example, metal oxides, metal sulfides, or lithium metal oxides. The lithium metal oxides may be, for example, lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate (LTO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the cathode active material is, for example, a layered transition metal oxide (such as LiCoO2 (LCO), Li(NiMnCo)O2 (NMC), and / or LiNi 0.8 Co 0.15 Al 0.05 O2 (NCA), etc.), spinel manganese oxide (such as LiMn2O4 (LMO) and / or LiMn 1.5 Ni 0. 5O4 (LMNO), etc.), olivine (such as LiFePO4), chalcogenide (LiTiS2), triphylite (LiFeSO4F), silicon, silicon oxide (SiOx), aluminum, tin, tin oxide (SnOx), manganese oxide (MnOx), molybdenum dioxide (MoO2), molybdenum disulfide (MoS2), nickel oxide (NiOx), or copper oxide (CuOx). The cathode active material may include a sulfur-containing material such as sulfur or lithium sulfide (Li2S), or other sulfur-based materials, or mixtures thereof. In some embodiments, the cathode film includes a material containing sulfur or a sulfur active material at a concentration of at least 50% by weight. In some embodiments, the cathode film containing a material containing sulfur or a sulfur active material has an areal capacity of at least 10 mAh / cm 2 2. In some embodiments, the cathode film containing a material containing sulfur or a sulfur active material has a mass loading of 1 g / cm 3has an electrode film density. In some embodiments, the cathode film containing sulfur or the material containing a sulfur active material further includes a binder. In some embodiments, the binder of the cathode film containing a material containing sulfur or a sulfur active material is selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), poly(ethylene oxide) (PEO), polyethylene (PE), polyacrylic acid (PAA), gelatin, other thermoplastics, or any combination thereof.

[0064] In some embodiments, the cathode electrode film of a lithium-ion battery or a hybrid energy storage device may include at least one active material in an amount of about 70 to about 98 wt%, about 70 to about 96 wt%, or about 70 to about 92 wt%. In some embodiments, the cathode electrode film may include at least one active material in an amount of about 70 wt% or up to about 70 wt%, about 90 wt% or up to about 90 wt%, about 92 wt% or up to about 92 wt%, about 94 wt%, about 95 wt%, about 96 wt% or up to about 96 wt%, or about 98 wt% or up to about 98 wt%, or any value within a range therebetween. In some embodiments, the cathode electrode film of a lithium-ion battery or a hybrid energy storage device may include at least one active material in an amount of about 40 to about 60 wt%. In some embodiments, the cathode electrode film may include a porous carbon material in an amount of up to about 10 wt%, including up to about 5 wt% or about 1 to about 5 wt%. In some embodiments, the cathode electrode film may include a porous carbon material in an amount of about 10 wt% or up to about 10 wt%, about 5 wt% or up to about 5 wt%, about 1 wt% or up to about 1 wt%, or about 0.5 wt% or up to about 0.5 wt%, or any value within a range therebetween. In some embodiments, the cathode electrode film includes a conductive additive in an amount of up to about 5 wt%, including about 1 to about 3 wt%. In some embodiments, the cathode electrode film may include a conductive additive in an amount of about 10 wt% or up to about 10 wt%, 5 wt%, about 3 wt% or up to about 3 wt%, or about 1 wt% or up to about 1 wt%, or any value within a range therebetween. In some embodiments, the cathode electrode film includes a binder in an amount of up to about 20 wt%, for example, about 1.5 to 10 wt%, about 1.5 to about 5 wt%, or about 1.5 to 3 wt%. In some embodiments, the cathode electrode film includes a binder in an amount of about 1.5 to about 3 wt%.In some embodiments, the cathode electrode film comprises a binder in an amount of about 20 wt% or up to about 20 wt%, about 15 wt% or up to about 15 wt%, about 10 wt% or up to about 10 wt%, about 5 wt% or up to about 5 wt%, about 3 wt% or about 3 wt%, about 1.5 wt% or up to about 1.5 wt% or about 1 wt% or up to about 1 wt%, or any value in between these ranges.

[0065] In some embodiments, the binder material may include one or more fibrillatable binder components. For example, the process for forming the electrode film may include fibrillating the fibrillatable binder component such that the electrode film includes a fibrillated binder. The binder component can be fibrillated to provide a plurality of fibrils, and mechanical support for one or more other components of the film is desired for those fibrils. The electrode film may include a structural matrix, lattice, and / or web of fibrils to support the other components of the electrode film. For example, a matrix, lattice, and / or web of fibrils can be formed to provide a desired mechanical structure to the electrode film. For example, the cathode and / or anode of a lithium ion capacitor may include one or more electrode films including one or more fibrillated binder components. In some embodiments, the cathode electrode film comprises a binder in an amount of about 20 wt% or up to about 20 wt%, about 15 wt% or up to about 15 wt%, about 10 wt% or up to about 10 wt%, about 5 wt% or up to about 5 wt%, about 3 wt% or about 3 wt%, about 1.5 wt% or up to about 1.5 wt% or about 1 wt% or up to about 1 wt%, or any value in between these ranges.

[0066] Some embodiments include an electrode film, such as an anode and / or a cathode, having one or more active layers that include a polymeric binder material. The binder can include polytetrafluoroethylene (PTFE), polyolefin, polyalkylene, polyether, styrene butadiene, a copolymer of polysiloxane, polysiloxane, branched polyether, polyvinyl ether, copolymers thereof and / or mixtures thereof. The binder can include cellulose, such as carboxymethyl cellulose (CMC). In some embodiments, the polyolefin can include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), copolymers thereof and / or mixtures thereof. For example, the binder can include polyvinyl chloride, poly(phenylene oxide) (PPO), polyethylene-block-poly(ethylene glycol), poly(ethylene oxide) (PEO), poly(phenylene oxide) (PPO), polyethylene-block-poly(ethylene glycol), polydimethylsiloxane (PDMS), polydimethylsiloxane-core alkylmethylsiloxane, copolymers thereof and / or mixtures thereof. In some embodiments, the binder can be a thermoplastic. In some embodiments, the binder includes a fibrillatable polymer. In certain embodiments, the binder comprises, consists essentially of or consists of PTFE.

[0067] In some embodiments, one or more of the electrode films described herein can be manufactured using a dry manufacturing process. As used herein, a dry manufacturing process can refer to a process in which no solvent or substantially no solvent is used in the formation of the electrode film. For example, the components of the active layer or electrode film, including the carbon material and the binder, can include dry particles. The dry particles for forming the active layer or electrode film can be combined to provide a particle active film mixture. In some embodiments, the active layer or electrode film can be formed from the particle active film mixture such that the weight percentages of the components of the active layer or electrode film and the weight percentages of the components of the dry particle active film mixture are substantially the same. In some embodiments, the active layer or electrode film formed from the dry particle active film mixture using a dry manufacturing process may not contain or may substantially not contain any processing solvent and the resulting solvent residues. In some embodiments, the active layer or electrode film is a self-standing dry particle electrode film formed using a drying process from a dry particle mixture. The process for forming the active layer or electrode film can include fibrillating a fibrillatable binder component such that the film includes a fibrillated binder. In further embodiments, the self-standing active layer or electrode film can be formed without a current collector. In further embodiments, the active layer or electrode film can include a fibrillated polymer matrix such that the film is self-supporting. It is believed that a matrix, lattice, or web of fibrils can be formed to provide a mechanical structure to the electrode film.

[0068] In some embodiments, the electrode film of an energy storage device, where the electrode film is a dry and / or self-standing film, is about 12 mg / cm 2 , about 13 mg / cm 2 , about 14 mg / cm 2 , about 15 mg / cm 2 , about 16 mg / cm 2 , about 17 mg / cm 2 , about 18 mg / cm 2 , about 19 mg / cm 2, approximately 20 mg / cm 2 , approximately 21 mg / cm 2 , approximately 22 mg / cm 2 , approximately 23 mg / cm 2 , approximately 24 mg / cm 2 , approximately 25 mg / cm 2 , approximately 26 mg / cm 2 , approximately 27 mg / cm 2 , approximately 28 mg / cm 2 , approximately 29 mg / cm 2 , approximately 30 mg / cm 2 , approximately 40 mg / cm 2 , approximately 50 mg / cm 2 , approximately 60 mg / cm 2 , approximately 70 mg / cm 2 , approximately 80 mg / cm 2 , approximately 90 mg / cm 2 or approximately 100 mg / cm 2 or may provide a high electrode material filling or a high active material filling (which may be expressed as the weight of the active material per unit area of the electrode film or current collector) of any value within that range. In some embodiments, the electrode film of an energy storage device, where the electrode film is a dry and / or self-supporting film, is at least about 12 mg / cm 2 , at least about 13 mg / cm 2 , at least about 14 mg / cm 2 , at least about 15 mg / cm 2 , at least about 16 mg / cm 2 , at least about 17 mg / cm 2 , at least about 18 mg / cm 2 , at least about 19 mg / cm 2 , at least about 20 mg / cm 2 , at least about 21 mg / cm 2 , at least about 22 mg / cm 2 , at least about 23 mg / cm 2 , at least about 24 mg / cm 2 , at least about 25 mg / cm 2 , at least about 26 mg / cm 2 , at least about 27 mg / cm 2 , at least about 28 mg / cm2 at least about 29 mg / cm 2 at least about 30 mg / cm 2 at least about 40 mg / cm 2 at least about 50 mg / cm 2 at least about 60 mg / cm 2 at least about 70 mg / cm 2 at least about 80 mg / cm 2 at least about 90 mg / cm 2 or at least about 100 mg / cm 2 can provide high electrode material filling, or high active material filling (which can be expressed as the weight per unit area of the electrode film or current collector), or any value range therebetween.

[0069] In some embodiments, an energy storage device electrode film in which the electrode film is a dry and / or self-supporting film has a capacity of about 3.5 mAh / cm 2 or at least about 3.5 mAh / cm 2 about 3.8 mAh / cm 2 or at least about 3.8 mAh / cm 2 about 4 mAh / cm 2 or at least about 4 mAh / cm 2 about 4.3 mAh / cm 2 or at least about 4.3 mAh / cm 2 about 4.5 mAh / cm 2 or at least about 4.5 mAh / cm 2 about 4.8 mAh / cm 2 or at least about 4.8 mAh / cm 2 about 5 mAh / cm 2 or at least about 5 mAh / cm 2 about 5.5 mAh / cm 2 or at least about 5.5 mAh / cm 2 about 6 mAh / cm 2 or at least about 6 mAh / cm 2 about 6.5 mAh / cm 2 or at least about 6.5 mAh / cm 2 about 6.6 mAh / cm 2or at least about 6.6 mAh / cm 2 about 7 mAh / cm 2 or at least about 7 mAh / cm 2 about 7.5 mAh / cm 2 or at least about 7.5 mAh / cm 2 about 8 mAh / cm 2 or at least about 8 mAh / cm 2 or about 10 mAh / cm 2 or at least about 10 mAh / cm 2 or can provide an areal capacity (which can be expressed as the capacity per unit area of the electrode film or current collector) of any value within these ranges. In a further embodiment, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, has at least about 8 mAh / cm 2 e.g., about 8 mAh / cm 2 about 10 mAh / cm 2 about 12 mAh / cm 2 about 14 mAh / cm 2 about 16 mAh / cm 2 about 18 mAh / cm 2 about 20 mAh / cm 2 or can provide an areal capacity (which can be expressed as the capacity per unit area of the electrode film or current collector) of any value within these ranges. In some embodiments, the areal capacity is a charge capacity. In a further embodiment, the areal capacity is a discharge capacity.

[0070] In some embodiments, the anode electrode film of a dry and / or self-supporting graphite battery has about 3.5 mAh / cm 2 about 4 mAh / cm 2 about 4.5 mAh / cm 2 about 5 mAh / cm 2 about 5.5 mAh / cm 2 about 6 mAh / cm 2 about 6.5 mAh / cm 2 about 7 mAh / cm 2 about 7.5 mAh / cm 2 about 8 mAh / cm 2 about 8.5 mAh / cm 2, about 9 mAh / cm 2 , about 10 mAh / cm 2 , or values in any range therebetween, can provide areal capacity. In some embodiments, the areal capacity is the charge capacity. In further embodiments, the areal capacity is the discharge capacity.

[0071] In some embodiments, an energy storage device electrode film in which the electrode film is a dry and / or self-supporting film can provide a specific capacity of about 150 mAh / g, about 160 mAh / g, about 170 mAh / g, about 175 mAh / g, about 176 mAh / g, about 177 mAh / g, about 179 m Ah / g, about 180 mAh / g, about 185 mAh / g, about 190 mAh / g, about 196 mAh / g, about 200 mAh / g, about 250 mAh / g, about 300 mAh / g, about 350 mAh / g, about 354 mAh / g or about 400 mAh / g, or values in any range therebetween (which can be expressed as the capacity per mass of the active material). In further embodiments, an energy storage device electrode film in which the electrode film is a dry and / or self-supporting film can provide a specific capacity of at least about 175 mAh / g or at least about 250 mAh / g, or values in any range therebetween (which can be expressed as the capacity per mass of the electrode film or current collector). In some embodiments, the specific capacity is the charge capacity. In further embodiments, the specific capacity is the discharge capacity. In some embodiments, the electrode can be an anode and / or a cathode. In some embodiments, the specific capacity can be the initial charge and / or discharge capacity. In further embodiments, the specific capacity can be the charge and / or discharge capacity measured after the initial charge and / or discharge.

[0072] In some embodiments, the self-supporting dry electrode film described herein may advantageously exhibit improved performance compared to typical electrode films. The performance can be, for example, tensile strength, elasticity (elongation), bendability, Coulombic efficiency, capacity, or conductivity. In some embodiments, an energy storage device electrode film in which the electrode film is a dry and / or self-supporting film may have a Coulombic efficiency of, for example, about 85% or at least about 85%, about 86% or at least about 86%, about 87% or at least about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, or about 95%, or any value in the range between these, such as 90.1%, 90.5%, and 91.9% or any value in the range between these, for the first cycle Coulombic efficiency (which can be expressed as the percentage of the discharge capacity divided by the charge capacity).

[0073] In some embodiments, an energy storage device electrode film or electrode in which the electrode film is a dry and / or self-supporting film or the electrode includes a dry and / or self-supporting film may have a discharge capacity retention percentage of, for example, about 10% or at least about 10%, about 20% or at least about 20%, about 30% or at least about 30%, about 40% or at least about 40%, about 50% or at least about 50%, about 60% or at least about 60%, about 70% or at least about 70%, about 80% or at least about 80%, about 90% or at least about 90%, about 98% or at least about 98%, about 99% or at least about 99%, about 99.9% or at least about 99.9%, or about 100% or at least about 100%, or any value in the range between these, which can be represented by dividing the discharge capacity at a given rate by the discharge capacity measured at C / 10. In some embodiments, the discharge rate of the charge capacity retention percentage is C / 10 or more, C / 5 or more, C / 3 or more, C / 2 or more, 1C or more, 1.5C or more, or 2C or more, or any value between these.

[0074] In some embodiments, an energy storage device electrode film or electrode, wherein the electrode film is a dry and / or self-supporting film or the electrode includes a dry and / or self-standing film, can provide a charge capacity generation percentage of about 10% or at least about 10%, about 20% or at least about 20%, about 30% or at least about 30%, about 40% or at least about 40%, about 50% or at least about 50%, about 60% or at least about 60%, about 70% or at least about 70%, about 80% or at least about 80%, about 90% or at least about 90%, about 98% or at least about 98%, about 99% or at least about 99%, about 99.9% or at least about 99.9%, about 100% or at least about 100%, or any value in between (which can be represented by dividing the charge capacity measured at a given constant current rate by the discharge capacity measured at C / 10). In some embodiments, the charge rate of the charge capacity generation percentage is at least C / 10, C / 5, C / 3, C / 2, 1C, 1.5C or 2C, or any value in between.

[0075] In some embodiments, an energy storage device electrode film, wherein the electrode film is a dry and / or self-supporting film, can have a specific energy density or mass energy density (which can be represented as the energy per unit mass of the electrode film) of about 200 Wh / kg, about 210 Wh / kg, about 220 Wh / kg, about 230 Wh / kg, about 240 Wh / kg, about 250 Wh / kg, about 260 Wh / kg, about 270 Wh / kg, about 280 Wh / kg, about 290 Wh / kg, about 300 Wh / kg, about 400 Wh / kg, about 500 Wh / kg, about 600 Wh / kg, about 650 Wh / kg, about 700 Wh / kg, about 750 Wh / kg, about 800 Wh / kg, about 825 Wh / kg, about 850 Wh / kg or about 900 Wh / kg, or any value in between.

[0076] In some embodiments, an energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, may have an energy density or volumetric energy density (which can be expressed as the energy per unit volume of the final or in situ electrode film) of about 550 Wh / L, about 600 Wh / L, about 630 Wh / L, about 650 Wh / L, about 680 Wh / L, about 700 Wh / L, about 750 Wh / L, about 850 Wh / L, about 950 Wh / L, about 1100 Wh / L, about 1400 Wh / L, about 1425 Wh / L, about 1450 Wh / L, about 1475 Wh / L, about 1500 Wh / L, about 1525 Wh / L or about 1550 Wh / L, or any value within a range between these.

[0077] FIG. 2 is a process flow diagram showing an example of a process 200 for manufacturing an electrode film according to some embodiments. In some embodiments, the process 200 for manufacturing an electrode film is a dry process that does not use a liquid or solvent such that the resulting electrode film does not contain or substantially contains no liquid, solvent, and resulting residue. At block 202, an electrode film mixture containing an electrode salt is formed. In some embodiments, the electrode film mixture may further contain an electrode active material. In some embodiments, the electrode film mixture may further contain carbon particles. In some embodiments, the electrode film mixture may further contain a binder material. Optionally, one or more conductive promoting additives may be combined, such as graphene, graphite, or carbon nanotubes. In some embodiments, the electrode film mixture is a dry particle mixture. In some embodiments, the binder material includes one or more fibrillatable polymers such as polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE). In some embodiments, the binder material is composed of or essentially composed of one type of polymer such as PTFE. In some embodiments, the conductive promoting additive may be one or more conductive carbons. For example, the conductive carbon may include one or more types of carbon black and / or graphite described herein.

[0078] In some embodiments, a continuous mixing process can be used. In such embodiments, the time for mixing and / or milling can be inversely proportional to the feed rate. Generally, the feed rate depends on the milling machinery and can be adjusted based on the operating parameters of that machine, taking into account the guidance provided herein. In further embodiments, an apparatus having a larger channel can be used to increase the time for mixing and / or milling. When using a batch mixing and / or milling process, the time can be increased by simply mixing and / or milling for a longer time and / or at a higher RPM.

[0079] In block 204, the electrode film mixture can be fibrillated to form fibrils from the binder material. The fibrillation process can reduce the speed and / or the processing pressure It can be done by raising it, etc. Lowering the speed and / or increasing the processing pressure can promote an increase in fibril formation so that an electrode film having a desired resistance to tensile, shear, compression, and / or torsional stress can be formed using a smaller amount of binder material. As described herein, in some embodiments, the fibrillation process can be a mechanical shearing process, including, for example, a mixing and / or grinding process. In some embodiments, the speed at which the particles of the electrode film mixture circulate through the blender and / or mill can be decreased during the fibrillation process. In some embodiments, the processing pressure within the blender and / or mill during the fibrillation process can be increased. In some embodiments, the forming step of block 202 and the fibrillation step of block 204 can be one or substantially one continuous process. Decreasing the speed and / or increasing the processing pressure can enable the production of an electrode film having sufficient strength, such as a self-supporting electrode film, for example, by either a single higher-pressure calendering process (a single step) or multiple calendering process steps, for example, at this time the film is unwound, and then the film is re-calendered one or more times after the first calendering process step.

[0080] In block 206, the electrode film mixture can be calendared in a calendaring apparatus to form a self - standing fibrillated electrode film. The calendaring apparatus is well - known in the art and generally comprises a pair of calendar rolls (having either a mechanically fixed spacing or a spacing fixed by hydraulic or pneumatic pressure) between which a raw material such as an electrode film mixture is supplied to form the electrode film. In some embodiments, the electrode film is formed in a first calendaring step without an additional calendaring step and can form a film with a desired minimum thickness as further described herein. In some embodiments, the calendared mixture forms a self - standing dry particle film that does not contain or substantially does not contain liquids, solvents, and residues resulting therefrom. In some embodiments, the electrode film is an anode electrode film. In some embodiments, the electrode film is a cathode electrode film.

[0081] In block 208, the electrode film is exposed to a solvent to form an electrode film exposed to the solvent. When the electrode film is exposed to the solvent, electrode salts can be extracted. In some embodiments, the extracted electrode salts can function as ionic components of the electrolyte system of the energy storage device. In some embodiments, the extraction of the electrode salts can result in an increase in pore volume and a decrease in the overall density of the electrode film. In some embodiments, the electrode film is exposed to a solvent within a container of the energy storage device, such as container 120 of the energy storage device shown in FIG. 1. In some embodiments, the electrode film is exposed to a solvent outside the container of the energy storage device. For example, the electrode film may be exposed to the solvent of an electrolyte bath. In some embodiments, the electrode film can be exposed to the solvent as a free-standing electrode film or as part of an electrode further including a current collector. In some embodiments, the electrode film can be simultaneously exposed to an electric current while being exposed to the solvent. In some embodiments, the electrode film can be simultaneously pre-lithiated while being exposed to the solvent. In some embodiments, block 208 is not executed, such as in a process for manufacturing a solid electrode film, thereby allowing the electrode salts to remain within the electrode film. In such embodiments, the electrode salts can function as a solid electrolyte in a solid energy storage device.

[0082] In some embodiments, the electrode film exposed to the solvent has a porosity in the range of 1 to 50% of the free pore volume in the electrode. In some embodiments, the electrode film exposed to the solvent has a porosity in the range of 1 to 10% of the free pore volume in the electrode. In some embodiments, the electrode film exposed to the solvent has a film thickness of 20 to 300 μm. In some embodiments, the electrode film exposed to the solvent has a film thickness of 50 to 150 μm.

[0083] In other examples, the dry electrode or dry electrode film may include a dry foam. In some embodiments, the foam may be a metal foam. In some embodiments, the foam may be a ceramic foam. In some conventional energy storage devices, for example, high-density aluminum is used as a current collector or in combination with a current collector and other electrode film materials, but the relatively small contact area between the surfaces of the electrode film and the current collector can result in insufficient electron transfer, and thus may result in insufficient rate capabilities. However, using a foam such as a metal foam as a current collector can significantly increase the power of the energy storage device by utilizing a three-dimensional interconnected porous structure that encapsulates the active material and increases the contact area between the foam current collector and the active material, thereby enhancing the rate performance of the energy storage device. Further, the use of a foam such as a ceramic foam can provide an ion source and act as an ion conductor. For example, a foam containing lithium lanthanum zirconate (LLZO) can conduct lithium ions. Further, by encapsulating the active material within a foam such as a metal foam and a ceramic foam, the need to include an inert component such as a binder in the electrode mixture can be reduced or eliminated. Minimization or elimination of the inert component can result in an increase in the energy density of the electrochemical device. Further, encapsulation of the active material within the foam can reduce at least a portion of the electrode volume strain associated with the charge / discharge process. As an example, the volume expansion and contraction of a conventional lithium-ion battery electrode during cycling can shorten the cycle life. In some embodiments, the electrode film mixture or self-standing electrode film may be encapsulated by the foam. In some embodiments, the electrode film mixture or self-standing electrode film may be pressed against the foam. In some embodiments, the electrode film mixture or self-standing electrode film may be calendered against the foam. In some embodiments, the foam may be commercially available.

[0084] In some embodiments, the foam functions as a housing for the active material. In some embodiments, the foam functions as a housing for the active material and provides sufficient conductivity such that no current collector need be used, even if an additional current collector is used. Such a foam-active material composite is characterized as a dry electrode for the purposes of the present disclosure. An example of such a composite is an active material encapsulated by a metal foam.

[0085] In some embodiments, the foam functions as a housing for the active material but requires a current collector without providing sufficient conductivity. Such a foam-active material composite is characterized as a dry electrode film for the purposes of the present disclosure. Since ceramics are typically electrically insulating, an example of such a composite is an active material encapsulated by a ceramic foam. Thus, in some embodiments, the foam-active material composite can be laminated to a current collector. In some embodiments, the current collector is a metal current collector. In some embodiments, the lamination can be performed by calendaring. In some embodiments, the calendaring can be performed using a two-roll calendar press.

[0086] Figure 3 is a process flow diagram showing an example of a process 300 for encapsulating an electrode film mixture within a foam. In some embodiments, the electrode film mixture in process 300 can be a cathode or anode electrode film mixture as described hereinabove. In some embodiments, the electrode film mixture in process 300 is a cathode electrode film mixture. In some embodiments, the process 300 for encapsulating the electrode film mixture within the foam is a dry process that does not use a liquid or solvent such that the resulting electrode film is free of or substantially free of liquid, solvent, and resulting residues. In block 302, an electrode film mixture is formed. In some embodiments, the electrode film mixture can include a lithium ion conductive ceramic material. In some embodiments, the lithium ion conductive ceramic material is lithium lanthanum zirconium It may be selected from at least one of zirconate (LLZO), lithium nitride, lithium aluminum phosphate germanium (LAGP), lithium zinc germanium oxide (LISICON), lithium germanium phosphorus sulfide (Thio-LISICON), lithium aluminum titanium phosphate (LATP), and lithium sulfide. In some embodiments, the amount of the lithium ion conductive ceramic material in the electrode film mixture is 0.5 wt% or about 0.5 wt%, 1 wt% or about 1 wt%, 5 wt% or about 5 wt%, 10 wt% or about 10 wt%, 20 wt% or about 20 wt%, 30 wt% or about 30 wt%, 40 wt% or about 40 wt%, 50 wt% or about 50 wt% or 60 wt% or about 60 wt%, or any value in the range therebetween. For example, in some embodiments, the amount of the lithium ion conductive ceramic material in the electrode film mixture may be in the range of about 1 to about 50 wt%. In some embodiments, the electrode film mixture may further comprise other materials described herein, such as, for example, an active material, carbon particles, and / or a binder material. In some embodiments, the active material may be selected from at least one metal oxide such as a lithium metal oxide. In some embodiments, the lithium metal oxide may be selected from at least one of lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium nickel manganese cobalt oxide, and lithium nickel cobalt aluminum oxide. Optionally, one or more conductive promoting additives may be combined. In some embodiments, the electrode film mixture is a dry particle mixture.

[0087] In some embodiments, the electrode film mixture does not contain a binder material, may substantially not contain a binder material, or has a lower amount of binder material compared to an electrode without a foam. In some embodiments, the electrode film mixture contains less binder material at about 0%, 0.5%, 1%, 1.5% or 2% or any value in the range therebetween compared to an electrode without a foam. In some embodiments, the binder material includes one or more fibrillatable polymers such as polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE). In some embodiments, the binder material is composed of or consists essentially of one type of polymer such as PTFE. In some embodiments, the conductivity enhancing additive can be one or more conductive carbons. For example, the conductive carbon can include one or more types of carbon black and / or graphite described herein.

[0088] In block 304, the electrode film mixture is encapsulated with a foam. In some embodiments, the foam is a metal foam or a ceramic foam. In some embodiments, the metal foam is selected from at least one of aluminum foam, nickel foam, titanium foam, silver foam, copper foam, cobalt foam, and steel foam. In some embodiments, the ceramic foam is selected from at least one of aluminum oxide foam, silicon dioxide foam, silicon carbide foam, boron nitride foam, and boron carbide foam. In some embodiments, the foam includes a porous structure. In some embodiments, the foam has a relative density between 0.03 and 0.3, where the relative density is defined as the ratio of the foam density to the density of a non-porous reference material such as non-porous metal or non-porous ceramic. In some embodiments, the foam is about 0.1 g / cm 3 or up to about 0.1 g / cm 3 , about 0.3 g / cm 3 or up to about 0.3 g / cm 3 , about 0.4 g / cm 3 or up to about 0.4 g / cm 3, about 0.5 / cm 3 or up to about 0.5 g / cm 3 , about 0.6 g / cm 3 or up to about 0.6 g / cm 3 , about 0.7 g / cm 3 or up to about 0.7 g / cm 3 , about 0.8 g / cm 3 or up to about 0.8 g / cm 3 , about 0.9 g / cm 3 or up to about 0.9 g / cm 3 , about 1.0 g / cm 3 or up to about 1.0 g / cm 3 , about 1.5 g / cm 3 or up to about 1.5 g / cm 3 , about 2.0 g / cm 3 or up to about 2.0 g / cm 3 , or has a density of any value between these. In some embodiments, the foam is about 25% or at least about 25%, about 2 It has a porosity of 8% or at least about 28%, about 30% or at least about 30%, about 40% or at least about 40%, about 50% or at least about 50%, about 60% or at least about 60%, about 70% or at least about 70%, about 80% or at least about 80%, about 85% or at least about 85%, about 90% or at least about 90%, about 95% or at least about 95% or about 98% or at least about 98%, or any value within the range therebetween. In some embodiments, the foam has a primary pore size or pore diameter of about 0.1 mm, up to about 0.1 mm or at least about 0.1 mm, about 0.2 mm, up to about 0.2 mm or at least about 0.2 mm, about 0.3 mm, up to about 0.3 mm or at least about 0.3 mm, about 0.4 mm, up to about 0.4 mm or at least about 0.4 mm, about 0.5 mm, up to about 0.5 mm or at least about 0.5 mm, about 0.6 mm, up to about 0.6 mm or at least about 0.6 mm, about 0.7 mm, up to about 0.7 mm or at least about 0.7 mm, about 0.8 mm, up to about 0.8 mm or at least about 0.8 mm, about 0.9 mm, up to about 0.9 mm or at least about 0.9 mm, about 1 mm, up to about 1 mm or at least about 1 mm, about 1.5 mm, up to about 1.5 mm or at least about 1.5 mm, about 1.6 mm, up to about 1.6 mm or at least about 1.6 mm, about 2 mm, up to about 2 mm or at least about 2 mm, about 3 mm, up to about 3 mm or at least about 3 mm, about 4 mm, up to about 4 mm or at least about 4 mm, about 5 mm, up to about 5 mm or at least about 5 mm, about 6 mm, up to about 6 mm or at least about 6 mm, about 7 mm, up to about 7 mm or at least about 7 mm, about 8 mm, up to about 8 mm or at least about 8 mm, about 9 mm, up to about 9 mm or at least about 9 mm, about 10 mm, up to about 10 mm or at least about 10 mm, about 15 mm, up to about 15 mm or at least about 15 mm, or any value within the range therebetween. In some embodiments, the foam may have open pores. In some embodiments, the foam may have closed pores. In some embodiments, the foam may have open macropores. In some embodiments, the foam may have closed macropores. In some embodiments, the non-porous reference material has a density of about 1 g / cm 3or a minimum of approximately 1 g / cm 3 , approximately 1.5 g / cm 3 or a minimum of approximately 1.5 g / cm 3 , approximately 2 g / cm 3 or a minimum of approximately 2 g / cm 3 , approximately 3 g / cm 3 or a minimum of approximately 3 g / cm 3 , approximately 4 g / cm 3 or a minimum of approximately 4 g / cm 3 , approximately 5 g / cm 3 or a minimum of approximately 5 g / cm 3 or approximately 10 g / cm 3 or a minimum of approximately 10 g / cm 3 , or a value within any range between these.

[0089] Figure 4 is a process flow diagram showing an example of process 400 for pressing a self-supporting electrode film onto a foam. In some embodiments, the self-supporting electrode film in process 400 can be a cathode or anode self-supporting electrode film as described herein. In some embodiments, the self-supporting electrode film in process 400 is a cathode self-supporting electrode film. At block 402, an electrode film mixture is formed. In some embodiments, the electrode film mixture is produced by any method or using any of the foregoing compositions. In some embodiments, the self-supporting electrode film is composed of an active material and a binder. In some embodiments, the self-supporting electrode film further includes conductive carbon. In some embodiments, the self-supporting electrode film further includes conductive carbon and a lithium ion conductive ceramic as described above. In some embodiments, the binder can be selected from at least one of poly(tetrafluoroethylene) (PTFE), polyvinylidene fluoride (PVDF), and carboxymethyl cellulose (CMC). In some embodiments, the total amount of binder in the film can be 0.5 wt% or about 0.5 wt%, 1 wt% or about 1 wt%, 5 wt% or about 5 wt%, 10 wt% or about 10 wt%, 15 wt% or about 15 wt% or 20 wt% or about 20 wt%, or any range of values therebetween. For example, in some embodiments, the total amount of binder in the film is about 1 to about 15 wt%. In some embodiments, the total amount of lithium ion conductive ceramic in the film can be 0.5 wt% or about 0.5 wt%, 1 wt% or about 1 wt%, 5 wt% or about 5 wt%, 10 wt% or about 10 wt%, 20 wt% or about 20 wt%, 30 wt% or about 30 wt%, 40 wt% or about 40 wt%, 50 wt% or about 50 wt% or 60 wt% or about 60 wt%, or any range of values therebetween. For example, in some embodiments, the total amount of lithium ion conductive ceramic in the film ranges from about 1 to about 50 wt%.

[0090] In block 404, the binder in the electrode film mixture is fibrillated. In some embodiments, the fibrillation can be performed by any of the aforementioned methods, such as the process described in block 204 of FIG. 2. In block 406, the electrode film mixture is calendared to form a self-supporting electrode film. In some embodiments, the self-supporting electrode film can be manufactured by any of the aforementioned methods. Without being limited by theory, in some embodiments, after applying a sufficiently high shear force and / or pressure to the electrode film mixture, particles of a sufficiently small size provided or formed within the electrode film mixture become attracted by their surface free energy, providing a support matrix in which other particles can be supported. Without being limited by theory, under sufficient shear force and / or pressure, the particles within the electrode film mixture described herein are theorized to be able to approach each other to a separation distance such that they interact by attractions (such as London - van der Waals forces) arising from the surface free energy inherent to the particles, forming a continuous self-supporting film. In block 408, the self-supporting electrode film is pressed and laminated to the foam. In some embodiments, the self-supporting electrode film is pressed onto the foam by calendaring. In some embodiments, the calendaring can be performed by a two-roll calendar press. In some embodiments, the foam can be manufactured using any method or any composition as described above. In some embodiments, the foam is a metal foam. In some embodiments, the foam is a ceramic foam. In some embodiments, the electrode film - foam composite can be laminated to a current collector. In some embodiments, the film - foam composite can function as an electrode without adding a current collector.

[0091] In some embodiments, when constructing a dry battery by a method known in the art such as winding or laminating electrodes with a separator layer therebetween, a selected solvent or combination of solvents can be added to the dry battery for immediate use. In some embodiments, such as when long calendar life storage is essential, the manufactured dry battery can be stored in a dry state with minimal degradation. In some embodiments, such as for solid energy storage devices, the manufactured dry battery may be ready for immediate use without the addition of a solvent or combination of solvents.

[0092] The electrodes and energy storage devices described herein can be described in the context of lithium-ion capacitors and batteries, but the embodiments can be implemented in any number of energy storage devices and systems, such as one or more batteries, capacitors, capacitor-battery hybrids, fuel cells, solid energy storage devices, combinations thereof, etc., with or without lithium.

[0093] Exposing an electrode film to a solvent within an energy storage device In some embodiments, a battery of an energy storage device comprising an electrode film containing an electrode salt is filled or saturated with one or more electrolyte solvents to extract the electrode salt from the electrode film and dissolve the electrode salt. The dissolved electrode salt can function as an ionic component or solute of the electrolyte system within the energy storage device. Further, extracting the electrode salt from the electrode film can result in an electrode film exposed to the solvent with an increased pore volume and a reduced density throughout the electrode film.

[0094] The salts, solvents, and processing conditions can be selected to achieve the intended function. In some embodiments In a form, the electrode salt and the solvent are selected to be compatible with each other. In some embodiments, an aqueous solvent miscible electrode salt and an aqueous solvent are selected. In some embodiments, a non-aqueous solvent miscible electrode salt and a non-aqueous solvent are selected. In some embodiments, an electrode salt that is susceptible to the influence of moisture is selected. In some embodiments, an electrode salt that is stable under the processing conditions of a normal device is selected. In some embodiments, an electrode salt that does not decompose under the operating conditions of a normal device is selected.

[0095] In some embodiments, the electrode salt is selected from at least one of LiPF6, LiBF4, LiBOB, LiN(SO2CF3)2, LiOSO2CF3, LiNO3, lithium acetate, lithium halide, tetraalkylammonium tetrafluoroborate, and tetraalkylammonium hexafluorophosphate.

[0096] In some embodiments, the solvent is selected from at least one of carbonates, esters, amides, ethers, alcohols, sulfones, and water. In some embodiments, the solvent is a volatile solvent. In some embodiments, the solvent is a highly volatile solvent, where the solvent is a gas at ambient temperature and pressure. In some embodiments, the highly volatile solvent is a liquid under a pressure exceeding 1 atmosphere. In some embodiments, the highly volatile solvent is a liquid at a temperature below 20°C. In some embodiments, the highly volatile solvent has a boiling point at ambient pressure of about 10°C or up to about 10°C, about 20°C or up to about 20°C, about 30°C or up to about 30°C, about 40°C or up to about 40°C, about 50°C or up to about 50°C, about 57°C or up to about 57°C, about 60°C or up to about 60°C, about 66°C or up to about 66°C, about 70°C or up to about 70°C, about 80°C or up to about 80°C, about 90°C or up to about 90°C, about 91°C or up to about 91°C, or about 95°C or up to about 95°C, or a value within any range therebetween. In some embodiments, the highly volatile solvent can be dimethyl carbonate, tetrahydrofuran (THF), methyl acetate, or a mixture thereof. In some embodiments, the highly volatile solvent produces an electrode film exposed to the solvent having an increased porosity compared to an electrode film exposed to a non-volatile solvent. In some embodiments, the highly volatile solvent has a lower melting point than the non-volatile solvent and remains liquid even at low temperatures, enabling the energy storage device to operate at a low temperature environment, such as about -150°C or at least about -150°C, about -110°C or at least about -110°C, about -108°C or at least about -108°C, about -100°C or at least about -100°C, about -98°C or at least about -98°C, about -75°C or at least about -75°C, about -50°C or at least about -50°C, about -25°C or at least about -25°C, about 0°C or at least about 0°C, about 2°C or at least about 2°C, about 4°C or at least about 4°C, about 5°C or at least about 5°C, or about 10°C or at least about 10°C, or any value therebetween. In some embodiments, the highly volatile solvent enables a higher concentration of electrolyte salt to be dissolved compared to the non-volatile solvent.

[0097] In some embodiments, a solvent is added to a dry energy storage device comprising a dry electrode film. In some embodiments, the total amount of the electrode salt is selected to provide an electrolyte within the energy storage device at a target molar concentration. In some embodiments, the total amount of the salt can be measured at the positive electrode. In some embodiments, the total amount of the salt can be measured at the negative electrode. In some embodiments, the total amount of the salt can be evenly measured at the positive and negative electrodes. In some embodiments, the total amount of the salt can be measured in any unequal amounts to the positive and negative electrodes, such as, for example, 10:90, 25:75, 45:55, 55:45, 75:25, and 90:10 or any range between any of these values.

[0098] In some embodiments, the electrode film is a cathode electrode film.

[0099] Washing of the Electrode Film In some embodiments, to extract and dissolve the electrode salt from the electrode film the electrode film containing the electrode salt is washed with one or more electrolyte solvents separate from the container of the energy storage device. Extracting the electrode salt from the electrode film can result in an electrode film exposed to the solvent with an increased pore volume and a reduced density throughout the electrode film. Further, in some embodiments, the use of the electrode salt material within the dry electrode film enables pre-lithiation of the electrode film simultaneously with the washing process. In other embodiments, the washed electrode film may be pre-lithiated after the washing process, for example, the pre-lithiation of the electrode film may be performed in a separate pre-lithiation device or within the container of the energy storage device.

[0100] FIG. 5 is a schematic diagram showing an embodiment of a cleaning device 500 that simultaneously performs a pre-lithiation process of an electrode film containing an electrode salt. An electrode film roll 501 containing a dry electrode salt is placed on an unwinder 502 and negatively polarized using a power source 503. The dry electrode film roll 501 can be prepared by any of the above methods. The dry electrode film roll 501 is unwound, wound into an electrode film sheet 504, and immersed in a solvent bath 505 containing a solvent 506. The electrode film sheet 504 is floated in the solvent 506 between rollers 507 and between at least one pair of counter electrodes 508 positively polarized by the power source 503. When the electrode film sheet 504 is floated in the solvent 506, the electrode salt dissolves from the electrode film sheet 504 into the solvent 506. At the same time, due to the negative polarization of the electrode film sheet 504 and the positive polarization of the pair of counter electrodes 508, the electrode film sheet 504 is electrochemically pre-lithiated with the lithium component of the electrode salt. The electrode film sheet exits the solvent 506 and the solvent bath 505 as a lithiated electrode film 509. The lithiated electrode film 509 is recovered and rewound at a rewinding portion 510 into a rewound lithiated electrode 511. In some embodiments not shown, the lithiated electrode film 509 may be rinsed in a rinsing bath before being rewound into the rewound lithiated electrode 511. In some embodiments not shown, the lithiated electrode film 509 may be dried to remove the solvent 506 from the solvent bath 505 or the rinsing bath before being rewound into the rewound lithiated electrode 511. In some embodiments, pre-lithiation of the electrode film sheet 504 is not performed, and thus the power source 503 and the pair of counter electrodes 508 are not utilized or are not present in the device 500.

[0101] In some embodiments, the solvent of the solvent bath is dimethyl carbonate. In some embodiments, the solvent does not contain an electrolyte salt. In some embodiments, the solvent further contains an electrolyte salt. In some embodiments, the electrolyte salt is lithium fluoride. In some embodiments, the electrolyte salt of the solvent is the same as the electrode salt of the electrode film or the electrode as described above.

[0102] In some embodiments, the dry electrode can be a cathode or an anode electrode. In some embodiments, the dry electrode is an anode electrode. In some embodiments, the dry electrode includes graphite. In some embodiments, the dry electrode includes silicon. In some embodiments, the counter electrode is a vitreous carbon electrode.

[0103] In some embodiments, the lithiated electrode film is substantially free of or does not contain electrode salts. In some embodiments, the rewound lithiated electrode film is substantially free of or does not contain electrode salts. In some embodiments, the lithiated electrode film has pores.

[0104] In some embodiments, an energy storage device comprising a lithiated electrode film further includes an added electrolyte salt. In some embodiments, the energy storage device includes an anode comprising the lithiated electrode film and a cathode comprising the cathode film such that the total amount of salt from the porous electrode can be measured at the anode. In some embodiments, the total amount of salt can be measured equally at the positive and negative electrodes. In some embodiments, the total amount of salt can be measured in any unequal amount to the positive and negative electrodes, such as, for example, 10:90, 25:75, 45:55, 55:45, 75:25 and 90:10 or any range between any of these values.

[0105] Solid electrode The electrode treatment method described in this specification includes mixing a dry solid electrolyte additive with a dry active material in a drying process to produce the dry electrode film. A close mixture of a solid electrolyte salt or a solid electrolyte additive and an active material of this nature can help reduce the electrolyte-active material interfacial resistance, which is known to be very high in typical solid lithium-ion batteries. Compared with the wet electrode process, the dry electrode process can also provide closer contact at the solid electrolyte-active material interface and reduce the solvent-induced degradation of the solid electrolyte that is susceptible to the influence of moisture. In some embodiments, no addition or removal of a solvent is performed. Furthermore, since the drying of the solvent is not required in the dry electrode coating process, a densely packed particle matrix can be produced to increase the contact between ions and electrons and the active material, and overall lower the resistance of the electrode.

[0106] In some embodiments, the solid electrode is formed from electrolyte electrode powder in a manner similar to that described above. In some embodiments, the electrolyte electrode powder is prepared by mixing an active material with a solid electrolyte additive. In some embodiments, the electrolyte electrode powder further includes a binder. In some embodiments, the binder is at least one of poly(ethylene oxide), poly(tetrafluoroethylene), poly(vinylidene difluoride), and carboxymethyl cellulose. In some embodiments, the binder is a fibrillatable binder. In some embodiments, the molecular weight of the binder is from about 1000 to about 5×10 6 g / mol. In some embodiments, the binder may include a polymer having a combination or range of multiple molecular weights. In some embodiments, the binder constitutes about 2 to about 40 wt% of the electrolyte electrode powder. In some embodiments, the binder constitutes about 1 to 15 wt% of the electrolyte electrode powder.

[0107] In some embodiments, the active material is lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium nickel manganese cobalt oxide, lithium nickel cobalt aluminum oxide, and LiNi such as NMC811 1-x-y Cox Mn y is at least one of O2 (NCM). In some embodiments, the cathode active material constitutes 40 to 90% by weight of the electrolyte electrode powder.

[0108] In some embodiments, the solid electrolyte additive is a lithium salt. In some embodiments, the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium perchlorate. In some embodiments, the solid electrolyte additive is a garnet ion conductor, such as Li5La3Ta2O 12 and Li3N. In some embodiments, the solid electrolyte additive is a sulfur-based ion conductor, such as Li2S-P2S5 and Li2S-P2S5-Li3PO4. In some embodiments, the solid electrolyte additive is another compound with high ionic conductivity, such as Li 0.5 La 0.5 TiO3 (LLTO) and / or Li7La3Zr2O 12 (LLZO). In some embodiments, the solid electrolyte additive is a lithium superionic conductor (LISCON). For example, LISCON may have a molecular formula of Li (2+2x) Zn (1-x) GeO4. In some embodiments, the lithium salt constitutes 1 to 10% by weight of the electrolyte electrode powder.

[0109] In some embodiments, the dry solid electrode film has a porosity in the range of about 1 to about 50% of the free void volume within the electrode film. In some embodiments, the dry solid electrode film has a porosity of about 1 to about 10% of the free void volume within the electrode film. In some embodiments In some embodiments, the dry solid electrode film has a film thickness of about 20 to about 300 μm. In some embodiments, the dry solid electrode film has a film thickness of about 50 to about 150 μm. In some embodiments, the porosity, density, and / or thickness of the dry solid electrode film can be any other value described throughout the present disclosure.

[0110] An exemplary drying procedure for preparing the solid electrode is as follows. The cathode active material of NMC811 is dry mixed with LLZO at a mass ratio of about 7:2 (NMC811:LLZO). Conductive carbon is added to the mixed electrolyte-electrode powder of the active material-LLZO powder at a ratio of about 0.5 parts by mass and further homogenized. About 0.5 parts by mass of a binder is added to the mixture and mixed under high shear force to produce a powder formulation prepared for manufacturing a free-standing electrode film. The prepared powder formulation is pressed against a free-standing solid electrode film by a two-roll calender press. Then, when the film is laminated onto a metal current collector by a two-roll calender press, a dried solid cathode is obtained.

[0111] In some embodiments, the solid battery is prepared by stacking a dried solid cathode with a lithium metal electrode sandwiching a thin solid electrolyte layer therebetween. The thin solid electrolyte layer can be pre-coated on the lithium metal or on the solid cathode using a solid electrolyte composition used in the cathode or an alternative solid electrolyte having similar ionic conductivity and similar operating voltage stability. In some embodiments, the solid battery does not contain a liquid solvent.

[0112] Solid polymer electrolyte The foregoing dry powder mixing and film calendering process can also be utilized to produce composite polymer films for use as ion-conductive solid separators or electrolytes in solid energy storage devices such as solid lithium metal batteries. The drying process of the solid polymer electrolyte membrane provides an environmentally friendly manufacturing process that minimizes the generation of toxic solvent waste, a process that does not include an additional time-consuming film drying step to evaporate solvents or residual water from the membrane, the ability to tailor thinner polymer membranes, high electrochemical performance due to the absence of residual organic solvents in the polymer electrolyte film, and the ability to enable a continuous roll-to-roll manufacturing process for both the polymer membrane and the complete cell assembly, offering many advantages compared to conventional wet solvent cast preparation. The drying process and solvent-free composite polymer films by the dry powder mixing and film calendering process are described, and the physical and electrochemical properties of such films are shown.

[0113] In some embodiments, the composite solid polymer electrolyte (SPE) comprises at least one ion-conductive polymer. In some embodiments, the SPE comprises at least one lithium source. In some embodiments, the SPE comprises at least one supporting polymer binder. In some embodiments, the SPE comprises at least one filler. In some embodiments, the SPE comprises at least one ion-conductive medium. In some embodiments, the SPE comprises at least one ion-conductive polymer and at least one lithium source. In some embodiments, the SPE comprises at least one ion-conductive polymer, at least one lithium source, and at least one supporting polymer. In some embodiments, the SPE comprises at least one ion-conductive polymer, at least one lithium source, at least one supporting polymer, and at least one filler. In some embodiments, the SPE comprises at least one ion-conductive polymer, at least one lithium source, at least one supporting polymer, at least one filler, and at least one ion-conductive medium.

[0114] In some embodiments, the ion-conducting polymer is polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly(methylene oxide), polyoxymethylene , poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone) (PVP), poly(methyl methacrylate), poly(vinyl acetate), poly(vinyl chloride), poly(vinyl acetate), poly(oxyethylene) 9 methacrylate, poly(ethylene oxide) methyl ether methacrylate, and poly(propylene imine).

[0115] In some embodiments, the lithium source is lithium perchlorate (LiClO), lithium tetrafluoroborate (LiBF), lithium hexafluorophosphate (LiPF), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (Li(CFSO)N), lithium bis(oxalato)borate (LiB(C0)), lithium trifluoromethanesulfonate (LiCFSO), lithium bis(pentafluoroethanesulfonyl)imide (CF 10 LiNO4S2), lithium bis(fluorosulfonyl)imide (F2LiNO4S2), lithium difluoro(oxalato)borate (LiBF2(C2O4), lithium difluorophosphate (F2LiO2P), lithium oxalyldifluoroborate, lithium trifluorochloroborate (LiBF3Cl), lithium hexafluoroarsenate (LiAsF6), Li 6.4 La3Zr 1.4 Ta 0.6 O 12 , Li7La3Zr2O 12 , Li 10 SnP2S 12 , Li 3x La 2 / 3-x TiO3, Li 0.8 La 0.6 Zr2(PO4)3, Li 1+x Ti 2-x Al x (PO4)3, Li 1+x+y Ti 2-x Al x Si y (PO4)3-y and LiTi x Zr 2-x is selected from at least one of (PO4)3. In some embodiments, the lithium source can be the lithium salt or others described above.

[0116] In some embodiments, the support polymer binder is selected from at least one of polyethylene (PE) and polytetrafluoroethylene (PTFE).

[0117] In some embodiments, the filler is a ceramic filler. In some embodiments, the ceramic filler is titanium oxide (TiO2), silica (SiO2), silicon monoxide (SiO), copper oxide (CuO), montmorillonite ((Na,Ca) 0.33 (Al,Mg)2(Si4O 10 ))), bentonite (Al2O 34 SiO2H2O), kaolinite (Al2Si2O5(OH)4), hectorite (Na 0.3 (Mg,Li)3Si4O 10 (OH)2) and halloysite (Al2Si2O5(OH)4), 4'-amino-2,3'-dimethylazobenzene (CH3C6H4N=NC6H3(CH3)NH2), yttrium aluminum oxide (Y3Al5O 12 ), yttrium iron oxide (Y3Fe5O 12 ) and at least one of nanoclay. Table 1 shows the specifications of the dry materials that can be used for the SPE film.

[0118] In some embodiments, the ion conductive medium is nanoclay, garnet or a mixture thereof.

[0119]

Table 1

[0120] In one example, polyethylene oxide (PEO) or polyvinylidene fluoride (PVDF) was used as the ion-conductive polymer, polyethylene (PE), PTFE, and mixtures thereof were used as the support matrix, silica was used as the ceramic filler, garnet was used as the ion-conductive medium, LiTFSI was used as the lithium source, and they were used in various combinations to produce a SPE dry powder formulation. Nanoclay was used as the ceramic filler, but advantageously and unexpectedly, it was found that nanoclay enhances the ionic conductivity of the SPE and thus also functions as an ion-conductive medium. Table 2 shows five such dry SPE formulations.

[0121]

Table 2

[0122] The dry powder mixing of the SPE dry powder formulation into the SPE dry powder mixture can be carried out by the above-described method or other methods. The dry powder mixing of the dry SPE formulations described in Table 2 was carried out according to the mixing procedures shown in Table 3. For example, typical mixing and blending methods such as tumbling, convection, hopper, and fluidization can be used for powder mixing. Resodyn powder mixing was carried out at 60 % strength (50 G) for 5 minutes. Some images of the obtained treated powders are shown in Figure 6. In Figure 6, powder (a) refers to SPE-2, powder (b) refers to SPE-3, powder (c) refers to SPE-4, and powder (d) refers to SPE-5.

[0123]

Table 3

[0124] The treated dry powder mixture can be formed into a dry self-supporting SPE film by the above-described method or other methods. It can be transformed into a mu. The dry SPE film was produced from some of the dry powder mixtures described in Table 3 after calendaring with the parameters shown in Table 4. Figure 7 shows the first-pass calendared SPE film transformed from the dry powder processed according to the first calendaring process in Table 4. In Figure 7, (a) shows SPE-2 (during calendaring), (b) shows SPE-1, (c) shows SPE-3, and (d) shows SPE-4; (b) to (d) all show after calendaring. Figure 8 shows the first-pass calendared SPE film of Figure 7 re-calendared according to the second calendaring process in Table 4 to achieve the desired film thickness.

[0125]

Table 4

[0126] Figure 9 shows the surface morphology of the SPE-4 film after the first calendaring step, and Figure 10 shows the surface morphology of the SPE-4 film after the second calendaring step. The first-pass calendared SPE-4 film shows a rough and irregular surface, seemingly suggesting phase separation between the ion-conductive polymer and the supporting polymer matrix. The second-pass calendared SPE-4 film shows a smoother surface than the first-pass calendared film and the PTFE fiber. Also, in Figure 10, a relatively high-density SPE film without pores is observed. This can increase the ionic conductivity and prevent the intrusion of lithium dendrites.

[0127] Furthermore, the films after the first pass calendar treatment steps of SPE-1, SPE-2, and SPE-3 were brittle, while the films after the second pass calendar treatment steps became more flexible. Additionally, in the SPE-4 and SPE-5 films, due to the presence of fibrillated PTFE within the film, very flexible and strong self-standing drying films were produced. As shown in Figure 11, the mechanical strength of the self-standing drying SPE-4 film by the ILLord tensile test had a very high tensile strength peak (10.3 N) and a relatively long elongation (2.3 mm). Table 5 shows the specifications of the drying SPE films used in the tensile strength measurement shown in Figure 11.

[0128]

Table 5

[0129] The ionic conductivity (σ) of the drying SPE film was calculated using the following equation.

[0130] σ=(1 / R s )x(L / A); where R s is the bulk impedance, L is the thickness of the SPE film, and A is the area of the SPE film.

[0131] The bulk impedance was measured using a symmetric Cu / SPE / Cu cell. Figure 12 shows the values of the room temperature ionic conductivity of the SPE-4 and SPE-5 films. The ionic conductivity of the dried SPE film is approximately one order of magnitude higher than that reported in the prior art using PEO-based polymer electrolytes.

[0132] The lithium stripping and deposition performance of the dried SPE film using a symmetric Li / SPE / Li cell was also investigated. Due to the low ionic conductivity of the SPE film at room temperature and the high interfacial impedance between the lithium metal and the SPE film, it was found that the cell voltage exceeded 2 V during the first lithium stripping process. As shown in Table 6, when approximately 0.8 mL of a carbonate solvent-based electrolyte was added to the Li / SPE / Li cell, the interfacial impedance decreased significantly, and stable polarization was obtained. Figure 13 shows the first Li stripping / deposition cycle of the SPE-4 and SPE-5 electrolyte films in the Li / Li cell. The voltage of the cell with SPE-5 is lower and more stable compared to the cell with SPE-4. This may be due to the presence of lithium salts in the SPE-5 film.

[0133]

Table 6

[0134] The SPE film was also characterized as a separator for a graphite electrode half-cell, assembled using a laminate of a dried graphite electrode / SPE-1 / Li foil, and sealed in a pouch form. As shown in Table 6, approximately 0.8 mL of a supporting lithium-ion electrolyte was added to the cell. Three different cell configurations used in this electrochemical study are shown in Figure 14. The specifications of the dried graphite electrode and the SPE film are shown in Table 7.

[0135] Figure 15 shows the electrochemical capacity and Coulombic efficiency of graphite electrodes having the three different cell configurations shown in Figure 14. Note that the SPE-1 film is a rigid and porous film and does not contain an ionic conductive medium or lithium salt. Cells 1 and 2 have low electrochemical performance because of the low wettability of the electrolyte with respect to the SPE-1 film and / or the low mechanical stability of the porous SPE-1 film, and thus there is a possibility that lithium dendrites may penetrate and / or immiscibility may occur between the carbonate solvent-based non-aqueous lithium ion electrolyte and the SPE-1 film. However, as shown in Table 6, Cell 3 showed capacities and efficiencies comparable to the prior art, composed of a dry graphite electrode incorporated with a lithium ion electrolyte and a commercially available polypropylene (PP) separator (from Celgard).

[0136]

Table 7

[0137] Figure 17 shows the solid structure of the direct lamination of the SPE layer using a dry electrode. Here, (a) shows a single-sided SPE / electrode, (b) shows a double-sided SPE / electrode, (c) shows a single-sided Li / SPE / electrode (SS), and (d) shows a double-sided Li / SPE / electrode. Also, as shown in Figure 17, the layers of the material can be laminated by a calendaring process.

[0138] Solid gradient electrode The solid electrode is a dry electrode film so as to achieve a gradient electrolyte additive distribution within the solid electrode To generate, as described above, a blend of a dry solid electrolyte additive and a dry active material in the drying process may be included. In some embodiments, to generate a gradient electrolyte additive distribution, a number of solid dry electrode films are generated in which the concentration of the solid electrolyte additive increases with each successive electrode film. In some embodiments, the number of solid dry electrode films are calendared together to form a solid dry electrode film having a gradient of solid electrolyte additive concentration in the direction of film thickness, or a stepped solid dry electrode film. In some embodiments, since the side of the stepped solid dry electrode film that includes the higher concentration of solid electrolyte additive functions as an electrolyte separator within the device, such a stepped solid dry electrode film can be used in a solid energy storage device that does not use a separate electrolyte separator.

[0139] In some embodiments, at least one of the layers of the stepped solid dry electrode film has a solid electrolyte additive concentration of about 20 wt% or more, about 30 wt% or more, about 40 wt% or more, about 50 wt% or more, about 60 wt% or more, about 70 wt% or more, about 80 wt% or more, about 90 wt% or more or about 100 wt% or more or any value in between these ranges. In some embodiments, at least one of the layers of the stepped solid dry electrode film has a solid electrolyte additive concentration of about 40 wt% or more. In some embodiments, one of the outer layers of the stepped solid dry electrode film has a solid electrolyte additive concentration of about 20 wt% or more, about 30 wt% or more, about 40 wt% or more, about 50 wt% or more, about 60 wt% or more, about 70 wt% or more, about 80 wt% or more, about 90 wt% or more or about 100 wt% or any value in between these ranges.

[0140] While specific embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the disclosure. In fact, the novel methods and systems described herein can be embodied in various other forms. Furthermore, various omissions, substitutions, and changes to the systems and methods described herein can be made without departing from the spirit of the disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the disclosure.

[0141] Features, materials, characteristics, or groups described in connection with a particular aspect, embodiment, or example are to be understood as applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless they are mutually incompatible. All features (including the appended claims, abstract, and drawings) disclosed herein and / or all steps of any method or process so disclosed are combinable in any combination, except for at least some combinations where such features and / or steps are mutually exclusive. The protection is not limited to the details of the above embodiments. The protection extends to any novel one or any novel combination of the features disclosed herein (including the appended claims, abstract, and drawings), or any novel one or any novel combination of the steps of any method or process so disclosed.

[0142] Furthermore, specific features described in the context of separate implementations of the disclosure may also be implemented in combination in a single implementation. In contrast, various features described in the context of a single implementation may also be implemented separately in multiple implementations, or in any suitable sub-combination. Additionally, although features may sometimes be described above as acting in a particular combination, one or more features from the claimed combination may in some cases be removed from the combination, and the combination may be claimed as a sub-combination or a variation of a sub-combination.

[0143] Further, operations may be illustrated or described in a particular order, but on the other hand, such operations need not be performed in the particular order shown or in a sequential order to achieve the desired result, nor do all operations need to be performed. Other operations not illustrated or described may be incorporated into the exemplary methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between the operations described. Further, the operations may be rearranged or reordered in other implementations. Those skilled in the art will understand that in some embodiments, the actual steps taken in the illustrated and / or disclosed processes may differ from those shown. Depending on the embodiment, the specific steps described above may be deleted and other steps may be added. Further, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Also, the separation of the various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the components and systems described generally may be integrated together in a single product or packaged in multiple products. For example, any component of the energy storage system described herein may be provided separately or integrated together (e.g., packaged together or attached together) to constitute an energy storage system.

[0144] For purposes of the present disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages may be achieved in accordance with a particular embodiment. Thus, for example, one skilled in the art will recognize that the present disclosure may be embodied or practiced in a manner that achieves one advantage or a group of advantages taught herein without necessarily achieving other advantages that may be taught or suggested herein.

[0145] Conditional language, such as "can", "able to", "might", "may", etc., generally means that other embodiments do not include a particular feature, element, and / or step, unless otherwise specified or understood in a different way within the context in which it is used, while a particular embodiment is intended to convey that it does include them. Thus, such conditional terms generally do not mean that a feature, element, and / or step is necessary in any sense for one or more embodiments, or that one or more embodiments necessarily include logic for determining whether these features, elements, and / or steps are included or are performed in a particular embodiment, regardless of the presence or absence of user input or prompts.

[0146] Connective language, such as the phrase "at least one of X, Y, and Z", is understood in the context in which it is generally used to convey that an item, term, etc. can be any of X, Y, or Z, unless otherwise specified. Thus, such connective language generally does not mean that a particular embodiment requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0147] Degree terms, such as the terms "about", "approximately", "generally", and "substantially" as used herein, represent a value, amount, or characteristic that is close to the recited value, amount, or characteristic and that also performs the desired function or achieves the desired result. For example, the terms "about", "approximately", "generally", and "substantially" may refer to an amount that is less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the recited amount, depending on the desired function or desired result.

[0148] The scope of the present disclosure is not intended to be limited by the specific disclosure of the preferred embodiments in this section or elsewhere in this specification, but may be defined by the claims presented or to be presented in this section or elsewhere in this specification. The language of the claims should be interpreted broadly based on the language used in the claims and not limited to the examples described herein or during the examination of the application, and these examples should be construed as non-exclusive.

[0149] The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the apparatus and methods disclosed herein.

Claims

1. A dry electrode film for an energy storage device, comprising: a dry active material; a dry binder; and a dry electrolyte salt wherein the dry electrode film is self-supporting.

2. The dry electrode film according to claim 1,

3. The dry electrolyte salt is LiPF ６ 、LiBF ４ 、LiBOB、LiN(SO ２ CF ３ ) ２ 、LiOSO ２ CF ３ 、LiNO ３ 、 lithium acetate, lithium halide, tetraalkylammonium tetrafluoroborate, tetraalkylammonium hexafluorophosphate, garnet ion conductor, sulfur-based ion conductor, Li ０．５ La ０．５ TiO ３ (LLTO), Li ７ La ３ Zr ２ O １２ (LLZO), lithium superionic conductor (LISCON), lithium hexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium perchlorate, lithium bis(trifluoromethanesulfonimide (LiTFSI), lithium bis(oxalato)borate, Li ６．４ La ３ Zr １．４ Ta ０．６ O １２ 、Li １０ SnP ２ S １２ 、Li ３ｘ La ２／３－ｘ TiO ３ 、Li ０．８ La ０．６ Zr ２ (PO ４ ) ３ 、Li １＋ｘ Ti ２－ｘ Al ｘ (PO ４ ) ３ 、Li １＋ｘ＋ｙ Ti ２－ｘ Al ｘ Si ｙ (PO ４ ) ３－ｙ and LiTi ｘ Zr ２－ｘ (PO ４ ) ３ A dry electrode film selected from or a combination of these. The dry electrode film according to claim 1 or 2,

4. wherein the dry electrolyte salt constitutes 1 to 10% by weight of the dry electrode film.

5. The dry electrode film according to any one of claims 1 to 3, having a thickness of at least 110 μm.

6. The dry electrode film according to any one of claims 1 to 4, At least 0.8 g / cm ３ Dry electrode film having an electrode film density of

7. A dry gradient electrode film for an energy storage device, comprising: a first dry electrode film according to any one of claims 1 to 5, containing an electrolyte salt of a first concentration; and a second dry electrode film according to any one of claims 1 to 5, containing an electrolyte salt of a second concentration, wherein the electrolyte salt of the first concentration is less than that of the second concentration wherein the dry gradient electrode film has the above components.

8. A solid energy storage device comprising the dry electrode film according to any one of claims 1 to 6, and not containing a liquid solvent.

9. An energy storage device comprising the dry electrode film according to any one of claims 1 to 6 and a solvent within a device housing wherein the energy storage device has the above components.

10. The energy storage device according to claim 8, wherein the solvent is a highly volatile solvent.

11. A battery comprising the dry electrode film according to any one of claims 1 to 6.

12. A method for manufacturing a dry electrode film for an energy storage device, comprising: preparing a dry active material, a dry binder, and a dry electrolyte salt; and forming a self-supporting dry electrode film from the dry active material, the dry binder, and the dry electrolyte salt wherein the method for manufacturing the dry electrode film includes the above steps.

13. The method for manufacturing a dry electrode film according to claim 12, further comprising exposing the dry electrode film to a solvent to dissolve the electrolyte salt therein.

14. The method for manufacturing a dry electrode film according to claim 13, The method for manufacturing a dry electrode film further includes disposing the dry electrode film within an energy storage device housing, and exposing the dry electrode film to a solvent within the energy storage device housing.

14. In the method for manufacturing a dry electrode film according to claim 12, The method further includes disposing the dry electrode film within an energy storage device housing, And exposing the dry electrode film to a solvent before disposing the dry electrode within the energy storage device housing. The method for manufacturing a dry electrode film.

15. In the method for manufacturing a dry electrode film according to claim 14, The method for manufacturing a dry electrode film further includes pre-lithiating the dry electrode film during the step of exposing the dry electrode film to a solvent.

16. In the method for manufacturing a dry electrode film according to claim 15, The method for manufacturing a dry electrode film further includes rolling the lithiated dry electrode.

17. A foam-active material composite for an energy storage device, comprising: A dry active material; and A foam The foam-active material composite.

18. In the material according to claim 17, The foam is a metal foam, a ceramic foam, or a combination thereof.

19. In the material according to claim 17 or 18, The dry active material is encapsulated by the foam.

20. In the material according to claim 17 or 18, The material further includes a dry binder.

21. In the material according to claim 20, The dry active material and the dry binder are encapsulated by the foam.

22. An electrode for an energy storage device, comprising the material according to any one of claims 17 to 21, and not including a separate current collector.

23. An electrode for an energy storage device, comprising the material according to any one of claims 17 to 21, and further including a current collector.

24. A dry composite solid polymer electrolyte (SPE) film for an energy storage device, comprising: A dry ion-conductive polymer; A dry lithium source; A dry binder; An ion-conductive medium; and A dry filler material The dry composite solid polymer electrolyte (SPE) film.

25. In the film according to claim 24,

25. In the film according to claim 24, The dry ion-conductive polymer is a film selected from polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly(methylene oxide), polyoxymethylene, poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), poly(methyl methacrylate), poly(vinyl acetate), poly(vinyl chloride), poly(vinyl acetate), poly(oxyethylene) 9 methacrylate, poly(ethylene oxide) methyl ether methacrylate, and poly(propylene imine), or a combination thereof.

26. In the film according to claim 24 or 25, The said dry lithium source is lithium perchlorate (LiClO ４ ), lithium tetrafluoroborate (LiBF ４ ), lithium hexafluorophosphate (LiPF ６ ), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (Li(C ２ F ５ SO ２ ), ２ N), lithium bis(oxalato)borate (LiB(C ２ O ４ ), ２ ), lithium trifluoromethanesulfonate (LiCF ３ SO ３ ), lithium bis(pentafluoroethanesulfonyl)imide (C ４ F １０ LiNO ４ S ２ ), lithium bis(fluorosulfonyl)imide (F ２ LiNO ４ S ２ ), lithium difluoro(oxalato)borate (LiBF ２ (C ２ O ４ ), lithium difluorophosphate (F ２ LiO ２ P), lithium oxalyldifluoroborate, lithium trifluorochloroborate (LiBF ３ Cl), lithium hexafluoroarsenate (LiAsF ６ ), Li ６．４ La ３ Zr １．４ Ta ０．６ O １２ ), Li ７ La ３ Zr ２ O １２ ), Li １０ SnP ２ S １２ ), Li ３ xLa ２／３－ｘ TiO ３ ), Li ０．８ La ０．６ Zr ２ (PO ４ ), ３ Li １＋ｘ Ti ２－ｘ Al ｘ (P.O. ４ ) ３ , Li １＋ｘ＋ｙ Ti ２－ｘ Al ｘ Si ｙ (P.O. ４ ) ３－ｙ and LiTi ｘ Zr ２－ｘ (P.O. ４ ) ３ or a combination thereof.

27. In the film according to any one of claims 24 to 26, The dry filler is titanium oxide (TiO ２ ), silica (SiO ２ ), silicon oxide (SiO), copper oxide (CuO), montmorillonite ((Na, Ca) ０．３３ (Al, Mg) ２ (Si ４ O １０ ), bentonite (Al ２ O ３４ SiO ２ H ２ O), kaolinite (Al ２ Si ２ O ５ (OH) ４ ), hectorite (Na ０．３ (Mg, Li) ３ Si ４ O １０ (OH) ２ ), halloysite (Al ２ Si ２ O ５ (OH) ４ ), 4'-amino-2,3'-dimethylazobenzene (CH ３ C ６ H ４ N=N C ６ H ３ (CH ３ )NH ２ ), yttrium aluminum oxide (Y ３ Al ５ O １２ ), yttrium iron oxide (Y ３ Fe ５ O １２ ) and nanoclay, or a combination thereof, a film.

28. In the film according to any one of claims 24 to 27, The ion-conductive medium is a film selected from nanoclay and garnet.

29. A dry cathode electrode including a dry electrode film; The dry composite SPE film according to any one of claims 24 to 28; and, A lithium metal anode An energy storage device comprising.

30. In the energy storage device according to claim 29, An energy storage device that is a solid energy storage device not containing a liquid solvent.

Images