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

Abstract

The energy storage device may include a cathode, an anode, and a separator between the cathode and anode. At least one of the electrodes may include an electrode film manufactured by a drying process. The electrode film, electrode, and / or separator may include a salt, improved porosity, increased density, may be pre-lithiated, and / or may include a foam. Processes and apparatus used to manufacture the electrodes and / or electrode films are also described herein.

Description

[Technical field]

[0001] INCORPORATION BY REFERENCE OF PRIORITY APPLICATIONS This application claims priority to U.S. Provisional Application No. 62 / 757,620, filed November 8, 2018, which is incorporated by reference in its entirety.

[0002] The present invention relates to energy storage devices, and more particularly to compositions for energy storage device electrodes and methods of making same. [Background technology]

[0003] 2. Description of Related Art Various types of energy storage devices can be used to power electronic devices, 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, with electrodes prepared using the improved electrode formulations and / or manufacturing processes can promote improved capacitor electrical performance. Lithium ion capacitors or batteries with electrodes manufactured using the 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. The improved electrode formulations and / or manufacturing processes can also help reduce the manufacturing costs of energy storage devices. Summary of the Invention

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

[0005] In a first aspect, a dry electrode film for 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 LiPF 6 , LiBF 4 , LiBOB, LiN(SO 2 CF 3 ) 2 , LiiOSO 2 CF 3 , LiNO 3 , lithium acetate, lithium halides, tetraalkylammonium tetrafluoroborates, tetraalkylammonium hexafluorophosphates, garnet ionic conductors, sulfur-based ionic conductors, 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 Ti2-x Al x S y (PO 4 ) 3-y and LiTi x Zr 2-x (PO 4 ) 3 Or a combination thereof.

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

[0008] In some embodiments, a dry gradient electrode film for an energy storage device is provided, the dry gradient electrode film having a first dry electrode film of the energy storage device comprising a first concentration of an electrolyte salt and a second dry electrode film of the energy storage device comprising a second concentration of an electrolyte salt, where the first concentration of the electrolyte salt is less than the second concentration of the electrolyte salt.

[0009] In some aspects, a solid state energy storage device is provided comprising a dry electrode film of an energy storage device, where the solid state energy storage device is free of a liquid solvent.

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

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

[0012] In a second aspect, a method of manufacturing a dry electrode film for an energy storage device is provided. The method includes providing 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 comprises exposing the dry electrode film to a solvent, thereby dissolving the electrolyte salt. In some embodiments, the method further comprises disposing the dry electrode film within an energy storage device housing, where the exposing of the dry electrode film to the solvent occurs within the energy storage device housing. In some embodiments, the method further comprises disposing the dry electrode film within an energy storage device housing, where the exposing of the dry electrode film to the solvent occurs prior to disposing the dry electrode in the energy storage device housing. In some embodiments, the method further comprises prelithiation of the dry electrode film during the step of exposing the dry electrode film to the solvent. In some embodiments, the method further comprises rolling the lithiated dry electrode.

[0014] In a third aspect, a foam-active material composite for an energy storage device is provided, the composite including a dry active material, a dry binder, and a foam.

[0015] In a fourth aspect, a foam-active material composite for an energy storage device is provided, the composite comprising 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 embodiments, an electrode of an energy storage device comprises a foam-active material composite and does not include a separate current collector.

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

[0019] In a fifth aspect, a dry composite solid polymer electrolyte (SPE) film for an energy storage device is provided, the SPE film comprising a dry ionically conductive polymer, a dry lithium source, a dry binder, an ionically conductive medium, and a dry filler.

[0020] In some aspects, the dry ionically conductive polymer is selected from 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), or combinations thereof. In some embodiments, the 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 (PO 4 ) 3 , Li 1+x+y Ti 2-x Al x S y (PO 4 ) 3-y and LiTi x Zr 2-x (PO 4 ) 3 or a combination thereof. In some embodiments, the dry filler is selected from titanium dioxide (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 S 2 O 5 (OH) 4 ), Hectorite (Na 0.3 (Mg,Li) 3 S 4 O 10 (OH) 2 ), Halloysite (Al 2 S 2 O 5 (OH) 4 )), 4'-amino-2,3'-dimethylazobenzene (CH 3 C 6 H 4 N=NC 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 nanoclays, or combinations thereof. In some embodiments, the ionically conductive medium is selected from nanoclays and garnets, or combinations thereof.

[0021] In some embodiments, an energy storage device is provided that 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-state 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 become readily apparent to those of ordinary skill in the art from the following detailed description of the preferred embodiments, which refer 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 now be described with reference to the drawings of specific embodiments, which are intended to illustrate particular embodiments and are not intended to limit the invention. [Figure 1] FIG. 1 is a schematic cross-sectional side view of an example energy storage device according to one embodiment. [Diagram 2] FIG. 2 is a process flow diagram illustrating an example of a process for producing an electrode film from an electrode film mixture containing an electrode salt. [Diagram 3] FIG. 3 is a process flow diagram illustrating an example of a process for encapsulating an electrode film mixture with a foam. [Figure 4] FIG. 4 is a process flow diagram illustrating an example of a process for pressing a free-standing electrode film against a foam. [Diagram 5] FIG. 5 shows the apparatus and process used to prelithiate the electrode film containing the electrode salt. [Figure 6] FIG. 6 shows the dry mix powders of the blends SPE-2 (panel a), SPE-3 (panel b), SPE-4 (panel c) and SPE-5 (panel d). [Figure 7] FIG. 7 shows an example of an SPE film transformed from the dry blend powder by calendaring (panel a), as well as films formed from the dried materials of SPE-1 (panel b), SPE-3 (panel c), and SPE-4 (panel d). [Figure 8] FIG. 8 shows films of SPE-1 (panel a), SPE-2 (panel b), SPE-4 (panel c) and SPE-5 (panel d) after the films were recalendered to the desired thickness. [Figure 9]FIG. 9 shows SEM images of the surfaces of films transformed from the SPE-4 powder mixture at magnifications of 20× (panel a), 200× (panel b), 500× (panel c), and 1000× (panel d). [Figure 10] FIG. 10 shows SEM images of the surface of a recalendered SPE-4 film at magnifications of 20× (panel a), 200× (panel b), 500× (panel c), and 1000× (panel d). [Figure 11] FIG. 11 shows mechanical strength measurements showing tensile (load) vs. elongation for recalendered SPE-4 films (panel a) and images of specimens after tensile measurements (panel b). Films SPE-4_3, SPE-4_4, and SPE-4_5 exceeded the load limit of the instrument (10 N). The peak tensile strength of 10.32 N is the average of five measurements, and the elongation of 2.91 mm is the average of measurements for SPE-4_1 and SPE-4_2, which did not exceed the load limit. [Figure 12] FIG. 12 shows the ionic conductivity of SPE-4 and SPE-5 films measured from the AC impedance of Cu / SPE / Cu. [Figure 13] FIG. 13 shows the voltage profiles of Li / SPE / Li cells for Li stripping and deposition of SPE-4 (panels a and b) and SPE-5 (panels c and d), where the current density was 0.2 mA / cm, Li stripping took 3 h, Li deposition took 3 h, and 5 min remained after each positive and negative polarization. [Figure 14] FIG. 14 shows the configurations of the Gr / SPE-1 / Li pouch cells used for electrochemical measurements: cell 1 with one SPE layer (panel a), cell 2 with two SPE layers (panel b) and cell 3 with Celgard / SPE layers (panel c). [Figure 15] FIG. 15 shows the first cycle capacity (panel a) and coulombic efficiency (panel b) for the graphite / SPE-1 / Li pouch cells shown in FIG. 14, cell 1, cell 2, and cell 3. [Figure 16]FIG. 16 shows several solid structures of direct lamination of an SPE layer with a dry electrode (panels a, b, c and d). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Detailed Description definition As used herein, the terms "battery" and "capacitor" should be given their ordinary and customary meaning to those of ordinary skill in the art. The terms "battery" and "capacitor" are not mutually exclusive. A capacitor or battery may refer to a single electrochemical cell that may 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 fall below the rated voltage under load or according to manufacturing tolerances.

[0027] A "self-supporting" electrode film as provided herein 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 is self-supporting. When incorporated into an energy storage device, a self-supporting electrode film or active layer is one that incorporates such a binder matrix structure. Generally, depending on the method employed, such an electrode film or active layer is strong enough to be used in the energy storage device manufacturing process without external support elements such as current collectors, support webs, or other structures, although support elements are used to facilitate the energy storage device manufacturing process. For example, a "self-supporting" electrode film may have sufficient strength to be wound, handled, and unrolled within the electrode manufacturing process without other support elements. A dry electrode film, such as a cathode electrode film or an anode electrode film, may be self-supporting.

[0028] As provided herein, a "solvent-free" electrode film is an electrode film that does not contain any detectable process solvent, process solvent residues, or process solvent impurities. A dry electrode film, such as a cathode electrode film or an anode electrode film, 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 active material, binder and optional additives. A wet electrode may contain processing solvent, processing solvent residues and / or processing solvent impurities.

[0030] explanation Although specific embodiments and examples are described below, those skilled in the art will recognize that the invention extends beyond the specifically disclosed embodiments and / or uses and obvious variations and equivalents thereof. Accordingly, it is not intended that the scope of the invention disclosed herein should be limited by any of the specific embodiments described below.

[0031] Electrode film packing density or electrode film porosity is an important characteristic in energy storage device components to achieve improved electrochemical performance. Therefore, it is necessary to determine and manufacture an appropriate electrode film density. The appropriate electrode film density is one that 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 the solvent is removed is usually smaller than that of the desired target electrode film density.

[0032] In dry electrode processes, control of the electrode film density and target electrode material packing weight is determined by controlling the free-standing film thickness and the amount of compression pressure applied, and is typically achieved by successive calender passes. Thus, unlike wet coating techniques, independent control of the electrode material packing weight and electrode film thickness is limited. Electrode film porosity in dry electrode film manufacture is primarily controlled by the powder formulation used to manufacture the free-standing film. Particle size, surface chemistry, and morphology are common characteristics that affect the electrode film density of the supplied dry free-standing electrode film.

[0033] In some cases, pore-forming materials can be added to the powder formulation and then removed, leaving a pore volume in the free-standing film. The pore-forming materials used are materials that may require a post-liquid extraction and rinsing step, such as salts, or pyrolysis into gaseous by-products. In some embodiments, the present disclosure provides materials and processes for producing dry-processed electrode films with high porosity (low density) but without such post-processing steps that increase production costs.

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

[0035] In another example, these materials and processes can be used to fabricate solid-state electrodes. Typical commercial lithium-ion batteries contain a flammable electrolyte, which can cause fires and explosions when overcharged. Typical lithium-ion battery electrodes are fabricated from a wet process, where a slurry is composed of active materials and a solvent. Not only does the solvent add cost to the procedure and can degrade the components of the solid-state energy storage device, but commonly used solvents such as N-methyl-2-pyrrolidone can cause adverse health effects with repeated exposure.

[0036] Solid-state batteries improve safety by using non-flammable components. In addition, solid-state batteries can safely utilize elemental lithium metal as an electrode since dendrite formation is less severe than in typical liquid-based lithium-ion batteries. Lithium metal offers significantly higher theoretical specific capacity compared to graphite, which may improve energy density over typical lithium-ion batteries. Furthermore, dry electrode processing methods are expected to be cheaper and safer than traditional methods. Typically, solid-state lithium batteries have an ionic and / or electronic conducting cathode, a solid electrolyte, and a lithium metal anode. In some embodiments, the solid electrode comprises a dry solid electrolyte salt. In some embodiments, the solid electrolyte is an ionically conducting inorganic solid electrolyte. In some embodiments, the solid electrolyte is a polymer-based film. In some embodiments, the solid electrolyte is a dry processed composite solid polymer electrolyte (SPE).

[0037] In some examples, embodiments include dry electrode formulations and manufacturing processes that achieve electrode films with denser active material, greater electrode film thickness, greater electrode film density, and / or greater electron density (e.g., energy density, specific energy density, areal energy density, areal capacity, and / or specific capacity, etc.). A denser electrode film will generally contain more active material in a smaller volume. Specifically, smaller particle size and more intimate contact of active material, binder, and additives may be achieved in the dry process. Dry processing methods traditionally use high shear and / or high pressure processing steps to break down and mix electrode film materials, which may contribute to structural advantages. The present disclosure teaches that in some embodiments, electrode density and porosity may be modified by changing the electrode material composition, for example, by changing the active material, polymer binder, and additives. Furthermore, it has been found that improved high electrode film density at high loading may also be produced by controlling the electrode calendering parameters, such as 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 loadings. In some embodiments, the calendering may occur at ambient temperature. In some embodiments, high loading and high electrode film density are achieved without issues such as cracking and / or delamination of the electrode film.

[0038] While many embodiments and examples are described throughout this disclosure, one skilled in the art will understand that the disclosed embodiments may be used alone or in combination. For example, a dense electrode film may be utilized in a solid-state system and / or a thick electrode film. In other examples, a thick electrode film may be utilized in an electrode film with an electrode salt, a solid-state system, a porous electrode film, and / or an electrode or electrode film with a foam. In other examples, an electrode or electrode film with a foam may be utilized in a solid-state system, an electrode film with an electrode salt, and / or a porous electrode film. Many non-limiting example combinations are provided herein, but other combinations are also possible.

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

[0040] Embodiments herein may include mixtures of materials for electrode films, energy storage devices, and related methods that include electrode salts. Many electrical, mechanical performance, and / or processing advantages can be realized by utilizing electrode salts.

[0041] For example, the dry electrode film may include an electrode salt, where 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 disposed such that it contacts the dry electrode film when placed in the energy storage device housing or container. For example, where the electrode salt remains in the device to act as an electrolyte. In other examples, the solvent containing the dissolved electrode salt is removed and / or washed from the energy storage device container. In some embodiments, the solvent is introduced to the dry electrode film outside the energy storage device container, thereby removing the electrode salt before the dry electrode film is laminated to a current collector as a dry electrode and / or placed in the energy storage device container. In some embodiments, the dry electrode film is washed with a solvent and simultaneously prelithiated when exposed to a current outside the energy storage device container. In some embodiments, the dry electrode film is prelithiated after washing with a solvent outside the energy storage device container, for example, the prelithiation may occur in a separate prelithiation device or in the energy storage device container.

[0042] In other examples, the dry electrode may include 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 operational within the energy storage device container. In some embodiments, the electrode salt is highly conductive. Highly conductive salts typically have relatively low lattice energies such that the salt dissolves in a solvent to produce a sufficient number of ions. For example, some highly conductive Li salts include LiPF 6 , LiClO 4 and LiN(SO 2 CF 3 ) 2 Includes:

[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 with high ionic conductivity. In some embodiments, the electrode salt can be a ceramic compound with high ionic conductivity. In some embodiments, the electrode salt can be LiPF 6 , LiBF 4 , LiBOB, LiN(SO 2 CF 3 ) 2 , LiiOSO 2 CF 3 , LiNO 3 , lithium acetate, lithium halides, tetraalkylammonium tetrafluoroborates, tetraalkylammonium hexafluorophosphates, lithium fluorides, garnet ionic conductors, e.g. Li 5 La 3 Ta 2 O 12 and Li 3 N, sulfur-based ionic conductors, e.g., Li 2 SP 2 S 5 and Li 2 SP 2 S 5 -Li 3 PO 4 , other compounds with high ionic conductivity, e.g. Li 0.5 La 0.5TiO 3 (LLTO), Li 7 La 3 Zr 2 O 12 (LLZO), lithium superionic conductor (LISCON), for example, LISCON has the chemical formula Li (2+2x) Zinc (l-x) GeO 4 In some embodiments, the electrode salt may be selected from at least one of LiPF 6 , LiBF 4 , LiBOB, LiN(SO 2 CF 3 ) 2 , LiiOSO 2 CF 3 , LiNO 3 , 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 salt is lithium perchlorate (LiClO 4 ), 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 ), Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 , Li 7 La 3 Zr 2 O 12 , Li10 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 S y (PO 4 ) 3-y and LiTi x Zr 2-x (PO 4 ) 3 In some embodiments, the electrode salt is lithium fluoride. In some embodiments, the electrode salt is a garnet ion conductor, e.g., Li 5 La 3 Ta 2 O 12 and Li 3 In some embodiments, the electrode salt is a sulfur-based ionic conductor, such as Li 2 SP 2 S 5 and Li 2 SP 2 S 5 -Li 3 PO 4 In some embodiments, the electrode salt may be other compounds with high ionic conductivity, such as Li 0.5 La 0.5 TiO 3 (LLTO) and / or Li 7 La 3 Zr 2 O 12 (lithium lanthanum zirconate or LLZO). In some embodiments, the electrode salt is a lithium superionic conductor (LISCON), e.g., Li (2+2x) Zinc (1-x) GeO 4In some embodiments, the electrode salt does not degrade under normal energy storage device operation.

[0044] In some embodiments, the electrode salt comprises at or about 0.5%, at or about 1%, at or about 2%, at or about 3%, at or about 4%, at or about 5%, at or about 6%, at or about 7%, at or about 8%, at or about 9%, at or about 10%, or at or about 11% by weight of the dry electrode mix, or any value between these values. For example, in some embodiments, the electrode salt comprises 1-10% by weight of the dry electrode mix.

[0045] In some embodiments, the solvent for use as an electrolyte in the device or for use as a wash off the device is selected from at least one of carbonates, esters, amides, ethers, alcohols, sulfones, and water. In some embodiments, the solvent is dimethyl carbonate. In some embodiments, the solvent is a highly volatile solvent, the solvent being a gas at ambient temperature and pressure. In some embodiments, the highly volatile solvent is a liquid at pressures above 1 atmosphere. In some embodiments, the highly volatile solvent is a liquid below 20° C. In some embodiments, the highly volatile solvent has a boiling point at atmospheric pressure of about or up to about 10° C., about or up to about 20° C., about or up to about 30° C., about or up to about 40° C., about or up to about 50° C., about or up to about 57° C., about or up to about 60° C., about or up to about 66° C., about or up to about 70° C., about or up to about 80° C., about or up to about 80° C., about or up to about 90° C., about or up to about 91° C., about 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 illustrating 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 as, for example, 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 respective opposing 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 to facilitate ion transport between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 122 may 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 contained within the energy storage device housing 120. For example, the energy storage device housing 120 may be sealed following insertion of the first electrode 102, the second electrode 104, and the separator 106 and impregnation of the energy storage device 100 with the electrolyte 122 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. While the energy storage device 100 is shown as a dual electrode, dual layer device, it will be understood that other types may be implemented, such as a single layer electrode.

[0047] The energy storage device 100 may include any number of different types of electrolyte 122. For example, the device 100 may include a lithium ion battery electrolyte, which may include a lithium source, such as a lithium salt, and a solvent, such as an organic solvent. In some embodiments, the device 100 may further include an additive, such as a solid electrolyte interphase (SEI)-forming additive, an electrode wetting additive, or a separator wetting additive. In some embodiments, the lithium salt is lithium hexafluorophosphate (LiPF6 ), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiClO 4 ), lithium bis(trifluoromethanesulfonyl)imide (LiN(SO 2 CF 3 ) 2 ), lithium trifluoromethanesulfonate (LiSO 3 CF 3 ), lithium bis(pentafluoroethanesulfonyl)imide (C 4 F 10 LiNO 4 S 2 ), lithium bis(fluorosulfonyl)imide (F 2 LiNO 4 S 2 ), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 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 ), 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 LiPF 6 , ethylene carbonate, propylene carbonate and diethyl carbonate.

[0048] In some embodiments, the electrolyte 122 of the energy storage device 100 comprises a solvent and at least one of the electrode salts described above. In some embodiments, the energy storage device 100 is a solid-state energy storage device, and thus the electrolyte 122 does not comprise a solvent.

[0049] The separator 106 may be configured to electrically insulate two adjacent electrodes, e.g., the first electrode 102 and the second electrode 104, on opposite sides of the separator 106 while allowing ion transport between the two adjacent electrodes. The separator 106 may include a suitable porous electrically insulating material. In some embodiments, the separator 106 may include a polymeric material. For example, the separator 106 may 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 may be a multi-layer material, e.g., PP / PE or PP / PE / PP. In some embodiments, the separator may be ceramic-coated, e.g., ceramic-coated PE, PP, or multi-layer material.

[0050] In some embodiments, particularly when energy storage device 100 is a solid-state energy storage device, 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 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, respectively. The first current collector 108 and the second current collector 110 can facilitate electrical coupling between the corresponding electrode film and an external circuit (not shown). The first current collector 108 and / or the second current collector 110 can include one or more conductive materials and have any suitable shape and size selected to facilitate the transfer of charge between the corresponding electrode and the external electrical circuit. For example, the current collector can include metallic materials such as aluminum, nickel, copper, rhenium, niobium, tantalum, and the like, precious 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 may comprise, for example, aluminum foil or copper foil. The first current collector 108 and / or the second current collector 110 may have a rectangular or substantially rectangular shape sized to provide for transfer of charge between the corresponding electrode and an external circuit. In some embodiments, the current collector may comprise 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., a top electrode film) on a first surface of the first current collector 108 (e.g., a top surface of the first current collector 108) and a second electrode film 114 (e.g., a bottom electrode film) on a second, opposing surface of the first current collector 108 (e.g., a bottom surface of the first current collector 108). Similarly, the second electrode 104 can have a third electrode film 116 (e.g., a top electrode film) on a first surface of the second current collector 110 (e.g., a top surface of the second current collector 110) and a fourth electrode film 118 on a second, opposing surface of the second current collector 110 (e.g., a bottom surface of the second current collector 110). For example, a first surface of the second current collector 110 may face a second surface of the first current collector 108 such that the separator 106 is adjacent to the second electrode film 114 of the first electrode 102 and the third electrode film 116 of the second electrode 104. In some embodiments, an electrode may include more than one electrode film, such as, for example, 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, an electrode may include only one electrode film, such as, for example, the first electrode 102 shown in FIG. 1 is composed of the first electrode film 112 and the first current collector 108.

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

[0054] The electrode film may have a selected thickness suitable for a particular application. The thickness of the electrode film provided herein may be greater than the thickness of electrode films prepared by conventional processes. In some embodiments, the electrode film may be 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 capacitance, specific capacitance, 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 thickness of multiple single electrode films that are formed together into 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 films may have an electrode film porosity (which may be expressed as the percentage of the volume of the electrode film occupied by pores) that may be 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. In some embodiments, the electrode film may have an electrode film porosity (which may be expressed as the percentage of the volume of the electrode film occupied by pores) 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. In some embodiments, the electrode film may have an electrode film porosity (which may be expressed as the percentage of the volume of the electrode film occupied by pores) of at most about 5%, at least about 8%, at least at most about 10%, at most about 12%, at most about 14%, at most about 16%, at most about 18%, at most about 20%, at most about 25%, at most about 30%, at most about 35%, or at most about 40%, or any range of values ​​therebetween.

[0056] In some embodiments, the electrode film density of the electrode films provided herein 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 1.0g / cm 3 , about 1.4g / cm3 , about 1.5g / cm 3 , about 1.6g / cm 3 , about 1.7g / cm 3 , about 1.8g / cm 3 , about 1.9g / cm 3 , about 2.0g / cm 3 , about 2.5g / cm 3 , about 3.0g / cm 3 , about 3.3g / cm 3 , about 3.4g / cm 3 , about 3.5g / cm 3 , about 3.6g / cm 3 , about 3.7g / cm 3 , about 3.8g / cm 3 , about 3.9g / cm 3 , about 4.0g / cm 3 , about 4.1g / cm 3 or about 4.2 g / cm 3 , or any range of values ​​therebetween. In some embodiments, the electrode film can have a density of at most about 0.8 g / cm 3 , about 1.0g / cm 3 , 1.4g / cm 3 , up to about 1.5g / cm 3 , up to about 1.6g / cm 3 , up to about 1.7g / cm 3 , up to about 1.8g / cm 3 , up to about 1.9g / cm 3 Or a maximum of about 2.0 g / cm 3 , or any range of values ​​therebetween. In some embodiments, the electrode film has a density of at least about 0.8 g / cm 3 , about 1.0g / cm 3 , about 1.4g / 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 / cm 3, 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 any range of values ​​therebetween.

[0057] In some embodiments, the electrode formulation may be calendered 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 calendered at about ambient or room temperature.

[0058] The electrode films generally include 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 may be prepared by processes described herein. The electrode films 112 and / or 114 may be wet or self-supporting dry electrodes, as described herein.

[0059] In some embodiments, an electrode film, such as one or more of electrode films 112 and / or 114, includes 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 an anode or cathode of a battery.

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

[0061] The anode active material may include, for example, an intercalation material (such as carbon, graphite (natural, synthetic, or blended), hard or amorphous carbon, and / or graphene), alloyed / dealloyed material (such as silicon, silicon oxide, tin, and / or tin oxide), metal element, metal alloy or compound (such as Si-Al and / or Si-Sn), and / or altered material (such as manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). 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).

[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, the 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, mixtures or composites of the above materials. In some embodiments, the anode electrode film may include about 80 to about 98 weight percent, including about 80 to about 98 weight percent or about 94 to about 97 weight percent, of the at least one active material. In some embodiments, the anode electrode film may include about 80 weight percent, about 85 weight percent, about 90 weight percent, about 92 weight percent, about 94 weight percent, about 95 weight percent, about 96 weight percent, about 97 weight percent, about 98 weight percent, or about 99 weight percent, or any range of values ​​therebetween, of the at least one active material. In some embodiments, the anode electrode film comprises up to about 5 wt %, including about 1 to about 3 wt %, of the conductive additive. In some embodiments, the anode electrode film can comprise 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 comprises up to about 20 wt %, including about 1.5 to about 10 wt %, about 1.5 to about 5 wt %, or about 3 to about 5 wt %, of the binder. In some embodiments, the anode electrode film comprises about 4 wt % of the binder. In some embodiments, the anode electrode film comprises about or up to about 20% by weight, about or up to about 15% by weight, about or up to about 10% by weight, about or up to about 5% by weight, about or up to about 3% by weight, about or up to about 1.5% by weight, or about or up to about 1.5% by weight, or about or up to about 1% by weight, or any range of values ​​therebetween, of a binder. In some embodiments, the anode film can be free of a conductive additive.

[0063] The cathode active material can include, for example, a metal oxide, a metal sulfide, or a lithium metal oxide. The lithium metal oxide can 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 can be, for example, a layered transition metal oxide (LiCoO 2 (LCO), Li(NiMnCo)O 2 (NMC) and / or LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA), etc.), spinel manganese oxide (LiMn 2 O 4 (LMO) and / or LiMn 1.5 Ni 0.5 O 4 (LMNO), olivine (LiFePO 4 etc.), chalcogenides (LiTiS 2 ), Tavorite (LiFeSO 4 F), silicon, silicon oxide (SiOx), aluminum, tin, tin oxide (SnOx), manganese oxide (MnOx), molybdenum oxide (MoO 2 ), molybdenum disulfide (MoS 2 ), nickel oxide (NiOx), or copper oxide (CuOx). The cathode active material may be sulfur or lithium sulfide (Li 2 S) or other sulfur-based materials, or mixtures thereof. In some embodiments, the cathode film comprises a material comprising sulfur or a sulfur active material at a concentration of at least 50% by weight. In some embodiments, the cathode film comprising a material comprising sulfur or a sulfur active material has a capacity of at least 10 mAh / cm 2 In some embodiments, the cathode film comprising sulfur or a material comprising a sulfur active material has an areal capacity of 1 g / cm 3In some embodiments, the cathode film comprising sulfur or the material comprising sulfur active material further comprises a binder. In some embodiments, the binder of the cathode film comprising sulfur or the material comprising 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 the lithium ion battery or hybrid energy storage device may comprise about 70 to about 98 wt%, including about 70 to about 92 wt%, or about 70 to about 96 wt%, of at least one active material. In some embodiments, the cathode electrode film may comprise 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 range of values ​​therebetween, of at least one active material. In some embodiments, the cathode electrode film of the lithium ion battery or hybrid energy storage device may comprise about 40 to about 60 wt% of at least one active material. In some embodiments, the cathode electrode film may comprise up to about 10 wt%, including up to about 5 wt%, or about 1 to about 5 wt%, of a porous carbon material. In some embodiments, the cathode electrode film may comprise 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 range of values ​​therebetween, of the porous carbon material. In some embodiments, the cathode electrode film comprises up to about 5 wt%, including about 1 to about 3 wt%, of the conductive additive. In some embodiments, the cathode electrode film comprises 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 range of values ​​therebetween. In some embodiments, the cathode electrode film comprises up to about 20 wt% of the binder, 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 comprises about 1.5 to about 3 wt% of the binder.In some embodiments, the cathode electrode film comprises about or up to about 20% by weight, about or up to about 15% by weight, about or up to about 10% by weight, about or up to about 5% by weight, about or up to about 3% by weight, about or up to about 1.5% by weight, or about or up to about 1.5% by weight, or about or up to about 1% by weight, of a binder, or any range of values ​​therebetween.

[0065] In some embodiments, the binder material may include one or more fibrillizable binder components. For example, a process for forming an electrode film may include fibrillizing the fibrillizable binder component such that the electrode film includes a fibrillized binder. The binder component may be fibrillized to provide a plurality of fibrils, where the mechanical support for one or more other components of the film is desired. 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 may 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 fibrillized binder components.

[0066] Some embodiments include an electrode film, such as an anode and / or a cathode, having one or more active layers that include a polymer binder material. The binder may include polytetrafluoroethylene (PTFE), polyolefin, polyalkylene, polyether, styrene butadiene, copolymers of polysiloxane, polysiloxane, branched polyether, polyvinyl ether, copolymers thereof, and / or mixtures thereof. The binder may include cellulose, such as carboxymethyl cellulose (CMC). In some embodiments, the polyolefin may include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), copolymers thereof, and / or mixtures thereof. For example, the binder may include polyvinylene 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-coalkylmethylsiloxane, copolymers thereof, and / or mixtures thereof. In some embodiments, the binder may be a thermoplastic. In some embodiments, the binder includes a fibrillizable polymer. In certain embodiments, the binder includes, consists essentially of, or consists of PTFE.

[0067] In some embodiments, one or more 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 or substantially no solvent is used to form 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 a 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 can be free or substantially free of any processing solvents and solvent residues resulting therefrom. In some embodiments, the active layer or electrode film is a free-standing dry particle electrode film formed using a dry process from a dry particle mixture. The process for forming the active layer or electrode film can include fibrillizing a fibrillizable binder component such that the film includes a fibrillated binder. In further embodiments, a free-standing active layer or electrode film may be formed without a current collector. In further embodiments, the active layer or electrode film may include a fibrillated polymer matrix such that the film is self-supporting. It is believed that a matrix, lattice, or web of fibrils may be formed to provide 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-supporting film, has a surface area of ​​about 12 mg / cm 2 , about 13mg / cm 2 , about 14mg / cm 2 , about 15mg / cm 2 , about 16mg / cm 2 , about 17mg / cm 2 , about 18mg / cm 2 , about 19mg / cm 2, about 20mg / cm 2 , about 21mg / cm 2 , about 22mg / cm 2 , about 23mg / cm 2 , about 24mg / cm 2 , about 25mg / cm 2 , about 26mg / cm 2 , about 27mg / cm 2 , about 28mg / cm 2 , about 29mg / cm 2 , about 30mg / cm 2 , about 40mg / cm 2 , about 50mg / cm 2 , about 60mg / cm 2 , about 70mg / cm 2 , about 80mg / cm 2 , about 90mg / cm 2 or about 100 mg / cm 2 or any range of values ​​therebetween. In some embodiments, the electrode film of an energy storage device, where the electrode film is a dry and / or self-supporting film, may provide a high electrode material loading, or high active material loading (which may be expressed as the weight of active material per unit area of ​​the electrode film or current collector), of 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 / cm 2, 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 or any value range therebetween.

[0069] In some embodiments, the energy storage device electrode film has a capacitance of about 3.5 mAh / cm, where the electrode film is a dry and / or self-supporting film. 2 or at least about 3.5 mAh / cm 2 , about 3.8mAh / cm 2 or at least about 3.8 mAh / cm 2 , about 4mAh / cm 2 or at least about 4 mAh / cm 2 , about 4.3mAh / cm 2 or at least about 4.3 mAh / cm 2 , about 4.5mAh / cm 2 or at least about 4.5 mAh / cm 2 , about 4.8mAh / cm 2 or at least about 4.8 mAh / cm 2 , about 5mAh / cm 2 or at least about 5 mAh / cm 2 , about 5.5mAh / cm 2 or at least about 5.5 mAh / cm 2 , about 6mAh / cm 2 or at least about 6 mAh / cm 2 , about 6.5mAh / cm 2 or at least about 6.5 mAh / cm 2 , about 6.6mAh / cm 2or at least about 6.6 mAh / cm 2 , about 7mAh / cm 2 or at least about 7 mAh / cm 2 , about 7.5mAh / cm 2 or at least about 7.5 mAh / cm 2 , about 8mAh / cm 2 Or at least about 8 mAh / cm 2 or about 10mAh / cm 2 Or at least about 10 mAh / cm 2 In a further embodiment, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, can provide an areal capacity (which can be expressed as capacity per unit area of ​​the electrode film or current collector) of at least about 8 mAh / cm 2 , for example, about 8 mAh / cm 2 , about 10mAh / cm 2 , about 12mAh / cm 2 , about 14mAh / cm 2 , about 16mAh / cm 2 , about 18mAh / cm 2 , about 20mAh / cm 2 or any range of values ​​therebetween. In some embodiments, the areal capacity is a charge capacity. In further embodiments, 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 a capacity of about 3.5 mAh / cm 2 , about 4mAh / cm 2 , about 4.5mAh / cm 2 , about 5mAh / cm 2 , about 5.5mAh / cm 2 , about 6mAh / cm 2 , about 6.5mAh / cm 2 , about 7mAh / cm 2 , about 7.5mAh / cm 2 , about 8mAh / cm 2 , about 8.5mAh / cm 2, about 9mAh / cm 2 , about 10mAh / cm 2 , or any range of values ​​therebetween. In some embodiments, the areal capacity is a charge capacity. In further embodiments, the areal capacity is a discharge capacity.

[0071] In some embodiments, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, may provide a specific capacity (which may be expressed as capacity per mass of active material) 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 mAh / 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 any range of values ​​therebetween. In further embodiments, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, may provide a specific capacity (which may be expressed as capacity per mass of the electrode film or current collector) of at least about 175 mAh / g or at least about 250 mAh / g, or any range of values ​​therebetween. In some embodiments, the specific capacity is a charge capacity. In further embodiments, the specific capacity is a discharge capacity. In some embodiments, the electrode may be an anode and / or a cathode. In some embodiments, the specific capacity may be an initial charge and / or discharge capacity. In further embodiments, the specific capacity may be a charge and / or discharge capacity measured after an initial charge and / or discharge.

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

[0073] In some embodiments, the energy storage device electrode film or electrode, where the electrode film is a dry and / or self-supporting film or the electrode comprises a dry and / or self-supporting film, may provide a percentage discharge capacity retention (which may be expressed by the discharge capacity at a given rate divided by the discharge capacity measured at C / 10) of about or at least about 10%, about or at least about 20%, about or at least about 30%, about or at least about 40%, about or at least about 50%, about or at least about 60%, about or at least about 70%, about or at least about 80%, about or at least about 90%, about or at least about 98%, about or at least about 98%, about or at least about 99%, about or at least about 99.9%, or about or at least about 100%, or any range of values ​​therebetween. In some embodiments, the discharge rate for the charge capacity retention percentage is C / 10 or greater, C / 5 or greater, C / 3 or greater, C / 2 or greater, 1C or greater, 1.5C or greater, or 2C or greater, or any value therebetween.

[0074] In some embodiments, the energy storage device electrode film or electrode, where the electrode film is a dry and / or self-supporting film or the electrode comprises a dry and / or self-supporting film, may provide a charge capacity generation percentage (which may be expressed as the charge capacity measured at a given constant current rate divided by the discharge capacity measured at C / 10) of about or at least about 10%, about or at least about 20%, about or at least about 30%, about or at least about 40%, about or at least about 50%, about or at least about 60%, about or at least about 70%, about or at least about 80%, about or at least about 90%, about or at least about 98%, about or at least about 99%, about or at least about 99.9%, about or at least about 100%, or any range of values ​​therebetween. In some embodiments, the charge rate for charge capacity generation percentage is at least C / 10, C / 5, C / 3, C / 2, 1C, 1.5C, or 2C, or any value therebetween.

[0075] In some embodiments, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, can have a specific energy density or mass energy density (which can be expressed as energy per 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 range of values ​​therebetween.

[0076] In some embodiments, the energy storage device electrode film, where the electrode film is a dry and / or free-standing film, can have an energy density or volumetric energy density (which can be expressed as 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 range of values ​​therebetween.

[0077] FIG. 2 is a process flow diagram illustrating 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 liquids or solvents, such that the resulting electrode film is free or substantially free of liquids, solvents, and resulting residues. In block 202, an electrode film mixture is formed that includes an electrode salt. In some embodiments, the electrode film mixture can further include an electrode active material. In some embodiments, the electrode film mixture can further include carbon particles. In some embodiments, the electrode film mixture can further include a binder material. Optionally, one or more conductivity-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 fibrillizable 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-promoting additive can 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 may be used. In such embodiments, the time to mix and / or grind may be inversely proportional to the feed rate. Generally, the feed rate will depend on the milling machinery and may be adjusted based on the operating parameters of the machine, taking into account the guidance provided herein. In further embodiments, equipment with larger channels may be used to increase the time to mix and / or grind. If a batch mixing and / or grinding process is used, the time may be increased by simply mixing and / or grinding for a longer time and / or at a higher RPM.

[0079] In block 204, the electrode film mixture may be fibrillated to form fibrils from the binder material. The fibrillation process may be performed at a reduced speed and / or increased processing pressure. Reducing the speed and / or increasing the processing pressure may promote increased formation of fibrils such that a lesser amount of binder material may be used to form an electrode film having a desired resistance to tensile, shear, compressive and / or torsional stresses. As described herein, in some embodiments, the fibrillation process may be a mechanical shear process, including, for example, a mixing and / or grinding process. In some embodiments, the rate at which the particles of the electrode film mixture circulate through the blender and / or mill may be reduced during the fibrillation process. In some embodiments, the processing pressure in the blender and / or mill during the fibrillation process may be increased. In some embodiments, the forming step of block 202 and the fibrillation step of block 204 may be one or substantially one continuous process. Reducing the speed and / or increasing the processing pressure can, for example, allow the production of electrode films with sufficient strength, e.g., free-standing electrode films, e.g., by either a single higher pressure calendering (single step) or multiple calendering steps, e.g., where the film is unwound and then re-calendered one or more times after the initial calendering step.

[0080] At block 206, the electrode film mixture can be calendered in a calendering device to form a free-standing fibrillated electrode film. Calendering devices are well known in the art and generally comprise a pair of calender rolls (having either a mechanically fixed spacing or a hydraulically or pneumatically fixed spacing) between which raw material, such as the electrode film mixture, is fed to form the electrode film. In some embodiments, the electrode film can be formed in a first calendering step without an additional calendering step to form a film with a desired minimum thickness, as further described herein. In some embodiments, the calendered mixture forms a free-standing dry particle film that is free or substantially free of 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 a solvent-exposed electrode film. Exposing the electrode film to the solvent may extract the electrode salt. In some embodiments, the extracted electrode salt may function as an ionic component of the electrolyte system of the energy storage device. In some embodiments, extraction of the electrode salt may 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 the solvent within an energy storage device container, such as the energy storage device container 120 shown in FIG. 1. In some embodiments, the electrode film is exposed to the solvent outside the energy storage device container. For example, the electrode film may be exposed to a solvent in an electrolyte bath. In some embodiments, the electrode film may be exposed to the solvent as a free-standing electrode film or as part of an electrode that further includes a current collector. In some embodiments, the electrode film may be exposed to a current while being exposed to the solvent. In some embodiments, the electrode film may be pre-lithiated while being exposed to the solvent. In some embodiments, such as in a process for manufacturing a solid electrode film, block 208 is not performed, thereby allowing the electrode salt to remain within the electrode film. In such embodiments, the electrode salt may function as a solid electrolyte in a solid state energy storage device.

[0082] In some embodiments, the solvent exposed electrode film has a porosity ranging from 1 to 50% of the free void volume of the electrode. In some embodiments, the solvent exposed electrode film has a porosity ranging from 1 to 10% of the free void volume of the electrode. In some embodiments, the solvent exposed electrode film has a film thickness ranging from 20 to 300 μm. In some embodiments, the solvent exposed electrode film has a film thickness ranging from 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. Some conventional energy storage devices use high density aluminum, for example, as a current collector or in combination with a current collector and other electrode film materials, but the relatively small contact area between the electrode film and current collector surfaces may result in poor electron transfer and therefore poor rate capabilities. However, the use of foams such as metal foams as current collectors can significantly increase the power of the energy storage device by utilizing a three-dimensionally interconnected porous structure that seals the active material and increases the contact area between the foam current collector and the active material, thereby increasing the rate capabilities of the energy storage device. Additionally, the use of foams such as ceramic foams can provide an ion source and act as an ion conductor, for example, foams including lithium lanthanum zirconate (LLZO) can conduct lithium ions. Furthermore, encapsulation of active materials within foams, such as metal and ceramic foams, may reduce or eliminate the need to include inactive ingredients, such as binders, in the electrode mix. Minimization or elimination of inactive ingredients may result in increased energy density of the electrochemical device. Furthermore, encapsulation of active materials within foams may alleviate at least a portion of the electrode volumetric strain associated with charge / discharge processes. As an example, volumetric expansion and contraction of conventional lithium ion battery electrodes during cycling may shorten cycle life. In some embodiments, the electrode film mixture or free-standing electrode film may be sealed by a foam. In some embodiments, the electrode film mixture or free-standing electrode film may be pressed against the foam. In some embodiments, the electrode film mixture or free-standing electrode film may be calendered against the foam. In some embodiments, the foam may be commercially available.

[0084] In some embodiments, the foam acts as a housing for the active material. In some embodiments, the foam acts as a housing for the active material and provides sufficient conductivity so that a current collector is not required, even if an additional current collector is used. Such foam-active material composites are characterized as dry electrodes for the purposes of this 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 does not provide sufficient electrical conductivity to require a current collector. Such foam active material composites are characterized as dry electrode films for the purposes of this disclosure. An example of such a composite is an active material encapsulated by a ceramic foam, since ceramics are typically electrically insulating. Thus, in some embodiments, the foam active material composite may be laminated to a current collector. In some embodiments, the current collector is a metal current collector. In some embodiments, the lamination may be performed by calendering. In some embodiments, the calendering may be performed using a two-roll calender press.

[0086] FIG. 3 is a process flow diagram illustrating an example of a process 300 for encapsulating an electrode film mixture in a foam. In some embodiments, the electrode film mixture in the process 300 can be a cathode or anode electrode film mixture, as described herein above. In some embodiments, the electrode film mixture in the process 300 is a cathode electrode film mixture. In some embodiments, the process 300 for encapsulating an electrode film mixture in a foam is a dry process that does not use liquids or solvents, such that the resulting electrode film is free or substantially free of liquids, solvents, 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 can be selected from at least one of lithium lanthanum zirconate (LLZO), lithium nitride, lithium aluminum germanium phosphate (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 lithium ion conductive ceramic material in the electrode film mixture can be at or about 0.5 wt%, at or about 1 wt%, at or about 5 wt%, at or about 10 wt%, at or about 20 wt%, at or about 30 wt%, at or about 40 wt%, at or about 50 wt%, or at or about 60 wt%, or any range of values ​​therebetween. For example, in some embodiments, the amount of lithium ion conductive ceramic material in the electrode film mixture can range from about 1 to about 50 wt%. In some embodiments, the electrode film mixture can further include other materials described herein, such as, for example, active materials, carbon particles, and / or binder materials. In some embodiments, the active material can 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 conductivity enhancing additives may be combined. In some embodiments, the electrode film mixture is a dry particle mixture.

[0087] In some embodiments, the electrode film mixture may be free of binder material, substantially free of binder material, or the amount of binder material is reduced compared to an electrode without foam. In some embodiments, the electrode film mixture includes less binder material, about 0%, 0.5%, 1%, 1.5%, or 2%, or any range of values ​​therebetween, compared to an electrode without foam. In some embodiments, the binder material includes one or more fibrillizable polymers, such as polytetrafluoroethylene (PTFE) and ultra-high molecular weight polyethylene (UHMWPE). In some embodiments, the binder material consists of, or consists essentially of, one type of polymer, such as PTFE. In some embodiments, the conductivity-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.

[0088] At block 304, the electrode film mixture is sealed 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 comprises a porous structure. In some embodiments, the foam has a relative density between 0.03 and 0.3, where relative density is defined as the ratio of the foam density to the density of a non-porous reference material, such as a non-porous metal or a non-porous ceramic. In some embodiments, the foam has a density of about 0.1 g / cm. 3 or up to about 0.1g / cm 3 , about 0.3g / cm 3 or up to about 0.3g / cm 3 , about 0.4g / cm 3 or up to about 0.4g / cm 3 , about 0.5 / cm 3 or up to about 0.5g / cm 3 , about 0.6g / cm 3 or up to about 0.6g / cm 3 , about 0.7g / cm 3 or up to about 0.7g / cm 3 , about 0.8g / cm 3 or up to about 0.8g / cm 3 , about 0.9g / cm 3 or up to about 0.9g / cm 3 , about 1.0g / cm 3 or up to about 1.0 g / cm 3 , about 1.5g / cm 3 or up to about 1.5g / cm 3 , about 2.0g / cm 3 or up to about 2.0g / cm 3In some embodiments, the foam has a porosity of about or at least about 25%, about or at least about 28%, about or at least about 30%, about or at least about 40%, about or at least about 50%, about or at least about 60%, about or at least about 70%, about or at least about 80%, about or at least about 85%, about or at least about 90%, about or at least about 95%, or about or at least about 98%, or any range of values ​​therebetween. In some embodiments, the foam has a predominant pore size or pore diameter of about 0.1 mm, up to about 0.1 mm or min. about 0.1 mm, about 0.2 mm, up to about 0.2 mm or min. about 0.2 mm, about 0.3 mm, up to about 0.3 mm or min. about 0.3 mm, about 0.4 mm, up to about 0.4 mm or min. about 0.5 mm, up to about 0.5 mm or min. about 0.5 mm, about 0.6 mm, up to about 0.6 mm or min. about 0.6 mm, about 0.7 mm, up to about 0.7 mm or min. about 0.7 mm, about 0.8 mm, up to about 0.8 mm or min. about 0.8 mm, about 0.9 mm, up to about 0.9 mm or min. about 1 mm, up to about 1 mm or min. mm, about 1.5 mm, up to about 1.5 mm or min about 1.5 mm, about 1.6 mm, up to about 1.6 mm or min about 1.6 mm, about 2 mm, up to about 2 mm or min about 2 mm, about 3 mm, up to about 3 mm or min about 3 mm, about 4 mm, up to about 4 mm or min about 4 mm, about 5 mm, up to about 5 mm or min about 5 mm, about 6 mm, up to about 6 mm or min about 6 mm, about 7 mm, up to about 7 mm or min about 7 mm, about 8 mm, up to about 8 mm or min about 8 mm, about 9 mm, up to about 9 mm or min about 9 mm, about 10 mm, up to about 10 mm or min about 10 mm, about 15 mm, up to about 15 mm or min about 15 mm, or any range of values ​​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. 3 Or a minimum of about 1g / cm 3 , about 1.5g / cm 3 Or a minimum of about 1.5g / cm 3 , about 2g / cm 3 Or a minimum of about 2g / cm 3 , about 3g / cm 3 Or a minimum of about 3g / cm 3 , about 4g / cm 3 Or a minimum of about 4g / cm 3 , about 5g / cm 3 Or a minimum of about 5g / cm 3 Or about 10g / cm 3 Or a minimum of about 10g / cm 3 , or any range of values ​​therebetween.

[0089] FIG. 4 is a process flow diagram illustrating an example of a process 400 for pressing a free-standing electrode film into a foam. In some embodiments, the free-standing electrode film in process 400 can be a cathode or an anode free-standing electrode film, as described herein. In some embodiments, the free-standing electrode film in process 400 is a cathode free-standing electrode film. In block 402, an electrode film mixture is formed. In some embodiments, the electrode film mixture is made by any method or with any composition described above. In some embodiments, the free-standing electrode film is composed of an active material and a binder. In some embodiments, the free-standing electrode film further comprises conductive carbon. In some embodiments, the free-standing electrode film further comprises conductive carbon and a lithium ion conducting 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% by weight, 1% by weight, 5% by weight, 10% by weight, 15% by weight, or 20% by weight, 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% by weight. In some embodiments, the total amount of lithium ion conductive ceramic in the film can be 0.5% by weight, 1% by weight, 5% by weight, 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, or 60% by weight, or any range of values ​​therebetween. For example, in some embodiments, the total amount of lithium ion conducting ceramic in the film ranges from about 1 to about 50 weight percent.

[0090] At block 404, the binder in the electrode film mixture is fibrillated. In some embodiments, fibrillation can be performed by any method described above, such as the process described in block 204 of FIG. 2. At block 406, the electrode film mixture is calendered to form a free-standing electrode film. In some embodiments, the free-standing electrode film can be produced by any method described above. Without being limited by theory, in some embodiments, after subjecting the electrode film mixture to a sufficiently high shear force and / or pressure, particles of a sufficiently small size provided or formed in the electrode film mixture become attracted by their surface free energy, providing a support matrix within which other particles can be supported. Without being limited by theory, it is theorized that under sufficient shear force and / or pressure, the particles in the electrode film mixture described herein can generally approach each other to a separation distance such that the particles are attracted to each other by attractive forces (such as London-van der Waals forces) resulting from the particles' intrinsic surface free energy to form a continuous, self-supporting film. At block 408, the free-standing electrode film is pressed and laminated to the foam. In some embodiments, the free-standing electrode film is pressed to the foam by calendaring. In some embodiments, the calendaring may be performed by a two-roll calendar press. In some embodiments, the foam may be made 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 may be laminated to a current collector. In some embodiments, the film-foam composite may function as an electrode without the addition of a current collector.

[0091] In some embodiments, once the dry cell has been constructed by methods known in the art, such as by winding or laminating the electrodes with the separator layers between them, a selected solvent or combination of solvents may be added to the dry cell for immediate use. In some embodiments, such as where long calendar life storage is essential, the fabricated dry cell may be stored dry with minimal degradation. In some embodiments, such as solid state energy storage devices, the fabricated dry cell may be ready for immediate use without the addition of a solvent or combination of solvents.

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

[0093] Exposing the electrode film to a solvent in the energy storage device In some embodiments, an energy storage device battery including an electrode film containing an electrode salt is filled or flooded with one or more electrolyte solvents to extract and dissolve the electrode salt from the electrode film. The dissolved electrode salt may serve as an ionic component or solute of an electrolyte system in the energy storage device. Additionally, extraction of the electrode salt from the electrode film may result in the electrode film being exposed to the solvent with increased pore volume and reduced overall density of the electrode film.

[0094] The salts, solvents and processing conditions may be selected to achieve the intended function. In some embodiments, the electrode salt and 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 is selected that is moisture sensitive. In some embodiments, an electrode salt is selected that is stable under normal device processing conditions. In some embodiments, an electrode salt is selected that does not decompose under normal device operating conditions.

[0095] In some embodiments, the electrode salt is LiPF 6 , LiBF 4 , LiBOB, LiN(SO 2 CF 3 ) 2 , LiiOSO 2 CF 3 , LiNO 3 , 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 pressures above 1 atmosphere. In some embodiments, the highly volatile solvent is a liquid below 20°C. In some embodiments, the highly volatile solvent has a boiling point at ambient pressure of about or up to about 10° C., about or up to about 20° C., about or up to about 30° C., about or up to about 40° C., about or up to about 50° C., about or up to about 57° C., about or up to about 60° C., about or up to about 66° C., about or up to about 66° C., about or up to about 70° C., about or up to about 80° C., about or up to about 90° C., about or up to about 91° C., or about or up to about 91° C., or about or up to about 95° C., or any range of values ​​therebetween. In some embodiments, the highly volatile solvent can be dimethyl carbonate, tetrahydrofuran (THF), methyl acetate, or mixtures thereof. In some embodiments, the highly volatile solvent produces a solvent-exposed electrode film with 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 at low temperatures, allowing the energy storage device to operate in low temperature environments, such as at or below about -150°C, at or below about -110°C, at or below about -108°C, at or below about -100°C, at or below about -98°C, at or below about -75°C, at or below about -75°C, at or below about -50°C, at or below about -25°C, at or below about -25°C, at or below about 0°C, at or below about 2°C, at or below about 2°C, at or below about 4°C, at or below about 5°C, or at or below about 10°C, or any value therebetween. In some embodiments, the highly volatile solvent allows 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 electrode salt is selected to provide electrolyte in the energy storage device at a target molar concentration. In some embodiments, the total amount of salt may be metered at the positive electrode. In some embodiments, the total amount of salt may be metered at the negative electrode. In some embodiments, the total amount of salt may be metered evenly at the positive and negative electrodes. In some embodiments, the total amount of salt may be metered 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.

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

[0099] Cleaning the electrode film In some embodiments, the electrode film containing the electrode salt is washed with one or more electrolyte solvents separate from the energy storage device container to extract and dissolve the electrode salt from the electrode film. Extracting the electrode salt from the electrode film may result in a solvent-exposed electrode film with increased pore volume and reduced overall density of the electrode film. Additionally, in some embodiments, the use of electrode salt material in the dry electrode film allows the electrode film to be prelithiated simultaneously with the washing process. In other embodiments, the washed electrode film may be prelithiated after the washing process, for example, the prelithiation of the electrode film may be performed in a separate prelithiation device or energy storage device container.

[0100] FIG. 5 is a schematic diagram showing an embodiment of a cleaning apparatus 500 for simultaneously performing 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 supply 503. The dry electrode film roll 501 can be prepared by any of the methods described above. The dry electrode film roll 501 is unrolled and unwound 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 a power supply 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, the negative polarization of the electrode film sheet 504 and the positive polarization of the pair of counter electrodes 508 electrochemically pre-lithiate the electrode film sheet 504 with the lithium component of the electrode salt. The electrode film sheet exits the solvent 506 and solvent bath 505 as a lithiated electrode film 509. The lithiated electrode film 509 is collected and rewound at a rewinding station 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 a rewound lithiated electrode 511. In some embodiments not shown, the lithiated electrode film 509 may be dried to remove solvent 506 from the solvent bath 505 or rinsing bath before being rewound into a rewound lithiated electrode 511. In some embodiments, pre-lithiation of the electrode film sheet 504 is not performed, and thus a power source 503 and counter electrode 508 pair is not utilized or is 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 include an electrolyte salt. In some embodiments, the solvent further comprises 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 electrode, as described above.

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

[0103] In some embodiments, the lithiated electrode film is substantially free or free of electrode salt. In some embodiments, the rewound lithiated electrode film is substantially free or free of electrode salt. In some embodiments, the lithiated electrode film has pores.

[0104] In some embodiments, the energy storage device with the lithiated electrode film further comprises an added electrolyte salt. In some embodiments, the energy storage device comprises 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 metered into the anode. In some embodiments, the total amount of salt can be metered evenly into the positive and negative electrodes. In some embodiments, the total amount of salt can be metered in any unequal amount into 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 herein includes mixing a dry solid electrolyte additive with a dry active material in a drying process to produce said dry electrode film. The intimate mixture of a solid electrolyte salt or solid electrolyte additive with 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-state lithium-ion batteries. Compared to wet electrode processes, dry electrode processes can also provide a more intimate contact at the solid electrolyte-active material interface, reducing solvent-induced degradation of moisture-sensitive solid electrolytes. In some embodiments, no solvent is added or removed. Furthermore, since the dry electrode coating process does not require drying of the solvent, a densely packed particle matrix can be produced, providing more contact of ions and electrons with the active material, resulting in an overall lower resistance of the electrode.

[0106] In some embodiments, the solid electrode is formed from the electrolyte electrode powder by methods similar to those 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 comprises 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 fibrillizable binder. In some embodiments, the molecular weight of the binder is about 1000 to about 5×10 6 g / mole. In some embodiments, the binder can include polymers having multiple molecular weight combinations or ranges. In some embodiments, the binder comprises about 2 to about 40% by weight of the electrolyte electrode powder. In some embodiments, the binder comprises about 1 to 15% by weight of the electrolyte electrode powder.

[0107] In some embodiments, the active material is LiNi, such as lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium nickel manganese cobalt oxide, lithium nickel cobalt aluminum oxide, and NMC811. 1-x-y Cox Mn y O 2 (NCM). In some embodiments, the cathode active material comprises 40-90% 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 Li 5 La 3 Ta 2 O 12 and Li 3 In some embodiments, the solid electrolyte additive is a sulfur-based ionic conductor, such as Li 2 SP 2 S 5 and Li 2 SP 2 S 5 -Li 3 PO 4 In some embodiments, the solid electrolyte additive may be other compounds with high ionic conductivity, such as Li 0.5 La 0.5 TiO 3 (LLTO) and / or Li 7 La 3 Zr 2 O 12 In some embodiments, the solid electrolyte additive is a lithium superionic conductor (LISCON), e.g., LISCON has the molecular formula Li (2+2x) Zinc (1-x) GeO 4 In some embodiments, the lithium salt comprises 1 to 10% by weight of the electrolyte electrode powder.

[0109] In some embodiments, the dry solid electrode film has a porosity ranging from about 1 to about 50% of the free void volume in 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 in the electrode film. 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 this disclosure.

[0110] An exemplary dry processing procedure for preparing a solid electrode is as follows: A cathode active material of NMC811 is dry mixed with LLZO in a ratio of about 7:2 (NMC811:LLZO) parts by weight. A conductive carbon is added to the mixed electrolyte-electrode powder of active material-LLZO powder in a ratio of about 0.5 parts by weight and further homogenized. About 0.5 parts by weight of a binder is added to the mixture and mixed under high shear to produce a powder blend prepared for self-supporting electrode film fabrication. The prepared powder blend is pressed against a self-supporting solid electrode film by a two-roll calender press. The film is then laminated to a metal current collector by a two-roll calender press to obtain a dry processed solid cathode.

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

[0112] Solid Polymer Electrolyte The dry powder mixing and film calendering process described above may also be utilized to produce composite polymer films for use as ionically conductive solid separators or electrolytes in solid energy storage devices such as solid lithium metal batteries. Dry processing of solid polymer electrolyte membranes may offer many advantages over typical wet solvent cast preparations, such as 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 the solvent or residual water from the membrane, the ability to prepare thinner polymer membranes, high electrochemical performance due to the absence of residual organic solvents in the polymer electrolyte film, and enabling a continuous roll-to-roll manufacturing process of both the polymer membrane and the complete cell assembly. Dry processed and solvent-free composite polymer films from the dry powder mixing and film calendering process are described, and the physical and electrochemical properties of such films are presented.

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

[0114] In some embodiments, the ion-conducting polymer is selected from at least one of 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(propyleneimine).

[0115] In some embodiments, the 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 Zr1.4 Ta 0.6 O 12 , Li 7 La 3 Zr 2 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 S y (PO 4 ) 3-y and LiTi x Zr 2-x (PO 4 ) 3 In some embodiments, the lithium source can be the lithium salts listed above or others.

[0116] In some embodiments, the supporting 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 dioxide (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 2S 2 O 5 (OH) 4 ), Hectorite (Na 0.3 (Mg,Li) 3 S 4 O 10 (OH) 2 ) and halloysite (Al 2 S 2 O 5 (OH) 4 ), 4'-amino-2,3'-dimethylazobenzene (CH 3 C 6 H 4 N=NC 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. Table 1 shows the specifications of the dry materials that can be used for the SPE film.

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

[0119] [Table 1]

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

[0121] [Table 2]

[0122] Dry powder mixing of the SPE dry powder formulations into the SPE dry powder mixtures can be done by the methods described above or by other methods. Dry powder mixing of the dry SPE formulations listed in Table 2 was done according to the mixing procedure shown in Table 3. Typical mixing and blending methods such as tumbler, convection, hopper and fluidization can be used to mix the powders. Resodyn powder mixing was done at 60% strength (50G) for 5 minutes. Some images of the resulting processed 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 processed dry powder mixtures may be converted into dry free-standing SPE films by the methods described above or other methods. Dry SPE films were produced from some of the dry powder mixtures described in Table 3 after calendering with the parameters shown in Table 4. FIG. 7 shows a first pass calendered SPE film converted from dry powders processed according to the first calendering process in Table 4. In FIG. 7, (a) shows SPE-2 (as calendered), (b) shows SPE-1, (c) shows SPE-3, and (d) shows SPE-4; (b)-(d) are all shown after calendering. FIG. 8 shows the first pass calendered SPE film of FIG. 7 that was recalendered according to the second calendering process in Table 4 to achieve the desired film thickness.

[0125] [Table 4]

[0126] FIG. 9 shows the surface morphology of the SPE-4 film after the first calendering step, and FIG. 10 shows the surface morphology of the SPE-4 film after the second calendering step. The first pass calendered SPE-4 film appears to have a rough and irregular surface, suggesting phase separation between the ion-conducting polymer and the supporting polymer matrix. The second pass calendered SPE-4 film shows a smoother surface than the first pass calendered film and the PTFE fibers. Also observed in FIG. 10 is a relatively dense SPE film without pores, which may allow for high ionic conductivity and prevent the ingress of lithium dendrites.

[0127] Furthermore, the films of SPE-1, SPE-2 and SPE-3 after the first pass calendering step were brittle, while the films after the second calendering step were more flexible. Furthermore, the SPE-4 and SPE-5 films produced very flexible and strong free-standing dried films due to the presence of fibrillated PTFE in the film. As shown in Figure 11, the mechanical strength of the free-standing dried SPE-4 film by ILLord tensile test showed a very high tensile strength peak (10.3 N) and a relatively long elongation (2.3 mm). Table 5 shows the specifications of the dried SPE films used in the tensile strength measurements shown in Figure 11.

[0128] [Table 5]

[0129] The ionic conductivity (σ) of the dry 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] Bulk impedance was measured using a symmetric Cu / SPE / Cu cell. Figure 12 shows the room temperature ionic conductivity values ​​of SPE-4 and SPE-5 films. The ionic conductivity of the dried SPE films is about an 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 films was also investigated using a symmetric Li / SPE / Li cell. It was found that the cell voltage exceeded 2 V during the first lithium stripping process due to the low ionic conductivity of the SPE film at room temperature and the high interfacial impedance between lithium metal and the SPE film. As shown in Table 6, the addition of about 0.8 mL of carbonate solvent-based electrolyte to the Li / SPE / Li cell significantly reduced the interfacial impedance and resulted in a stable polarization. Figure 13 shows the first Li stripping / deposition cycle of SPE-4 and SPE-5 electrolyte films in a 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 salt in the SPE-5 film.

[0133] [Table 6]

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

[0135] FIG. 15 shows the electrochemical capacity and coulombic efficiency of the graphite electrode with the three different cell configurations shown in FIG. 14. Note that the SPE-1 film is a rigid and porous film and does not contain an ionically conductive medium or lithium salt. Cells 1 and 2 have poor electrochemical performance due to poor electrolyte wettability to the SPE-1 film and / or poor mechanical stability of the porous SPE-1 film, which may lead to lithium dendrite infiltration and / or incompatibility of the carbonate solvent-based non-aqueous lithium-ion electrolyte with the SPE-1 film. However, cell 3 showed comparable capacity and efficiency to the prior art, which consists of a dry graphite electrode with lithium-ion electrolyte incorporated and a commercial polypropylene (PP) separator (from Celgard), as shown in Table 6.

[0136] [Table 7]

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

[0138] Solid Gradient Electrodes The solid electrode may include blending of dry solid electrolyte additive with dry active material in a drying process as described above to produce a dry electrode film to achieve a gradient electrolyte additive distribution within the solid electrode. In some embodiments, multiple solid dry electrode films are produced in which the concentration of solid electrolyte additive increases with each successive electrode film to produce a gradient electrolyte additive distribution. In some embodiments, multiple solid dry electrode films are calendered together to form a solid dry electrode film having a gradient of solid electrolyte additive concentration through the thickness of the film, or a graded solid dry electrode film. In some embodiments, such graded solid dry electrode films can be used in solid energy storage devices without a separate electrolyte separator, since the side of the graded solid dry electrode film containing the higher concentration of solid electrolyte additive functions as the electrolyte separator in the device.

[0139] In some embodiments, at least one of the layers of the graded solid dry electrode film has a solid electrolyte additive concentration of about 20% or more, about 30% or more, about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 80% or more, about 90% or more, or about 100% or more by weight, or any range of values ​​therebetween. In some embodiments, at least one of the layers of the graded solid dry electrode film has a solid electrolyte additive concentration of about 40% or more by weight. In some embodiments, one of the outer layers of the graded solid dry electrode film has a solid electrolyte additive concentration of about 20% or more, about 30% or more, about 40% or more, about 50% or more, about 60% or more, about 70% or more, about 80% or more, about 90% or more, or about 100% by weight, or any range of values ​​therebetween.

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

[0141] Features, materials, properties or groups described in connection with a particular aspect, embodiment or example should be understood to be applicable to any other aspect, embodiment or example described in this section or elsewhere in this specification, except where mutually incompatible. All features disclosed herein (including any accompanying claims, abstract and drawings) and / or all steps of any method or process so disclosed may be combined in any combination, except at least some combinations in which such features and / or steps are mutually exclusive. Protection is not limited to the details of the embodiments described. Protection extends to any novel or any novel combination of features disclosed herein (including any accompanying claims, abstract and drawings) or any novel or any novel combination of steps of any method or process so disclosed.

[0142] Moreover, certain features that are described in the disclosure in the context of separate implementations may also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation may also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in a particular combination, one or more features from a claimed combination may in some cases be deleted from the combination and the combination may be claimed as a subcombination or a variation of the subcombination.

[0143] Additionally, while operations may be illustrated or described in a particular order, such operations need not be performed in the particular order or sequential order shown, nor need all operations be performed, to achieve desirable results. 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. Additionally, operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that in some embodiments, the actual steps taken in the illustrated and / or disclosed processes may differ from those illustrated. Depending on the embodiment, certain steps may be omitted and other steps may be added. Additionally, features and attributes of certain embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Additionally, the separation of various system components in the above implementations should not be understood as requiring such separation in all implementations, and it should be understood that the components and systems described may generally be integrated together in a single product or packaged in multiple products. For example, any of the components of the energy storage systems described herein may be provided separately or integrated together (e.g., packaged together or mounted together) to form an energy storage system.

[0144] For purposes of this 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 disclosure may be embodied or carried out in a manner that achieves one advantage or group of advantages taught herein without necessarily achieving other advantages that may be taught or suggested herein.

[0145] Conditional language such as "may," "can," "might," "may," and "may," unless expressly stated otherwise or understood otherwise within the context in which it is used, is generally intended to convey that a particular embodiment includes certain features, elements, and / or steps, while other embodiments do not include them. Thus, such conditional language is not generally intended to imply that features, elements, and / or steps are in any way required by one or more embodiments, or that one or more embodiments necessarily include logic for determining whether those features, elements, and / or steps are included or performed in a particular embodiment, with or without user input or prompting.

[0146] Conjunctive language, such as the phrase "at least one of X, Y, and Z," is understood in the context in which it is commonly used to convey that an item, term, etc., can be either X, Y, or Z, unless otherwise noted. Thus, such conjunctive language is generally not intended to imply 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] As used herein, terms of degree, such as "approximately," "about," "generally," and "substantially," indicate that a value, amount, or characteristic near the recited value, amount, or characteristic also performs a desired function or achieves a desired result. For example, the terms "approximately," "about," "generally," and "substantially" can refer to amounts that are 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 result.

[0148] The scope of the present disclosure is not intended to be limited by the specific disclosure of preferred embodiments in this section or elsewhere herein, but may be defined by the claims, whether presented in this section or elsewhere herein, or presented in the future. 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 prosecution of the application, which examples should be interpreted 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 solid-state structure for an energy storage device, comprising: A dry electrode film and a dry composite solid polymer electrolyte (SPE) film laminated with the dry electrode film, The dry electrode film comprises: Dry active material; a fibrillated dry binder; and Dry electrolyte salt Equipped with The dry electrode film is free-standing and free of solvent residues and has a density of at least 0.8 g / cm ３ and having an electrode film density of The dry composite solid polymer electrolyte (SPE) film comprises: A dry ionically conductive polymer; A dry lithium source; a fibrillated second dry binder; an ionically conductive medium; and Dry Filler Materials Equipped with the ionically conductive medium is selected from nanoclays and garnets, or combinations thereof; the dry ionically conductive polymer is polyethylene oxide (PEO); The fibrillated second dry binder is a solid structure comprising polytetrafluoroethylene (PTFE).

2. 2. The solid structure of claim 1, 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, Li ２ S-P ２ S ５ , Li ２ S-P ２ S ５ -Li ３ P.O. ４ , Li ０．５ La ０．５ TiO3, Li ７ La ３ Zr ２ O １２ , lithium superionic conductor, 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 T ０．６ O １２ , Li １０ SnP ２ S １２ , Li ３ｘ La ２／３－ｘ TiO ３ (0<x<2 / 3), Li ０．８ La ０．６ Zr ２ (P.O. ４ ) ３ , Li １＋ｘ Ti ２－ｘ A ｘ (P.O. ４ ) ３ (0<x<2), Li １＋ｘ＋ｙ Ti ２－ｘ A ｘ S ｙ (P.O. ４ ) ３－ｙ (0<x<2, 0<y<3) and LiTi ｘ Zr ２－ｘ (P.O. ４ ) ３ (0<x<2), and combinations thereof.

3. 3. The solid structure according to claim 1 or 2, A solid structure, wherein the dry electrolyte salt comprises 1-10% by weight of the dry electrode film.

4. The solid structure according to any one of claims 1 to 3, The dry electrode film has a thickness of at least 110 μm.

5. A solid-state structure according to any one of claims 1 to 4, The dry electrode film comprises: A first dry electrode film, the dry electrode film of any one of claims 1 to 4, comprising a first concentration of the dry electrolyte salt; and A second dry electrode film comprising a second concentration of electrolyte salt, the first concentration of the electrolyte salt being less than the second concentration of the electrolyte salt. A solid structure that is a dry gradient electrode film having

6. An energy storage device comprising the solid structure of any one of claims 1 to 5, wherein the dry electrode film is free of liquid solvent.

7. A solid structure according to any one of claims 1 to 5, Solvent in the device housing and An energy storage device comprising:

8. 8. The energy storage device of claim 7, The solvent is a highly volatile solvent.

9. A battery comprising a solid-state structure according to any one of claims 1 to 5.

10. 1. A method for manufacturing a solid-state structure for an energy storage device, comprising the steps of: The method includes the steps of: preparing a dry electrode; preparing a dry composite solid polymer electrolyte (SPE) film; and laminating the dry electrode and the dry composite solid polymer electrolyte (SPE) film; The manufacture of the dry electrode comprises: Providing a dry active material, a dry fibrillated binder, and a dry electrolyte salt; and The dry active material, the fibrillated dry binder, and the dry electrolyte salt are free of solvent residues and have a density of at least 0.8 g / cm ３ forming a free-standing dry electrode film having an electrode film density of Including, The preparation of the dry composite solid polymer electrolyte (SPE) film includes: a mixture of a dry ionically conductive polymer, a dry lithium source, a dry fibrillated second binder, an ionically conductive medium, and a dry filler material; the ionically conductive medium is selected from nanoclays and garnets, or combinations thereof; the dry ionically conductive polymer is polyethylene oxide (PEO); 11. A method for producing a solid structure, wherein the fibrillated second dry binder comprises polytetrafluoroethylene (PTFE).

11. 11. The method of claim 10, further comprising the steps of: The method of making a solid-state structure further comprising exposing the free-standing dry electrode film to a solvent, thereby dissolving the dry electrolyte salt.

12. 12. The method of claim 11, further comprising the steps of: further comprising disposing the solid-state structure within an energy storage device housing; The method of manufacturing a solid-state structure, wherein exposing the free-standing dry electrode film to a solvent occurs within the energy storage device housing.

13. 12. The method of claim 11, further comprising the steps of: further comprising disposing the solid-state structure within an energy storage device housing; exposing the free-standing dry electrode film to a solvent prior to placing the solid-state structure in the energy storage device housing. A method for manufacturing solid structures.

14. 14. The method of claim 13, further comprising the steps of:

4. A method for fabricating a solid-state structure, further comprising pre-lithiating the free-standing dry electrode film during the step of exposing the free-standing dry electrode film to a solvent.

15. 15. The method of claim 14, further comprising the steps of: The method of making a solid-state structure further comprising rolling the lithiated free-standing dry electrode film.

16. A solid-state structure for an energy storage device, comprising: A dry electrode film and a dry composite solid polymer electrolyte (SPE) film laminated with the dry electrode film, the dry electrode film comprises a foam-active material composite; The foam-active material composite is Dry active material; a fibrillated dry binder; and Including foam, the dry active material and the fibrillated dry binder are sealed by the foam; The dry composite solid polymer electrolyte (SPE) film comprises: A dry ionically conductive polymer; A dry lithium source; a fibrillated second dry binder; an ionically conductive medium; and Dry Filler Materials Including, the ionically conductive medium is selected from nanoclays and garnets, or combinations thereof; the dry ionically conductive polymer is polyethylene oxide (PEO); The fibrillated second dry binder is a solid structure comprising polytetrafluoroethylene (PTFE).

17. 17. The solid structure of claim 16, The foam is a metal foam, a ceramic foam, or a combination thereof.

18. 18. A solid structure according to claim 16 or 17, An electrode of an energy storage device that does not include a separate current collector.

19. 18. A solid structure according to claim 16 or 17, The electrode of the energy storage device further comprises a current collector.

20. 1. A dry composite solid polymer electrolyte (SPE) film for an energy storage device, comprising: A dry ionically conductive polymer; A dry lithium source; A fibrillated dry binder; an ionically conductive medium; and Dry Filler Materials Including, the ionically conductive medium is selected from nanoclays and garnets, or combinations thereof; the dry ionically conductive polymer is polyethylene oxide (PEO); A dry composite solid polymer electrolyte (SPE) film, wherein the dry fibrillated binder comprises polytetrafluoroethylene (PTFE).

21. 21. The dry composite solid polymer electrolyte (SPE) film of claim 20, The 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 T ０．６ O １２ , Li ７ La ３ Zr ２ O １２ , Li １０ SnP ２ S １２ , Li ３ xL ２／３－ｘ TiO ３ (0<x<2 / 3), Li ０．８ La ０．６ Zr ２ (P.O. ４ ) ３ , Li １＋ｘ Ti ２－ｘ A ｘ (P.O. ４ ) ３ (0<x<2), Li １＋ｘ＋ｙ Ti ２－ｘ A ｘ S ｙ (P.O. ４ ) ３－ｙ (0<x<2, 0<y<3) and LiTi ｘ Zr ２－ｘ (P.O. ４ ) ３ (0<x<2), and combinations thereof.

22. 22. The dry composite solid polymer electrolyte (SPE) film of claim 20 or 21, The dry filler material is titanium dioxide (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 S ２ O ５ (OH) ４ ), Hectorite (Na ０．３ (Mg, Li) ３ S ４ O １０ (OH) ２ ), Halloysite (Al ２ S ２ O ５ (OH) ４ )), 4'-amino-2,3'-dimethylazobenzene (CH ３ C ６ H ４ N=NC ６ H ３ (CH ３ ) N.H. ２ ), yttrium aluminum oxide (Y ３ A ５ O １２ ), yttrium iron oxide (Y ３ Fe ５ O １２ ) and nanoclays, and combinations thereof.

23. a dry cathode electrode comprising a dry electrode film; A dry composite solid polymer electrolyte (SPE) film according to any one of claims 20 to 22; and Lithium Metal Anode An energy storage device comprising:

24. 24. The energy storage device of claim 23, An energy storage device that is a solid-state energy storage device that does not contain a liquid solvent.

Images