Compositions and methods for prelithiated energy storage devices

Abstract

To provide a dry electrode film for an energy storage device.SOLUTION: An energy storage device may include a cathode, an anode, and a separator between the cathode and the anode. At least one of electrodes may include an electrode film prepared by a drying process. The electrode film and / or the electrode may include prelithiating materials. A process and a device used to make electrodes and / or electrode films are also described.SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] Incorporation by reference of any priority application This application claims the benefit of U.S. Provisional Application No. 62 / 792,544, filed January 15, 2019, the entire contents of which are incorporated herein by reference. [Background technology]

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

[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 prepared using the improved electrode formulations and / or manufacturing processes can exhibit improved cycling 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 promote lower costs of energy storage device manufacturing. 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 practiced in a manner that achieves or optimizes one advantage or advantages taught herein without necessarily achieving other objects or advantages that may be 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. The dry electrode film further includes a dry binder. The dry electrode further includes a dry pre-lithiated material distributed throughout the dry active material and the dry binder. The dry electrode film is free-standing.

[0006] In some embodiments of the dry electrode film, the dry pre-lithiated material is Li2O2. In some embodiments, the dry active material is a dry cathode active material. In some embodiments, the dry cathode active material comprises sulfur or a sulfur-containing material.

[0007] In a second aspect, a method for manufacturing a dry electrode film for an energy storage device is provided. The method includes mixing a dry prelithiated material and a dry conductive carbon additive to form a first dry mixture. The method further includes mixing the first dry mixture with a dry active material to form a second dry mixture. The method further includes adding a dry fibrillizable binder to the second dry mixture to form a dry electrode film mixture. The method further includes fibrillating the dry binder in the dry electrode film mixture.

[0008] In some embodiments of the method, the method further comprises calendering the dry electrode film mixture. and forming a free-standing dry electrode film. In some embodiments, combining the first dry mixture with the dry active material further comprises combining a dry carbon material with a dry conductive carbon material to form a second dry mixture. In some embodiments, combining the dry pre-lithiated material with the dry conductive carbon additive is performed such that the temperature of the first mixture is at most about 100°C. In some embodiments, combining the dry pre-lithiated material with the dry conductive carbon additive creates electrical contact between the primary particles of the pre-lithiated material and the conductive carbon additive. In some embodiments, combining the dry pre-lithiated material with the dry conductive carbon additive is performed without excessively heating the first dry mixture. In some embodiments, the ratio of dry pre-lithiated material to dry conductive carbon additive is from about 5:1 to about 5:3.

[0009] All of these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments will become readily apparent to those skilled in the art from the following detailed description of the preferred embodiments, which refers to the accompanying drawings, and the invention is not limited to any particular preferred embodiment disclosed. [Brief explanation of the drawings]

[0010] These and other features, aspects, and advantages of the present disclosure will be described with reference to 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 view of a pre-lithiated energy storage device according to one embodiment. [Figure 2] FIG. 1 is a process flow diagram illustrating an example process for producing an electrode film from an electrode film mixture that includes prelithiated materials. [Figure 3A] 1 is an SEM image of as-received lithium peroxide. [Figure 3B] 1 is an SEM image of lithium peroxide mixed with SuperP® carbon black in a 5 to 2 ratio. [Figure 4] 1 is an image of a laminate electrode containing lithium peroxide submerged in water. [Figure 5] Electrochemical profiles of an electrochemical cell containing 2% lithium peroxide compared to a control cell containing no lithium peroxide. DETAILED DESCRIPTION OF THE INVENTION

[0011] Detailed Description The present disclosure relates to electrode films including prelithiated materials for use in energy storage devices, and methods for making the same. For example, the prelithiated materials may be incorporated into electrode films to replace lithium consumed in forming a solid electrolyte interphase (SEI) layer on the electrode during initial cycling of the corresponding energy storage device. The reaction of the prelithiated materials may also produce gas, which may beneficially increase the porosity of the electrode.

[0012] definition As used herein, the terms "battery" and "capacitor" should be given their ordinary and customary meaning to those skilled in the art. The terms "battery" and "capacitor" are not mutually exclusive. A capacitor or battery may refer to a single electrochemical cell that can operate alone or as a component of a multi-cell system.

[0013] As provided herein, a "self-supporting" electrode film is an electrode film that incorporates a binder matrix structure sufficient to support the film or layer and maintain its shape so that the electrode film or layer 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. Although support elements are used to facilitate the energy storage device manufacturing process, generally, and depending on the method employed, such electrode films or active layers have sufficient strength to be used in the energy storage device manufacturing process without any external support elements, such as current collectors, support webs, or other structures. For example, a "self-supporting" electrode film may have sufficient strength to be rolled, 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.

[0014] As provided herein, a "solvent-free" electrode film is an electrode film that does not contain any detectable process solvent, process solvent residue, or process solvent impurities. A dry electrode film, such as a cathode electrode film or an anode electrode film made with only dry components, can be solvent-free.

[0015] A "wet" electrode, "wet process" electrode, or slurry electrode comprises an electrode film or electrode prepared by at least one step involving a slurry of active material, binder, and optional additives, even if a subsequent drying step removes water from the electrode or electrode film. Thus, a wet electrode or wet electrode film will contain at least one or more processing solvents, processing solvent residues, and / or processing solvent impurities.

[0016] Conditional language such as "may," "could," "might," and "could," unless otherwise specified or understood otherwise within the context in which it is used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements, and / or steps. Thus, such conditional language is generally not intended to imply that features, elements, and / or steps are in any way required by one or more embodiments, nor is it generally intended to imply 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.

[0017] Transitive language such as the phrase "at least one of X, Y, and Z," unless otherwise specified, is otherwise understood in the context in which it is generally used to convey that an item, term, etc. can be either X, Y, or Z. Thus, such transitive 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.

[0018] As used herein, words of degree, such as "approximately," "about," "generally," and "substantially," refer to a value, amount, or characteristic that approaches the stated value, amount, or characteristic and performs a desired function or achieves a desired result. For example, the terms "approximately," "about," "generally," and "substantially" can refer to an amount that is less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the stated amount, depending on the desired function or desired result.

[0019] 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 modifications and equivalents thereof. Accordingly, the scope of the invention disclosed herein extends beyond the specific embodiments and / or uses described below. It is not intended to be limited by any embodiment.

[0020] In an attempt to increase the energy density of lithium-ion electrochemical devices, anode materials with high specific energy density, such as silicon, have been considered. During the first charge, lithium from the cathode material is consumed during the process of forming a solid electrolyte interphase (SEI) layer, which acts as a protective layer around the anode. However, the lithium ions consumed in this formation of the SEI layer are unavailable for cycling during normal operation of the electrochemical device, reducing its performance potential. Described below are electrode film compositions and formation processes that enable the incorporation of prelithiated materials into the electrode film mixture used to form the prelithiated electrode film. Some embodiments avoid or reduce decomposition of the prelithiated material due to exposure to solvents and high temperatures. Furthermore, in some embodiments, such prelithiated materials may have the added benefit of producing prelithiated electrodes with increased porosity.

[0021] 1 is a side cross-sectional schematic diagram of an example of a pre-lithiated energy storage device 100 comprising a pre-lithiated electrode film. Energy storage device 100 may be classified as, for example, a capacitor, a battery, a capacitor-battery hybrid, or a fuel cell. In some embodiments, device 100 is a lithium-ion battery.

[0022] The device includes a first electrode 102, a second electrode 104, and a separator 106 disposed between the first electrode 102 and the second electrode 104. The first electrode 102 and the second electrode 104 are adjacent to opposite surfaces of the separator 106. The energy storage device 100 includes an electrolyte 118 to facilitate ionic transfer between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 118 may be in contact with the first electrode 102, the second electrode 104, and the separator 106. The electrolyte 118, the first electrode 102, the second electrode 104, and the separator 106 are contained within an energy storage device housing 120.

[0023] One or more of the first electrode 102, second electrode 104, and separator 106, or components thereof, may comprise a porous material. Pores within the porous material may provide containment and / or increased surface area for contacting the electrolyte 118 within the housing 120. The energy storage device housing 120 may be sealed around the first electrode 102, second electrode 104, and separator 106 and may be physically sealed from the surrounding environment.

[0024] 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 separator 106 can 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 ionic communication between the two adjacent electrodes. The separator 106 can include a suitable porous, electrically insulating material. In some embodiments, the separator 106 can include a polymeric material. For example, the separator 106 can include a cellulose material (e.g., paper), a polyethylene (PE) material, a polypropylene (PP) material, and / or a polyethylene and polypropylene material.

[0025] Generally, the first electrode 102 and the second electrode 104 each comprise a current collector and an electrode film. The electrodes 102 and 104 comprise electrode films 112 and 114, respectively, having high electrode film density and / or high electron density. While the electrodes 102 and 104 each comprise a single electrode film 112 and 114 as shown, other combinations of two or more electrode films for each electrode 102 and 104 are possible. While the device 100 is shown with a single electrode 102 and a single electrode 104, other combinations are possible. The electrode films 112 and 114 can each have any suitable shape, size, and thickness. For example, The electrode films can each have a thickness of about 30 microns (μm) to about 250 microns, e.g., about or at least about 50 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, about 300 microns, about 400 microns, about 500 microns, about 750 microns, about 1000 microns, about 2000 microns, or any range of values ​​therebetween. For single electrode films, additional electrode film thicknesses are described throughout this disclosure. Electrode films generally include one or more active materials, such as anode active materials or cathode active materials, as provided herein. The electrode films 112 and / or 114 can be dry and / or self-supporting electrode films as provided herein and can have advantageous properties, such as thickness, increased electrode film density, energy density, specific energy density, areal energy density, areal capacitance, or specific capacitance, as provided herein. The first electrode films 112 and / or 114 can also include one or more binders as provided herein. The electrode films 112 and / or 114 can be prepared by the processes described herein. The electrode films 112 and / or 114 can be wet or self-supporting dry electrodes as described herein.

[0026] As shown in FIG. 1 , the first electrode 102 and the second electrode 104 each include a first current collector 108 in contact with the first electrode film 112 and a second current collector 110 in contact with the second electrode film 114. The first current collector 108 and the second current collector 110 facilitate electrical coupling between the corresponding electrode film and an external electrical circuit (not shown). The first current collector 108 and / or the second current collector 110 may comprise 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 circuit. For example, the current collectors may include metallic materials such as aluminum, nickel, copper, rhenium, niobium, tantalum, and materials including 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 can comprise, for example, aluminum foil or copper foil. The first current collector 108 and / or the second current collector 110 can have a rectangular or substantially rectangular shape sized to provide for the transfer of charge between the corresponding electrode and an external circuit.

[0027] 1, the second electrode film 114 is prelithiated. However, it should be understood that the first electrode film 112 can be prelithiated, or both electrode films 112 and 114 can be prelithiated. Electrode films 112 and / or 114 can be prelithiated as described herein.

[0028] In some embodiments, the energy storage device 100 is filled with a suitable lithium-containing electrolyte 118. For example, the device 100 may include a lithium salt and a solvent, such as a non-aqueous or organic solvent. Generally, the lithium salt may include a redox-stable anion. In some embodiments, the anion may be monovalent. In some embodiments, the lithium salt may be selected from hexafluorophosphate (LiPF), lithium tetrafluoroborate (LiBF), lithium perchlorate (LiClO), lithium bis(trifluoromethanesulfonyl)imide (LiN(SOCF)), lithium trifluoromethanesulfonate (LiSOCF), lithium bis(oxalato)borate (LiBOB), and combinations thereof. In some embodiments, the electrolyte may include a quaternary ammonium cation and an anion selected from the group consisting of hexafluorophosphate, tetrafluoroborate, and iodide. In some embodiments, the salt concentration can be about 0.1 mol / L (M) to about 5 M, about 0.2 to about 3 M, or about 0.3 to about 2 M. In further embodiments, the salt concentration of the electrolyte can be about 0.7 to about 1 M. In certain embodiments, the salt concentration of the electrolyte can be about 0.2 M, about 0.3 M, about 0.4 M, about 0.5 M, about 0.6 M, about 0.7 M, about 0.8 M, about 0.9 M, about 1 M, about 1.1 M, about 1.2 M, or any range of values ​​therebetween.

[0029] In some embodiments, the energy storage device electrolytes provided herein can include a liquid solvent. The solvents provided herein need not dissolve all components of the electrolyte, and need not completely dissolve any component. In further embodiments, the solvent can be an organic solvent. In some embodiments, the solvent can have one or more functional groups selected from carbonates, ethers, and / or esters. In some embodiments, the solvent can include a carbonate. In further embodiments, the carbonate can be selected from cyclic carbonates such as, for example, ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof, or acyclic carbonates such as, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and combinations thereof. In certain embodiments, the electrolyte can include LiPF and one or more carbonates.

[0030] In some embodiments, the lithium ion battery is configured to operate between about 2.5 and 4.5 V or between 3.0 and 4.2 V. In further embodiments, the lithium ion battery is configured to have a minimum operating voltage between about 2.5 and about 3 V, respectively. In yet other embodiments, the lithium ion battery is configured to have a maximum operating voltage between about 4.1 and about 4.4 V, respectively.

[0031] In some embodiments, a method for manufacturing an energy storage device is provided. In further embodiments, the method includes selecting an anode and a cathode. In some embodiments, selecting the anode includes selecting a dry self-supporting anode or a wet anode. In further embodiments, selecting the cathode includes selecting a dry self-supporting cathode or a wet cathode. The step of selecting the dry anode can include selecting an active material processing method and selecting a binder processing method.

[0032] In some embodiments, the electrode films provided herein include 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 a battery anode or cathode. The anode active material can include, for example, an intercalation material (such as carbon, graphite, and / or graphene), an alloying / dealloying material (such as silicon, silicon oxide, tin, and / or tin oxide), a metal alloy or compound (such as Si-Al and / or Si-Sn), and / or a conversion material (such as manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anode active materials may be used alone or mixed to form multiphase materials (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).

[0033] 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 (LCO), Li(NiMnCo)O (NMC), and / or LiNi 0.8 Co 0.15 Al 0.05 O2 (NCA), etc.), spinel manganese oxide (LiMn2O4 (LMO) and / or LiMn 1.5 Ni 0.5 O4 (e.g., LMNO) or olivine (e.g., LiFePO4). The active material can include sulfur or a sulfur-containing material such as lithium sulfide (LiS) or other sulfur-based materials or mixtures thereof. In some embodiments, the cathode film includes sulfur or a sulfur-containing material at a concentration of at least 50% by weight. In some embodiments, the cathode film including sulfur or a sulfur-containing material has a capacity of at least 6 mAh / cm. 2 In some embodiments, the cathode film comprising sulfur or a sulfur active material-containing material has an areal capacity of 1 g / cm 3 In some embodiments, the cathode film comprising sulfur or a sulfur active material-containing material further comprises a binder. In some embodiments, the binder of the cathode film comprising sulfur or a sulfur active material-containing material is selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), other thermoplastic materials, or any combination thereof.

[0034] The electrode film may include at least one active material combined with 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 may be, for example, activated carbon 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. In some embodiments, these carbon materials described herein may be different from the conductive carbon additive and / or conductive carbon material described in more detail below with respect to Examples 1 and 2 and the process shown in FIG. 2.

[0035] In some embodiments, the cathode electrode film of a 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 a 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 %, including, for example, about 1.5 to 10 wt %, about 1.5 to 5 wt %, or about 1.5 to 3 wt %, of the binder. 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 20% by weight or up to about 20% by weight, about 15% by weight or up to about 15% by weight, about 10% by weight or up to about 10% by weight, about 5% by weight or up to about 5% by weight, about 3% by weight or up to about 3% by weight, about 1% by weight or up to about 1% by weight 0.5% by weight or up to about 1.5% by weight or about 1% by weight or up to about 1% by weight, or any range of values ​​therebetween, of binder.

[0036] In some embodiments, the anode electrode film may include at least one active material, a binder, and optional conductive additives and / or conductive materials. In some embodiments, the conductive additive may include a conductive carbon additive such as carbon black. In some embodiments, the conductive material may include a conductive carbon material such as carbon black. In some embodiments, the conductive carbon additive is a different type and / or amount of material from the conductive carbon material. For example, in some embodiments, the conductive carbon additive and the conductive carbon material are different carbon black materials. 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, a mixture, or a composite of the foregoing materials. In some embodiments, the anode electrode film may include about 80 to about 98 wt %, including about 80 to about 98 wt %, or about 94 to about 97 wt %, of the at least one active material. In some embodiments, the anode electrode film may comprise about 80 wt%, about 85 wt%, about 90 wt%, about 92 wt%, about 94 wt%, about 95 wt%, about 96 wt%, about 97 wt%, about 98 wt%, or about 99 wt%, or any range of values ​​therebetween, of at least one active material. In some embodiments, the anode electrode film may comprise up to about 5 wt%, including about 1 to about 3 wt%, of a conductive additive. In some embodiments, the anode electrode film may 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 may comprise 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 a binder. In some embodiments, the anode electrode film comprises about 4 wt. % of a 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 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 the binder, or any range of values ​​therebetween. In some embodiments, the anode film can be free of conductive additives.

[0037] Some embodiments include electrode films, such as anodes and / or cathodes, having one or more active layers comprising a polymer binder material. The binder may include polytetrafluoroethylene (PTFE), polyolefins, polyalkylenes, polyethers, styrene-butadiene, polysiloxanes and copolymers of polysiloxanes, branched polyethers, polyvinyl ethers, 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 material. In some embodiments, the binder includes a fibrillizable polymer. In certain embodiments, the binder includes, consists essentially of, or consists of a single fibrillizable binder, such as PTFE.

[0038] In some embodiments, the binder may include PTFE and optionally one or more additional binder components. In some embodiments, the binder may include one or more polyolefins and / or copolymers thereof and PTFE. In some embodiments, the binder may include PTFE and one or more of cellulose, polyolefin, polyether, polyether precursor, polysiloxane, copolymers thereof, and / or mixtures thereof. The mixture of polymers may include interpenetrating networks of the aforementioned polymers or copolymers.

[0039] The binder may contain various suitable ratios of polymer components, for example, PTFE may be up to about 98% by weight of the binder, such as about 20 to about 95% by weight, about 20 to about 90% by weight, about 20 to about 80% by weight, about 30 to about 70% by weight, about 30 to about 50% by weight, or about 50 to about 90% by weight. In some embodiments, the PTFE can be about or up to about 99%, about 98%, or up to about 98%, about 95%, or up to about 95%, about 90%, or up to about 90%, about 80%, or up to about 80%, about 70%, or up to about 70%, about 60%, or up to about 60%, about 50%, or up to about 50%, about 40%, or up to about 40%, about 30%, or up to about 30%, or about 20%, or up to about 20% by weight of the binder, or any range of values ​​therebetween.

[0040] In some embodiments, the electrode film mixture can include binder particles having a selected size, such as about 50 nm, about 100 nm, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350 nm, about 400 nm, about 450 nm, about 500 nm, about 1 μm, about 2 μm, about 3 μm, about 4 μm, about 5 μm, about 10 μm, about 50 μm, about 100 μm, or any range of values ​​therebetween.

[0041] As used herein, a dry electrode manufacturing process may refer to a process that uses no, or substantially no, solvents to form a dry electrode film. For example, the components of an active layer or electrode film, including the carbon material and binder, may comprise, consist of, or consist essentially of dry particles. The dry particles for forming an active layer or electrode film may be combined to provide a dry particle active layer mixture. In some embodiments, an active layer or electrode film may be formed from a dry particle active layer 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 layer mixture are substantially the same. In some embodiments, an active layer or electrode film formed from a dry particle active layer mixture using a dry manufacturing process may be free or substantially free of any processing additives, such as solvents and solvent residues resulting therefrom. In some embodiments, the resulting active layer or electrode film is a self-supporting film formed from a dry particle mixture using a drying process. In some embodiments, the resulting active layer or electrode film is a free-standing film formed from a dry particle mixture using a drying process. The process for forming the active layer or electrode film may include fibrillating a fibrillizable binder component such that the film comprises the fibrillated binder. In a further embodiment, a free-standing active layer or electrode film may be formed in the absence of a current collector. In yet another embodiment, the active layer or electrode film may comprise a polymer matrix that is fibrillated 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.

[0042] 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 14 mg / 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 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 the electrode film per unit area of ​​the electrode film or current collector) of at least about 12 mg / cm or any range of values ​​therebetween. 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 / cm2 , 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 range of values ​​therebetween, the electrode material loading or active material loading (which may be expressed as the weight of the electrode film per unit area of ​​the electrode film or current collector).

[0043] The electrode film can have a selected thickness suitable for a particular application. The thickness of the electrode films provided herein can be thicker than the thickness of electrode films prepared by conventional processes. In some embodiments, the electrode film can be about 110 microns or more, about 115 microns, about 120 microns, about 130 microns, about 135 microns, about 150 microns, about 155 microns, about 160 microns, about 170 microns, about 200 microns, about 250 microns, about 260 microns, about 265 microns, about 270 microns, about 280 microns, about 290 microns, about 300 microns, about 350 microns, about 400 microns, about 450 microns, about 500 microns, about 750 microns, about 1 mm, or about 2 mm, or any range of values ​​therebetween. The thickness of the electrode film can be selected to correspond to a desired areal capacitance, specific capacitance, areal energy density, energy density, or specific energy density.

[0044] 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) of about 10%, about 12%, about 14%, about 16%, about 18%, or about 20%, or any range of values ​​therebetween. 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) of at least about 10%, at least about 12%, at least about 14%, at least about 16%, at least about 18%, or at least about 20%, 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 that is occupied by pores) of at most about 10%, at most about 12%, at most about 14%, at most about 16%, at most about 18%, or at most about 20%, or any range of values ​​therebetween.

[0045] 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 , approximately 1.4 g / cm 3 , 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 / cm3 , about 3.0g / cm 3 , about 3.3g / cm 3 , approximately 3.4 g / cm 3 , about 3.5g / cm 3 , about 3.6g / cm 3 , about 3.7g / cm 3 or approximately 3.8 g / cm 3 In some embodiments, the electrode film has a density of at most about 0.8 g / cm. 3 , 1.0g / cm 3 , 1.4g / cm 3 , at most about 1.5 g / cm 3 , at most about 1.6 g / cm 3 , at most about 1.7 g / cm 3 , maximum of about 1.8 g / cm 3 , maximum of about 1.9 g / cm 3 Or at most 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 , 1.0g / cm 3 , 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 or at least about 3.5 g / cm 3 , or any range of values ​​therebetween.

[0046] In some embodiments, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, has an energy storage capacity of about 3.5 mAh / cm 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 2 or 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 2In a further embodiment, the energy storage device electrode film, where the electrode film is a dry and / or self-supporting film, may provide an areal capacity (which may 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 8mAh / 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.

[0047] In some embodiments, the anode electrode film of the 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 , approximately 9mAh / cm 2 , about 10mAh / cm 2 or any of the above Any range of values ​​of areal capacitance may be provided. In some embodiments, the areal capacitance is a charge capacity. In further embodiments, the areal capacitance is a discharge capacity.

[0048] 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 specific capacity (which may be expressed as capacity per mass of the electrode film or current collector) 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 electrode film of an energy storage device, 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.

[0049] 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 electrode film of an energy storage device, where the electrode film is a dry and / or self-supporting film, may provide a coulombic efficiency (which may be expressed as a percentage of discharge capacity divided by charge capacity) of about or at least about 85%, about 86%, or at least about 86%, about 87%, or at least about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, or about 95%, or any range of values ​​therebetween, such as 90.1%, 90.5%, and 91.9%, or any range of values ​​therebetween.

[0050] In some embodiments, the electrode film or electrode of an energy storage device, 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 retention percentage (which may be expressed as the discharge capacity at a predetermined 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 30%, about or at least about 40%, about or at least about 40%, about or at least about 50%, about or at least about 50%, about or at least about 60%, about or at least about 60%, about or at least about 70%, about or at least about 70%, about or at least about 80%, 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%, or about or at least about 100%, or any range of values ​​therebetween. In some embodiments, the discharge rate for percentage charge capacity retention is about or at least about C / 10, about or greater than about C / 5, about or at least about C / 3, about or at least about C / 2, about or greater than about 1 C, about or at least about 1.5 C, or 2 C, or at least about 2 C, or any value therebetween.

[0051] In some embodiments, the electrode film or electrode of an energy storage device, where the electrode film is a dry and / or self-supporting film or the electrode comprises a dry and / or self-supporting film, has about 10%, or at least about 10%, about 20%, or less The charge capacity generating percentage (which may be expressed as the charge capacity measured at a predetermined constant current rate divided by the discharge capacity measured at C / 10) may be at least about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 98%, about 99%, about 99.9%, or about 100%, or any range of values ​​therebetween. In some embodiments, the charge rate for the charge capacity generating percentage is at least C / 10, C / 5, C / 3, C / 2, 1 C, 1.5 C, or 2 C, or any value therebetween.

[0052] In some embodiments, the electrode film of an energy storage device, where the electrode film is a dry and / or self-supporting film, can provide a specific energy density or gravimetric 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.

[0053] 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 an energy density or volumetric energy density (which may 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.

[0054] In some embodiments, a self-supporting dry battery cathode may exhibit reduced ohmic resistance and / or improved voltage polarization characteristics compared to a wet battery cathode. In further embodiments, a lithium ion battery incorporating a self-supporting dry cathode may advantageously exhibit reduced ohmic resistance and / or improved voltage polarization characteristics compared to a lithium ion battery with a wet cathode and a wet anode. In yet other embodiments, a lithium ion battery incorporating a self-supporting dry cathode may exhibit improved energy density and / or specific energy density compared to a lithium ion battery with a wet cathode.

[0055] In some embodiments, aged self-supporting dry battery electrodes may exhibit reduced ohmic resistance, improved voltage polarization characteristics, and / or improved capacity compared to aged wet battery electrodes. In some embodiments, aged dry battery electrodes exhibit a reduction in ohmic resistance that is about 5 times, about 10 times, about 15 times, or about 20 times less than the reduction in ohmic resistance of similarly aged wet battery electrodes, or any range of values ​​therebetween. In some embodiments, aged dry battery electrodes exhibit a voltage drop that is about 1.5 times, about 2 times, about 3 times, or about 5 times less than the voltage drop of similarly aged wet battery electrodes, or any range of values ​​therebetween. In some embodiments, aged dry battery electrodes exhibit a voltage drop that is about 1.5 times, about 2 times, about 3 times, or about 5 times less than the voltage drop of similarly aged wet battery electrodes, or any range of values ​​therebetween. The capacity loss is about 1.5 times, about 2 times, about 3 times, or about 5 times less, or any range of values ​​therebetween, than that of a modified wet battery electrode.

[0056] Prelithiated Prelithiation of an electrode can make it possible to replace lithium consumed during the first cycle of an electrochemical device, which is no longer available for subsequent cycles. A sacrificial prelithiation material can be incorporated into the electrode to replace lithium consumed, for example, during the formation of a solid electrolyte interphase (SEI) layer on the anode during the first cycle.

[0057] As defined herein, a prelithiated material is a material containing lithium that is oxidized when the electrochemical device is cycled to form free lithium ions and by-products. The lithium ions may be solvated by the device's electrolyte. In this manner, the prelithiated material serves as a source of lithium from within the electrode film, replacing lithium ions consumed during the initial charging process of the electrochemical device. In some embodiments, the prelithiated material is a strong reducing agent. In some embodiments, the prelithiated material is lithium oxide. In some embodiments, the prelithiated material is lithium oxide (LiO), lithium peroxide (LiO), LiS, LiN, LiN, LiF, LiFeO, LiNiO, LiCO, LiMoO, or mixtures thereof. In some embodiments, the prelithiated material is LiO. It is understood that the prelithiated material does not include elemental lithium metal, which is lithium metal in its zero oxidation state.

[0058] In addition to lithiating the electrode, the reaction of the prelithiated material may also produce beneficial by-products. In some embodiments, the by-products may be gases. For example, the decomposition of lithium peroxide produces oxygen gas. The production of gas from the prelithiated material in the electrode may beneficially increase the porosity of the electrode.

[0059] In some embodiments, the electrode film mixture can include 0.5% by weight or about 0.5% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, or about 10% by weight, or any range of values ​​therebetween.

[0060] 2 is a process flow diagram illustrating an example process 200 for manufacturing an electrode film including a prelithiated material, according to some embodiments. In block 202, a mixing step forms a first mixture including the prelithiated material and a conductive carbon additive. In some embodiments, the prelithiated material is lithium peroxide. In some embodiments, the conductive carbon additive is carbon black, as described herein. In some embodiments, the mixing shown in block 202 is performed without excessively heating the first mixture. In some embodiments, the mixing indicated in block 202 is performed such that the temperature of the first mixture is at most or at most about 200°C, at most or at most about 150°C, at most or at most about 150°C, at most or at most about 140°C, at most or at most about 140°C, at most or at most about 130°C, at most or at most about 130°C, at most or at most about 120°C, at most or at most about 120°C, at most or at most about 110°C, at most or at most about 110°C, at most or at most about 100°C, at most or at most about 90°C, at most or at most about 90°C, at most or at most about 80°C, at most or at most about 70°C, at most or at most about 60°C, or at most or at most about 60°C, or at most or at most about 50°C, or any range of values ​​therebetween. In some embodiments, the mixing shown in block 202 is performed by heating the first mixture at a temperature of less than or about 200°C, less than or about 150°C, less than or about 150°C, less than or about 140°C, less than or about 130°C, less than or about 120°C, less than or about 110°C, less than or about 110°C, less than or about 100°C, or The prelithiated material is mixed at a temperature of at most about 100°C, at or below 90°C, at or below 80°C, at or below 70°C, at or below 60°C, or at or below 50°C, or any range of values ​​therebetween. In some embodiments, the mixing indicated in block 202 is performed by blending. In some embodiments, the weight ratio of the prelithiated material to the conductive carbon additive is about 10:1, about 5:1, about 5:2, about 5:3, about 5:4, or about 1:1, or any range of values ​​therebetween. In some embodiments, the prelithiated material and the conductive carbon additive are intimately mixed to uniformly distribute the components throughout the first mixture. In some embodiments, the prelithiated material and the conductive carbon additive are mixed to provide electrical contact between the primary particles of the prelithiated material and the conductive carbon additive.

[0061] In block 208, the first mixture of block 202 is mixed with an active material, a carbon material, and a conductive carbon material to form a second mixture. In some embodiments, the active material, the carbon material, and the conductive carbon material are first mixed to form an additional mixture before being mixed with the first mixture of block 202. In some embodiments, the conductive carbon material is carbon black, as described herein. In some embodiments, no carbon material and / or conductive carbon material is used in block 208 to form the second mixture. In some embodiments, the mixing indicated in block 208 is performed by blending. In some embodiments, the mixing indicated in block 208 is performed such that the temperature of the first mixture is at most or at most about 200°C, at most or at most about 150°C, at most or at most about 150°C, at most or at most about 140°C, at most or at most about 140°C, at most or at most about 130°C, at most or at most about 130°C, at most or at most about 120°C, at most or at most about 120°C, at most or at most about 110°C, at most or at most about 110°C, at most or at most about 100°C, at most or at most about 90°C, at most or at most about 90°C, at most or at most about 80°C, at most or at most about 70°C, at most or at most about 60°C, or at most or at most about 60°C, or at most or at most about 50°C, or any range of values ​​therebetween. In some embodiments, the mixing indicated in block 208 is performed such that the temperature of the first mixture is less than or about 200°C, less than or about 150°C, less than or about 140°C, less than or about 140°C, less than or about 130°C, less than or about 120°C, less than or about 120°C, less than or about 110°C, less than or about 100°C, less than or about 90°C, less than or about 80°C, less than or about 70°C, less than or about 60°C, or less than or about 50°C, or any range of values ​​therebetween. In some embodiments, the first mixture, active material, carbon material, and conductive carbon material are intimately mixed to uniformly distribute the components throughout the second mixture. In some embodiments, the mixing process of block 208 is utilized to break down or alter particles of the active material.In some embodiments, the modified particles of active material act to catalyze the reaction of the prelithiated material during the first cycle of the electrochemical device.

[0062] In some embodiments, the mixing steps of blocks 202 and 208 may utilize a continuous mixing process. In such embodiments, the duration of blending and / or grinding may be inversely proportional to the feed rate. Generally, the feed rate depends on the milling machinery and may be adjusted based on the machine's operating parameters in light of the guidance provided herein. In further embodiments, equipment with larger channels may be used to increase the duration of blending and / or grinding. When a batch blending and / or grinding process is utilized, the duration may be increased simply by blending and / or grinding for a longer time and / or at a higher RPM.

[0063] In block 210, the electrode film mixture is prepared by adding a fibrillizable binder to the mixture in block 2. The electrode film mixture is formed by adding the fibrillizable binder to the second mixture of block 210. In some embodiments, the fibrillizable binder and the second mixture may be intimately mixed to uniformly distribute the components throughout the electrode film mixture. At block 212, the fibrillizable binder in the electrode film mixture may be fibrillized to form fibrils from the binder material. The fibrillation process may be performed by reducing the speed and / or increasing the process pressure. Reducing the speed and / or increasing the process pressure may promote increased fibril formation, thereby allowing a lesser amount of binder material to 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 blending and / or milling process, and in some embodiments, a high shear process, such as jet milling. 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 process pressure in the blender and / or mill during the fibrillation process can be increased. In some embodiments, the addition step of block 210 and the fibrillation step of block 212 can be one or substantially one continuous step. By reducing the speed and / or increasing the process pressure, electrode films with sufficient strength, such as freestanding electrode films, can be produced either by a single, higher pressure calendering process (in a single step) or by multiple calendering steps, for example, by unwounding the film and then re-calendering it one or more times after the initial calendering step.

[0064] At block 214, the electrode film mixture may 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 gap or a hydraulically or pneumatically fixed gap) 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, forming 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 their resulting residues. In some embodiments, the electrode film is an anode electrode film. In some embodiments, the electrode film is a cathode electrode film.

[0065] In some embodiments, the process 200 for manufacturing an electrode film is a dry process, does not use liquids or solvents, the listed raw materials are dry (e.g., one or more are dry powders), and the resulting electrode film is free or substantially free of liquids, solvents, and resulting residues. In other wet electrode film processes, prelithiated materials can react with solvents, such as PVDF and N-methyl-2-pyrrolidone (NMP), which can produce by-products that can adversely affect the performance of the energy storage device. Thus, the dry electrode process can provide a unique method for incorporating prelithiated materials into an electrode film without exposure to solvents. Furthermore, polytetrafluoroethylene (PTFE) can be advantageously utilized because it is resistant to some acceptable prelithiated materials, such as lithium peroxide.

[0066] In the following specific examples, battery electrodes were produced with high energy density, high specific energy density, high thickness and / or high electrode film density. [Example]

[0067] Example 1 Example 1 describes an electrode film formed according to the process shown in Figure 2. Lithium peroxide was mixed with SuperP® carbon black in a 5:2 ratio in a Waring blender on a low setting in an argon glove box for 10 minutes. Figure 3A shows an SEM image of lithium peroxide, which shows submicron primary particles. Figure 3B shows an SEM image of lithium peroxide mixed with SuperP® carbon black in a 5:2 ratio, which shows intimate mixing and uniform distribution of both components. This first dry mixture was mixed as described with reference to Figure 2 to ensure dispersion of the lithium peroxide and conductive carbon black. Here, the lithium peroxide and SuperP® were mixed in intermittent pulses at 3000 rpm for 30 seconds with 30-second cooling periods in between. The blending was limited to a temperature of the lithium peroxide and SuperP® mixture below approximately 100°C to avoid excessive heating of the mixture during blending.

[0068] A pre-densified mixture of cathode active material NMC-622, activated carbon, and Ketjen Black® was formed, to which the lithium peroxide / SuperP® mixture was added and blended for 5 minutes at a low setting in an argon glove box. During the first cycle of the electrochemical device, the blending was partially performed to decompose a small portion of the secondary particles of the cathode active material so that the smaller primary particles could act as catalysts for the oxygen evolution reaction of the lithium peroxide. Finally, a PTFE binder was added to the mixture, which fibrillated the binder to form the electrode film mixture.

[0069] Calendering of the electrode film mixture was performed in a dry room to minimize exposure of the powder to moisture to form a free-standing electrode film, which was then further calendered to the desired load and laminated onto aluminum foil with an adhesive coating to form the cathode electrode.

[0070] Figure 4 shows an image of such a laminated electrode submerged in water. In Figure 4, oxygen bubbles are visible on the surface of the laminated electrode, indicating that the lithium peroxide present in the electrode is still active and has not been decomposed. The reaction between lithium peroxide and water follows the following chemical equation: 2Li2O2+2H2O→4LiOH+O2

[0071] Example 2 Figure 5 shows the electrochemical profiles of the 2% lithium peroxide cell prepared in Example 1 and a control cell containing no lithium peroxide. Electrochemical cycling of the lithium peroxide cathode electrode containing lithium ions shows an increase in initial charge capacity due to the electrochemical release of oxygen from the lithium peroxide, with the addition of 2% lithium peroxide resulting in an increase in charge capacity of approximately 10 mAh / g. This corresponds to approximately 45% of the theoretical 22 mAh / g if all the lithium peroxide is utilized. This additional charge capacity can be used to compensate for the irreversible capacity of the anode during the formation cycle.

[0072] While specific embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. Indeed, 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 accompanying claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure.

[0073] Any feature, material, characteristic or grouping described in connection with a particular aspect, embodiment or example may be Except where mutually incompatible, they should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification. All features disclosed in this specification (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 above. Protection extends to any novel or any novel combination of features disclosed in this specification (including any accompanying claims, abstract, and drawings), or any novel or any novel combination of steps of any method or process so disclosed.

[0074] Furthermore, certain features that are described in this 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. Furthermore, while features may be described 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.

[0075] Furthermore, while operations may be illustrated or described herein in a particular order, such operations need not be performed in the particular order shown or sequential order, nor need all operations be performed, to achieve desirable results. Other operations not shown or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, simultaneously with, or between the operations described. Furthermore, operations may be rearranged or reordered in other implementations. Those skilled in the art will appreciate that, in some embodiments, the actual steps employed 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. Furthermore, features and attributes of specific embodiments disclosed above may be combined in different ways to form additional embodiments, all of which are within the scope of the present disclosure. Also, the separation of various system components in the above implementations should not be construed as requiring such separation in all implementations, and it should be understood that the described components and systems 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.

[0076] For purposes of this disclosure, certain aspects, advantages, and novel features will be described herein. Not necessarily all such advantages may be achieved in accordance with a particular embodiment. Thus, for example, one skilled in the art will recognize that the present disclosure can be embodied or carried out in a way that achieves one advantage or group of advantages taught herein, without necessarily achieving other advantages that may be taught or suggested herein.

[0077] The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the devices and methods disclosed herein.

[0078] 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. Claim language is to be interpreted broadly based on the language used in the claims, and not limited to the examples set forth herein or during prosecution of the application, and those examples are to be construed as non-exclusive.

Claims

1. 1. A dry electrode film for an energy storage device, comprising: A dry active material; a dry binder; a dry prelithiated material distributed throughout the dry active material and the dry binder; the dry prelithiated material comprises 0.5% to 10% by weight of the dry electrode film; Dry electrode film, free of solvent residue.

2. The dry electrode film according to claim 1 , The dry prelithiated material is Li ２ O, Li ２ O ２ , Li ２ S., Li. ３ N, LiN ３ , LiF, Li ５ FeO ４ , Li ２ NiO ２ , Li ６ CoO ４ and Li ２ MoO ３ and combinations thereof.

3. The dry prelithiated material is Li ２ O ２ The dry electrode film according to claim 1 or 2,

4. 4. The dry electrode film of claim 1, wherein the dry prelithiated material comprises 1-3% by weight of the dry electrode film.

5. The dry electrode film of any one of claims 1 to 4, wherein the dry active material is a dry cathode active material.

6. 6. The dry electrode film of claim 5, wherein the dry cathode active material comprises sulfur or a sulfur-containing material.

7. 7. The dry electrode film of claim 1, wherein the dry pre-lithiated material does not include elemental lithium metal.

8. 8. The dry electrode film of claim 1, wherein the dry prelithiated material is uniformly distributed throughout the dry active material and the dry binder.

9. The dry electrode film of any one of claims 1 to 8, which is self-supporting.

10. The dry electrode film of any one of claims 1 to 9, which is self-supporting.

11. 11. The dry electrode film of claim 1, wherein the dry pre-lithiated material comprises lithium cations.

12. further comprising a dry conductive carbon additive; 12. The dry electrode film of claim 1, wherein the weight ratio of the dry prelithiated material to the dry conductive carbon additive is from 10:1 to 1:

1.

13. 13. The dry electrode film of claim 1, wherein the dry prelithiated material comprises submicron-sized particles.

14. The dry electrode film of any one of claims 1 to 13, wherein the dry binder comprises particles of 50 nm to 10 μm.

15. 15. The dry electrode film of claim 14, having a thickness of at least 110 μm.

16. An energy storage device comprising the dry electrode film of any one of claims 1 to 15.

17. 17. The energy storage device of claim 16, wherein the energy storage device is a battery.

18. 1. A method for dry manufacturing of a dry electrode film for an energy storage device, comprising: forming a dry electrode film mixture by combining a dry prelithiated material, a dry conductive carbon additive, a dry active material, and a dry fibrillizable binder; fibrillating the dry fibrillizable binder in the dry electrode film mixture; Including, the dry prelithiated material comprises 0.5% to 10% by weight of the dry electrode film; Dry manufacturing method, which is a solvent-free dry manufacturing process.

19. 19. The dry manufacturing method according to claim 18, mixing the dry prelithiated material, the dry conductive carbon additive, the dry active material, and the dry fibrillizable binder comprises: combining the dry prelithiated material, the dry conductive carbon additive, and the dry active material to form a dry mixture; combining the dry fibrillizable binder with the dry mixture to form the dry electrode film mixture; A dry manufacturing method comprising:

20. 20. The dry production method according to claim 19, forming the dry mixture by combining the dry prelithiated material, the dry conductive carbon additive, and the dry active material; combining the dry prelithiated material with the dry conductive carbon additive to form a first mixture; mixing the first mixture with the dry active material to form the dry mixture; A dry manufacturing method comprising:

21. 21. The dry production method according to claim 20, The dry manufacturing method wherein combining the first mixture with the dry active material comprises combining a dry carbon material with a dry conductive carbon additive to form the dry mixture.

22. 22. The dry manufacturing method of any one of claims 18 to 21, wherein the dry pre-lithiated material and the dry conductive carbon additive are mixed at a temperature of 200°C or less.

23. 23. The dry manufacturing method of any one of claims 18 to 22, wherein the dry pre-lithiated material and the dry conductive carbon additive are mixed at a temperature of 150°C or less.

24. 24. The dry manufacturing method of any one of claims 18 to 23, wherein the dry prelithiated material and the dry conductive carbon additive are mixed at a temperature of 100°C or less.

25. The dry production method according to any one of claims 18 to 24, a dry manufacturing method in which the dry prelithiated material and the dry conductive carbon additive are mixed together to form electrical contact between primary particles of the dry prelithiated material and the dry conductive carbon additive.

26. 26. The dry manufacturing method of any one of claims 18 to 25, wherein the dry pre-lithiated material and the dry conductive carbon additive are mixed without excessive heating.

27. 27. The dry manufacturing method of any one of claims 18 to 26, wherein the ratio of the dry prelithiated material to the dry conductive carbon additive is from 10:1 to 1:

1.

28. 28. The dry manufacturing method of any one of claims 18 to 27, wherein the ratio of the dry prelithiated material to the dry conductive carbon additive is from 5:1 to 5:

3.

29. 22. The dry manufacturing method according to claim 20 or 21, wherein the mixing of the first mixture and the dry active material is carried out so that the temperature of the dry mixture is 100°C or less.

30. 30. The dry manufacturing method of any one of claims 18 to 29, wherein the dry pre-lithiated material does not contain elemental lithium metal.

31. 31. The dry manufacturing method of any one of claims 18 to 30, further comprising calendering the dry electrode film mixture to form a dry electrode film.

32. 32. The dry manufacturing method of claim 31, further comprising disposing the dry electrode film on a current collector to form an electrode.

33. 33. The dry manufacturing method of claim 32, incorporating the electrode into an energy storage device; performing an initial cycle of said energy storage device, thereby oxidizing said dry pre-lithiated material; The dry manufacturing method further comprises:

34. The electrode film according to any one of claims 1 to 15, The dry electrode film, wherein the dry prelithiated material replaces lithium ions consumed during the first cycle of the energy storage device.

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