Compositions and methods for dry electrode films comprising elastic polymer binders

Abstract

The present application relates to compositions and methods for dry electrode films comprising an elastomeric polymer binder. Dry electrode films and energy storage devices including the same are provided that include an elastomeric polymer binder. In some embodiments, the dry electrode film is free of PTFE or contains a trace amount of PTFE. The electrode films exhibit improved mechanical and processing characteristics. Also provided are methods of processing such elastomeric binders and incorporating elastomeric polymeric binders into electrode films.

Description

[0001] This application is a divisional application of Chinese Patent Application 202080039473.6, entitled "Composition and method for dry electrode film comprising elastic polymer binder", filed on March 26, 2020.

[0002] Citations of priority claims

[0003] This application claims priority to U.S. Provisional Patent Application No. 62 / 826,273, filed March 29, 2019, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0004] This disclosure generally relates to electrodes for dry energy storage devices, energy storage devices for implementing such electrodes, and related methods. Background Technology

[0005] Conventional energy storage devices and related methods typically involve binder materials combined with active electrode materials and other additives, and processed in a manner to form an electrode film. The electrode film is usually applied to one or more layers of material to form an electrode. Typically, a negative electrode (anode) and a positive electrode (cathode) are formed, a diaphragm is placed between them, and an electrolyte-containing casing is inserted to form various types of energy storage devices.

[0006] Electrode films used within the electrodes of energy storage devices can be formed using either wet or dry methods. For example, active electrode materials can be combined with binder materials, solvents, and other additives using a wet coating method, which requires extensive subsequent drying techniques to fabricate the electrode film.

[0007] Dry electrode processes have been developed to reduce the time-consuming and expensive drying procedures required by the aforementioned wet processes. For example, the electrode process may include combining a polytetrafluoroethylene (PTFE) binder with an active electrode material and calendering it to form an electrode film. However, energy storage devices that include electrodes containing PTFE binders may exhibit undesirable device performance, such as increased irreversible capacity loss during redox processes. Summary of the Invention

[0008] To outline the invention and its advantages over prior art implementations, certain objects and advantages of the invention are described herein. Not all of these objects or advantages may be achieved in any particular embodiment of the invention. Therefore, for example, those skilled in the art will recognize that the invention may be implemented or performed in a manner that achieves or optimizes one or more advantages taught herein, without necessarily achieving other objects or advantages taught or suggested herein.

[0009] In a first aspect, a dry electrode membrane for an energy storage device is provided. The dry electrode membrane comprises a dry active material and a dry binder containing an elastic polymer, wherein the dry binder is free of PTFE or contains trace amounts of PTFE, and wherein the dry electrode membrane is self-supporting.

[0010] In some embodiments, the elastic polymer is selected from at least one of PE, PEO, and PVDF. In some embodiments, the dry electrode membrane comprises about 0-5 wt.% PE and about 0-2 wt.% PVDF. In some embodiments, the dry active material comprises graphite. In some embodiments, the dry electrode membrane comprises about 96 wt.% graphite and about 4 wt.% PE. In some embodiments, the dry electrode membrane comprises about 96 wt.% graphite, about 3 wt.% PE, and about 1 wt.% PVDF.

[0011] On the other hand, a dry electrode membrane for use in an energy storage device is provided. The dry electrode membrane comprises a dry active material and a dry binder containing an elastic polymer, wherein the dry electrode membrane is self-standing and contains at most trace amounts of polytetrafluoroethylene (PTFE).

[0012] In some embodiments, the elastic polymer is selected from the group consisting of cellulose, polyolefins, polyethers, polyether precursors, polysiloxanes, copolymers thereof, and mixtures thereof. In some embodiments, the elastic polymer is selected from the group consisting of polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), poly(ethylene oxide) (PEO), poly(phenylene ether) (PPO), polyethylene-block-poly(ethylene glycol), polydimethylsiloxane (PDMS), polydimethylsiloxane-co-alkylmethylsiloxane, carboxymethyl cellulose (CMC), copolymers thereof, and mixtures thereof. In some embodiments, the elastic polymer is selected from the group consisting of PE, PEO, PVDF, and mixtures thereof. In some embodiments, the dry electrode membrane comprises about 0.5-10 wt.% of the elastic polymer.

[0013] In some embodiments, the dry electrode membrane is PTFE-free. In some embodiments, the dry electrode membrane is free of processing solvent residues. In some embodiments, the dry electrode membrane contains at least about 95 wt.% dry active material. In some embodiments, the dry active material is graphite. In some embodiments, the dry electrode membrane has a tensile strength of at least about 1 N. In some embodiments, the dry electrode membrane is virtually defect-free.

[0014] In some embodiments, an electrode comprising a current collector and a dry electrode membrane is provided. In some embodiments, a battery comprising an electrode is provided.

[0015] In another aspect, a method for manufacturing a dry electrode film is provided. The method includes mixing a dried active material and a dry binder to form a dry first mixture, wherein the dry binder comprises an elastic polymer, and calendering the dry first mixture to form a dry electrode film, wherein the dry electrode film is self-standing and contains at most trace amounts of polytetrafluoroethylene (PTFE).

[0016] In some embodiments, mixing is performed using a non-destructive mixing process. In some embodiments, mixing does not involve high-shear mixing. In some embodiments, mixing is carried out at a temperature of at least about room temperature.

[0017] In some embodiments, the dry active material has a first particle size distribution before mixing and a second particle size distribution after mixing, wherein the first and second particle size distributions are substantially similar. In some embodiments, calendering is performed at a temperature of about 150-250°C. In some embodiments, the method further includes calendering a dry electrode film.

[0018] All of these embodiments are intended to fall within the scope of the invention disclosed herein. These and other embodiments of the invention will become apparent to those skilled in the art from the following detailed description of preferred embodiments with reference to the accompanying drawings, and the invention is not limited to any particular preferred embodiment disclosed. Attached Figure Description

[0019] Figure 1 An embodiment of an energy storage device having an electrode membrane comprising an elastic polymer binder is described.

[0020] Figures 2A-2H A photograph shows an embodiment of an electrode membrane fabricated from powder into a self-standing membrane. Figure 2A The final formulation powder after processing is shown. Figure 2B The final powder between the two rollers before calendering is shown. Figures 2C-2F Formulation 1 is shown. Figure 2C ), Formulation 4 ( Figure 2D ), Formulation 5 ( Figure 2E ), and formulation 6 ( Figure 2F Calendered self-standing film. Figure 2G and Figure 2H Formulation 5 is shown. Figure 2G ) and formulation 6 ( Figure 2H ( ) flexible self-supporting membrane.

[0021] Figure 3A A graph showing the tensile strength of various self-supporting graphite electrode film implementation schemes is provided. Figure 3B Extended figures are provided to show various implementation schemes of self-supporting graphite electrode films.

[0022] Figure 4A A graph is provided showing the charge and discharge capacity of an embodiment of a graphite electrode half-cell with electrolyte A. Figure 4B A graph is provided showing the efficiency of a half-cell embodiment with a graphite electrode having electrolyte A.

[0023] Figure 5A A graph is provided showing the capacity of an embodiment of a graphite electrode half-cell with electrolyte B. Figure 5B A graph is provided showing the efficiency of a half-cell embodiment with a graphite electrode having electrolyte B.

[0024] Figures 6A-6C Formulation 1, which shows the presence of electrolyte A, is provided. Figure 6A ), Formulation 2 ( Figure 6B ) and formulation 3 ( Figure 6C Figures showing different capacities of graphite electrode half-cell implementation schemes.

[0025] Figures 7A-7C Formulation 1, which shows the presence of electrolyte B, is provided. Figure 7A ), Formulation 2 ( Figure 7B ) and formulation 3 ( Figure 7C Figures showing different capacities of graphite electrode half-cell implementation schemes.

[0026] Figures 8A-8C Formulation 1, which shows the presence of electrolyte A, is provided. Figure 8A ), Formulation 2 ( Figure 8B ), and formulation 3 ( Figure 8C The graph shows the first cycle voltage curve of the graphite electrode half-cell implementation scheme.

[0027] Figures 9A-9C Formulation 1 (showing electrolyte B) is provided. Figure 9A Formulation 2 () Figure 9B ), and formulation 3 ( Figure 9C The graph shows the first cycle voltage curve of the graphite electrode half-cell implementation scheme.

[0028] Figures 10A-10C Formulation 1 (showing electrolyte B) is provided. Figure 10A ), Formulation 2 ( Figure 10B ), and formulation 3 ( Figure 10C The graph shows the first formation of a graphite electrode half-cell embodiment, followed by continuous cycling at a rate of 0.1C. Detailed Implementation

[0029] A self-standing electrode membrane for lithium-ion batteries is disclosed, which is prepared by a dry process and contains little or no polytetrafluoroethylene (PTFE) binder. The electrode membrane can be prepared by a process that avoids the use of solvents, hence it is a “dry” process. In some embodiments, the electrode membrane includes one or more alternative binders, such as polyethylene (PE), polyethylene oxide (PEO), and polyvinylidene fluoride (PVDF), which have been found to be usable in dry manufacturing processes, as described below. In one embodiment, the PTFE-free electrode membrane is used to prepare anode or cathode assemblies for lithium-ion batteries or other electronic storage devices.

[0030] definition

[0031] The terms "battery" and "capacitor" should be given the common and customary meanings as understood by one of ordinary skill in the art. The terms "battery pack" and "capacitor" are not mutually exclusive. A capacitor or battery pack can refer to a single electrochemical cell that can operate independently or as a component of a multi-cell system.

[0032] The voltage of an energy storage device is the operating voltage of a single battery or capacitor cell. Under load or depending on manufacturing tolerances, the voltage may exceed or fall below the rated voltage.

[0033] A "self-supporting" electrode film is an electrode film incorporating an adhesive matrix structure sufficient to support the film or layer and maintain its shape, allowing the electrode film or layer to be self-supporting. Self-supporting electrode films or active layers are a type of adhesive matrix structure incorporated when incorporated into energy storage devices. Typically, and depending on the method employed, such electrode films or active layers are robust enough to be used in the energy storage device manufacturing process without any external support elements (such as current collectors or other membranes). For example, a "self-supporting" electrode film may have sufficient strength to be rolled up, handled, and unrolled during electrode manufacturing without other support elements. Dry electrode films, such as cathode or anode electrode films, can be self-supporting.

[0034] A "solvent-free" electrode membrane is an electrode membrane that contains no detectable or substantially no processing solvent, processing solvent residues, and / or processing solvent impurities. This "solvent-free" electrode membrane differs from conventional electrode membranes based on conventional solvent-based processes, which contain detectable or substantial amounts of processing solvent, processing solvent residues, and / or processing solvent impurities, even after the solvent-based membrane has undergone a drying process. Dry electrode membranes, such as cathode or anodic electrode membranes, can be solvent-free. Solvent-free dry electrode membranes can be made from dry components, such as dry active materials and dry binders (e.g., powders), which are also solvent-free as defined above. In some embodiments, the dry components may contain a certain amount of atmospheric moisture due to the absorption of trace amounts of moisture from the surrounding air. In some embodiments, the solvent-free component and / or solvent-free electrode membrane contains a moisture content of about, up to or up to about 2000 ppm, 1500 ppm, 1000 ppm, 900 ppm, 800 ppm, 700 ppm, 600 ppm, 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm or 10 ppm, or any value range thereof.

[0035] A “wet” electrode, a “wet process” electrode, or a slurry electrode is an electrode prepared by at least one step involving a slurry of active materials (multiple types), binders (multiple types), and optional additives (multiple types). A wet electrode may include a processing solvent, processing solvent residues, and / or processing solvent impurities.

[0036] A “PTFE-free” membrane describes a membrane that does not contain polytetrafluoroethylene (PTFE). A “trace PTFE” membrane describes a membrane containing a small amount of PTFE, where the amount of PTFE, if present, substantially does not affect the performance of the membrane or the electrochemical device containing such a membrane. For example, a membrane with trace or at most trace PTFE may contain less than 0.5 wt.% PTFE, which includes PTFE-free membranes.

[0037] A “non-destructive” process is one in which the electrode active material, including its surface, is substantially unmodified during the process. Therefore, the analytical properties and / or performance of the active material in its application (e.g., incorporation in an energy storage device) are the same or nearly the same as those that have not undergone the process. For example, in this process, the coating on the active material may be undisturbed or substantially undisturbed. A non-limiting example of a non-destructive process is “non-destructive mixing or blending,” or jet milling under reduced pressure, increased feed rate, reduced speed (e.g., mixer speed), and / or variations of other process parameters, such that when applied to an energy storage device, the shear force applied to the active material remains below a threshold that adversely affects the analytical properties and / or performance of the active material. An example of an effective non-destructive mixing process is the use of a blade mixer with a tip speed range from about 10 m / min to about 40 m / min. A “non-destructive” process can differ from a high-shear process, which substantially modifies the electrode active material, such as its surface, and substantially affects its analytical properties and / or performance. For example, high-shear blending or high-shear jet milling can have detrimental effects on the surface of the electrode active material. High-shear processes can be implemented, which impair the surface properties of the active material, to provide additional benefits, such as fibrillation of the binder material, or additional formation of a binder / active material matrix to aid in the formation of a self-supporting electrode film. The embodiments described herein can provide similar benefits while avoiding the detrimental effects of overuse of high-shear processes. Typically, the non-destructive processes described herein are carried out at one or more of higher feed rates, lower speeds, and / or lower pressures, resulting in less shearing than more destructive processes that would otherwise substantially modify the electrode active material and thus affect its performance.

[0038] describe

[0039] Although certain embodiments and examples are described below, those skilled in the art will understand that the invention extends beyond the specific disclosed embodiments and / or uses and their obvious modifications and equivalents. Therefore, it is intended that the scope of the invention disclosed herein should not be limited to any particular embodiments described below.

[0040] As described herein, dry electrode processes have been developed to reduce the time-consuming and expensive drying procedures required by the aforementioned wet processes. Dry electrode processes have also been developed that eliminate the need for using polytetrafluoroethylene (PTFE) binders to hold the active electrode materials together before calendering them to form an electrode film. Embodiments described herein include alternative binder materials for the electrode film that can reduce the aforementioned degradation drawbacks and the irreversible capacity loss inherent in using PTFE alone as an electrode binder, for example, in dry electrode processes. Some embodiments provide electrode binder materials that allow electrochemical operation at low voltages with reduced or almost no significant additional energy loss. Some embodiments provide self-standing dry-processed electrodes with binders comprising elastic polymer binders. In some embodiments, the self-standing electrode comprises a graphite active material and an elastic polymer binder, such as high molecular weight polyethylene (PE), polyethylene oxide (PEO), and poly(vinylidene fluoride) (PVDF). In some embodiments, the electrode film is PTFE-free, and therefore PTFE is absent. In some embodiments, the electrode film may contain trace amounts of PTFE. In some embodiments, the electrode membrane may contain at most trace amounts of PTFE. This paper investigates the material properties of such self-supporting electrode membranes, such as mechanical strength and electrochemical performance. For example, electrode membranes with an elastic polymer binder and containing trace amounts of PTFE can exhibit equal or higher tensile strength and / or ductility relative to comparable electrode membranes containing PTFE, which can facilitate the fabrication of energy storage devices. Specifically, electrode membranes with higher tensile strength and / or ductility can be more easily applied to current collectors or other substrates. These factors are particularly relevant when using dry electrode processing techniques, as the electrode membrane can be treated as a self-supporting membrane, further defined herein as a “self-supporting membrane.”

[0041] One embodiment is a method of manufacturing an anode and / or electrode film comprising a PTFE-free binder composition. In some embodiments, the manufacturing process or a portion thereof may be carried out at room temperature or higher to facilitate the formation of an electrode exhibiting desired electrical properties. In some embodiments, the manufacturing process or a portion thereof is carried out at about, at least, or at least about 18°C, 20°C, 25°C, 30°C, 40°C, 60°C, or 80°C, or any value range therebetween. In some embodiments, a method of manufacturing an anode electrode film comprising the binder composition described herein is provided. In some embodiments, the anode electrode film manufacturing process includes jet milling, blending, tumbling, or acoustic mixing steps to facilitate the formation of a defect-reduced or virtually defect-free electrode film using a dry manufacturing method. In some embodiments, the electrode film manufacturing process does not include a high-shear mixing step (e.g., high-shear jet milling), and the dry electrode components may be mixed under milder conditions, such as a non-destructive mixing process, to form a defect-free or virtually defect-free electrode film using a dry manufacturing method. In some implementations, the electrode film manufacturing process may consist of or consist substantially of a single mixing step of active materials and elastic polymer binders prior to the formation of the electrode film.

[0042] Other mechanical and electrical properties may also be considered when developing composite binder materials and processes for forming electrodes. For example, the ductility and / or porosity of the binder material may be selected to provide improved mechanical integrity and / or ionic conductivity of the electrode. In some embodiments, the binder material may be selected to provide a resulting electrode film with desired electrical properties while also exhibiting desired interactions with one or more other components of the device (e.g., electrolyte), and / or providing desired effectiveness as a binder material.

[0043] In one embodiment, a non-destructive-processed active material, such as the undamaged and / or pristine surface of active material particles, is incorporated into the electrode film mixture. The undamaged and / or pristine active material may include materials with substantially similar particle size distribution, surface area distribution, surface chemical reactivation, and / or surface chemical composition to commercially purchased materials and / or materials prior to processing that may alter these physical properties of the active material. Thus, bulk active materials (of various types) with reduced surface degradation are provided. In some embodiments, non-destructive mixing may include blending, tumbling, or acoustic mixing. In some embodiments, non-destructive mixing may be performed using a resonant acoustic mixer.

[0044] The materials and methods provided herein can be implemented in a variety of energy storage devices. For example, the energy storage device may be a capacitor, lithium-ion capacitor (LIC), supercapacitor, battery, or hybrid energy storage device and / or hybrid battery, combining two or more of the above aspects. In some embodiments, the device is a battery. The energy storage device may be characterized by an operating voltage. In some embodiments, the energy storage device described herein may have an operating voltage of about 0 V to about 5 V. In further embodiments, the operating voltage may be about 2.7 V to about 4.2 V, about 3.0 V to about 4.2 V, or any value between these.

[0045] In one embodiment, the energy storage device includes one or more electrodes. The electrodes typically include an electrode membrane and a current collector. The electrode membrane may be formed from a mixture of one or more binders and one or more active electrode materials. It should be understood that elastic polymer binders and electrodes including elastic polymer binders can be used in various embodiments having any of a variety of energy storage devices and systems, such as one or more batteries, capacitors, capacitor-battery hybrids, fuel cells, or other energy storage systems or devices, and combinations thereof. In some embodiments, the electrode membrane mixture and the electrodes made from the electrode membrane mixture described herein may be components of a lithium-ion capacitor, a lithium-ion battery, a supercapacitor, or a hybrid energy storage device combining two or more of the above aspects.

[0046] Energy storage devices can have any suitable construction, such as planar, spiral-wound, button-shaped, or bag-shaped. Energy storage devices can also be components of systems, such as power generation systems, uninterruptible power supply (UPS) systems, photovoltaic power generation systems, and energy recovery systems for, for example, industrial machinery and / or transportation. Energy storage devices can be used to power various electronic devices and / or motor vehicles, including hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and / or electric vehicles (EVs).

[0047] In one embodiment, the energy storage device may include a decrease in the equivalent series resistance over the device's lifetime. This can allow the device to have increased power density over its lifetime. In some embodiments, these types of energy storage devices may have reduced capacity loss over the device's lifetime. These devices may also include improved cycling performance, including improved storage stability and reduced capacity decay during cycling.

[0048] Figure 1A side cross-sectional schematic diagram of an example of an energy storage device 100 having an electrode film comprising an elastic polymer binder is shown. The energy storage device 100 can be classified, for example, as a capacitor, a battery, a capacitor-battery hybrid, or a fuel cell. In one embodiment, device 100 is a lithium-ion battery.

[0049] The device has a first electrode 102, a second electrode 104, and a diaphragm 106 located between the first electrode 102 and the second electrode 104. The first electrode 102 and the second electrode 104 are adjacent to their respective opposing surfaces with respect to the diaphragm 106. The energy storage device 100 includes an electrolyte 118 to facilitate ion communication between the electrodes 102 and 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 diaphragm 106. The electrolyte 118, the first electrode 102, the second electrode 104, and the diaphragm 106 are housed within an energy storage device housing 120.

[0050] One or more of the first electrode 102, the second electrode 104, and the diaphragm 106, or a combination thereof, may comprise a porous material. The pores within the porous material can provide a containment for and / or increase the surface area for contact with the electrolyte 118 within the housing 120. The energy storage device housing 120 may be sealed around the first electrode 102, the second electrode 104, and the diaphragm 106, and may be physically sealed from the surrounding environment.

[0051] In some embodiments, the first electrode 102 may be an anode (“negative electrode”) and the second electrode 104 may be a cathode (“positive electrode”). The diaphragm 106 may be configured to electrically isolate two electrodes adjacent to opposite sides of the diaphragm 106, such as the first electrode 102 and the second electrode 104, while allowing ion communication between the two adjacent electrodes. The diaphragm 106 may comprise a suitable porous electrically insulating material. In some embodiments, the diaphragm 106 may comprise a polymeric material. For example, the diaphragm 106 may comprise a cellulose material (e.g., paper), a polyethylene (PE) material, a polypropylene (PP) material, and / or a combination of polyethylene and polypropylene.

[0052] Typically, the first electrode 102 and the second electrode 104 each include a current collector and an electrode film. Electrodes 102 and 104 include electrode films 112 and 114, wherein the first electrode film 112 is depicted as including an elastic polymer binder and including trace amounts of PTFE. Although the second electrode film 114 is not depicted as containing an elastic polymer binder and / or containing trace amounts of PTFE, it should be understood that either or both of electrode films 112 and / or 114 may contain an elastic polymer binder and / or contain trace amounts of PTFE. As shown, electrodes 102 and 104 each have a single electrode film 112 and 114, but other combinations of two or more electrode films for each electrode 102 and 104 are possible. The device 100 is shown as having a single electrode 102 and a single electrode 104, but other combinations are possible. Electrode films 112 and 114 may each have any suitable shape, size, and thickness. For example, the electrode films may each have a thickness from about 30 micrometers (μm) to about 250 micrometers, for example, a range of values ​​from about 50 micrometers, about 100 micrometers, about 150 micrometers, about 200 micrometers, about 250 micrometers, about 300 micrometers, about 400 micrometers, about 500 micrometers, about 750 micrometers, about 1000 micrometers, about 2000 micrometers, or any values ​​between these ranges. Additional electrode film thicknesses are described throughout the disclosure for individual electrode films. The electrode films typically comprise one or more active materials, such as anodic or cathodic active materials. Electrode films 112 and / or 114 may be dry and / or self-supporting electrode films with reduced thickness, increased electrode film density, high energy density, high specific energy density, areal energy density, areal capacity, or specific capacity. The first electrode film 112 and / or the second electrode film 114 may also include one or more binders. Electrode films 112 and / or 114 can be prepared by the methods described herein. Electrode films 112 and / or 114 can be wet or self-supporting dry electrodes as described herein.

[0053] In some embodiments, the active material may be a carbon-based material or a battery material. In some embodiments, the active material may include lithium metal oxides, sulfur-carbon composites, and / or lithium sulfide. In some embodiments, the active material may include lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate (LTO), lithium nickel manganese oxide (LNMO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the active material may include other materials described herein. In some embodiments, the active material may include one or more carbon materials. The carbon material may be selected from, for example, graphite materials, graphene-containing materials, hard carbon, soft carbon, carbon nanotubes, porous carbon, conductive carbon, or combinations thereof. Activated carbon may be derived from steam processes or acid / etching processes. In some embodiments, the graphite material may be a surface-treated material. In some embodiments, porous carbon may comprise activated carbon. In some embodiments, porous carbon may comprise layered carbon structures. In some embodiments, porous carbon may comprise structured carbon nanotubes, structured carbon nanowires, and / or structured carbon nanosheets. In some embodiments, the porous carbon may comprise graphene sheets. In some embodiments, the porous carbon may be surface-treated carbon. In preferred embodiments, the active material comprises graphite, is substantially composed of graphite, or is composed of graphite.

[0054] Typically, the electrode films described herein can be manufactured using a modified dry manufacturing process. For example, some steps for manufacturing the components described in this application can be found in U.S. Patent Publication Nos. 2005 / 0266298 and 2006 / 0146479. The entire contents of these, as well as any other references to external literature, are incorporated herein by reference. As used herein, a dry manufacturing process can refer to a process in which no solvent is used or substantially no solvent is used in the formation of the electrode film. For example, the components of an electrode film comprising carbon materials and a binder may include dried particles. The dry particles used to form the electrode film can be combined to provide a dry particle electrode film mixture. In some embodiments, the electrode film may be formed from a dry particle electrode film mixture such that the weight percentage of the components of the electrode film and the weight percentage of the components of the dry particle electrode film mixture are substantially the same. In some embodiments, the electrode film formed from the dry particle electrode film mixture using a dry manufacturing process may be free of or substantially free of any processing additives, such as solvents and resulting solvent residues. In some embodiments, the resulting electrode film is a self-supporting electrode film formed from a dry particle mixture using a dry process. In some embodiments, the resulting electrode film is a self-supporting electrode film formed from a dry particulate mixture using a dry process. As described herein, the electrode film may contain an elastic polymer binder and / or contain trace amounts of PTFE. In some embodiments, the self-supporting electrode film can be formed in the absence of a current collector. In further embodiments, the electrode film may be a self-supporting electrode film. In some embodiments, the dry particulate electrode film mixture is calendered by a first calendering process to form the electrode film. In some embodiments, the formed electrode film is further calendered by a second calendering process. In some embodiments, the calendering processes (e.g., the first and / or second calendering processes) are performed at, or at, a range of about 100°C, 150°C, 165°C, 185°C, 200°C, 215°C, 230°C, 250°C, or 280°C, or any value between these ranges.

[0055] like Figure 1As shown, the first electrode 102 and the second electrode 104 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, respectively. The first current collector 108 and the second current collector 110 facilitate electrical coupling between each corresponding electrode film and an external circuit (not shown). The first current collector 108 and / or the second current collector 110 comprise one or more conductive materials and may have any suitable shape and size selected to facilitate charge transfer between the respective electrode and the external circuit. For example, the current collector may comprise a metallic material, such as materials including aluminum, nickel, copper, rhenium, niobium, tantalum, and noble metals and alloys such as silver, gold, platinum, palladium, rhodium, osmium, iridium, 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 charge transfer between the respective electrode and the external circuit.

[0056] In some embodiments, the energy storage device 100 is a lithium-ion battery or hybrid energy storage device including a cathode containing active material. In some embodiments, the lithium-ion battery is configured to operate at about 2.5 to 5 V or 2.7 to 4.2 V.

[0057] In some embodiments, the energy storage device is configured to operate at 3 volts or higher. In further embodiments, the energy storage device is configured to operate at 2.7 volts or higher. In some embodiments, the energy storage device is configured to operate under selected voltage and temperature conditions. For example, the energy storage device may be configured to operate at temperatures ranging from 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, or higher, or any value between these ranges. The energy storage device may be configured to operate continuously at 2.7 V at 60 to 85°C, 2.8 V at 60 to 85°C, 2.9 V at 60 to 85°C, or 3 V at 60 to 85°C, or any selected temperature and voltage value between these ranges. In some implementations, the voltage and temperature conditions are about 2.7 V and about 85°C, about 2.8 V and about 80°C, about 2.9 V and about 75°C, about 3 V and about 70°C, or about 3.1 V and about 65°C.

[0058] Lithium-ion energy storage devices

[0059] In some embodiments, the energy storage device 100 may be a lithium-ion energy storage device, such as a lithium-ion capacitor, a lithium-ion battery, or a hybrid lithium-ion device. In some embodiments, the electrode film of the lithium-ion energy storage device electrode may contain one or more active materials, include an elastic polymer binder, and / or be PTFE-free or contain trace amounts of PTFE.

[0060] In some embodiments, the electrode film of a lithium-ion energy storage device may comprise an anolyte active material. The anolyte active material may include, for example, intercalation materials (e.g., carbon, graphite, and / or graphene), alloying / dealloying materials (e.g., silicon, silicon oxide, tin, and / or tin oxide), metal alloys or compounds (e.g., Si-Al and / or Si-Sn), and / or conversion materials (e.g., manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anolyte active material may be used alone or mixed together to form a multiphase material (e.g., 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).

[0061] In some embodiments, the electrode membrane of a lithium-ion energy storage device may comprise an active cathode material. In some embodiments, the electrode membrane may further comprise a binder, and optionally a porous carbon material, and optionally a conductive additive. In some embodiments, the conductive additive may comprise a conductive carbon additive, such as carbon black. In some embodiments, the porous carbon material may comprise activated carbon. In some embodiments, the cathode active material may comprise lithium metal oxide and / or lithium sulfide. In some embodiments, the cathode active material may comprise lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate (LTO), lithium nickel manganese oxide, and / or lithium nickel cobalt aluminum oxide (NCA). The cathode active material may comprise sulfur or sulfur-containing materials, such as lithium sulfide (Li2S), or other sulfur-based materials, or mixtures thereof. In some embodiments, the cathode membrane comprises at least 50 wt.% sulfur or a material containing sulfur active materials. In some embodiments, the cathode membrane comprising sulfur or a material containing sulfur active materials has a concentration of at least 10 mAh / cm³. 2 The area capacity. In some embodiments, the cathode membrane containing sulfur or a sulfur-containing active material has an area capacity of 1 g / cm³. 3 The electrode film density. In some embodiments, the cathode film containing sulfur or a sulfur-containing active material also includes a binder.

[0062] In some embodiments, the cathode electrode film of a lithium-ion battery or hybrid energy storage device may comprise about 70 wt% to about 99 wt% of active material, comprising about 70 wt% to about 96 wt%, or about 70 wt% to about 88 wt%. In some embodiments, the cathode electrode film may comprise up to about 10 wt.% of porous carbon material, comprising up to about 5 wt.%, or about 1 wt.% to about 5 wt.%. In some embodiments, the cathode electrode film comprises up to about 5 wt%, including about 1 wt% to about 3 wt% of conductive additives. In some embodiments, the cathode electrode film comprises up to about 20 wt.% of binder, for example, about 1.5 wt.% to 10 wt.%, about 1.5 wt.% to 5 wt.%, or about 1.5 wt.% to 3 wt.%. In some embodiments, the cathode electrode film comprises about 1.5 wt.% to about 3 wt.% of binder.

[0063] In some embodiments, the anode electrode film may comprise an active material, a binder, and optional conductive additives. In some embodiments, the conductive additives may include conductive carbon additives, such as carbon black. In some embodiments, the active material of the anode may include graphitic carbon, 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 comprise about 80 wt.% to about 99 wt.% of the active material, including about 90 wt.% to about 98 wt.%, or about 94 wt.% to about 97 wt.%. In some embodiments, the anode electrode film comprises up to about 5 wt.%, including about 1 wt.% to about 3 wt.% of the conductive additives. In some embodiments, the anode electrode film comprises up to about 20 wt% of the binder, including about 1.5 wt% to 10 wt%, about 1.5 wt% to 5 wt%, or about 3 wt% to 5 wt%. In some embodiments, the anode electrode film contains about 4 wt.% binder. In some embodiments, the anode film may not include conductive additives.

[0064] In some embodiments, the electrode membrane comprises active material in weight percentages of 90 wt.%, 92 wt.%, 94 wt.%, 95 wt.%, 96 wt.%, 97 wt.%, 98 wt.%, or 99 wt.%, or any value range thereof.

[0065] In some embodiments, the electrode film of the lithium-ion energy storage device electrode comprises an electrode film mixture containing carbon configured to reversibly intercalate lithium ions. In some embodiments, the lithium-intercalated carbon is selected from graphitic carbon, graphite, hard carbon, soft carbon, and combinations thereof. For example, the electrode film may include one or more of a binder material, graphitic carbon, graphite, graphene-containing carbon, hard carbon, and soft carbon, as well as a conductivity-promoting material. In some embodiments, the electrode is mixed with lithium metal and / or lithium ions.

[0066] In a further embodiment, the energy storage device 100 is filled with a suitable lithium-containing electrolyte. For example, device 100 may include a lithium salt and a solvent, such as a non-aqueous or organic solvent. Typically, the lithium salt comprises a redox-stable anion. In some embodiments, the anion may be monovalent. In some embodiments, the lithium salt may be selected from hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2), lithium trifluoromethanesulfonate (LiSO3CF3), lithium bis(oxaloyl)borate (LiB(C2O4)2), lithium bis(fluorosulfonyl)imide (LiN(SO2F)2), lithium difluoro(oxaloyl)borate (LiC2BF2O4), and combinations thereof. In some embodiments, the electrolyte may comprise a quaternary ammonium cation and an anion selected from the group consisting of hexafluorophosphate, tetrafluoroborate, and iodide anions. In some embodiments, the salt concentration may be from about 0.1 mol / L (M) to about 5 M, from about 0.2 M to about 3 M, or from about 0.3 M to about 2 M. In further embodiments, the salt concentration of the electrolyte may be from about 0.7 M to about 1 M. In some embodiments, the salt concentration of the electrolyte may be about 0.2 mol / L (M). M, approximately 0.3 M, approximately 0.4 M, approximately 0.5 M, approximately 0.6 M, approximately 0.7 M, approximately 0.8 M, approximately 0.9 M, approximately 1 M, approximately 1.1 M, approximately 1.2 M, or values ​​between these.

[0067] In some embodiments, the energy storage device may include a liquid solvent. The solvent does not need to dissolve every component of the electrolyte, nor does it need to completely dissolve any component of the electrolyte. In other embodiments, the solvent may be an organic solvent. In some embodiments, the solvent may contain one or more functional groups selected from carbonates, ethers, and / or esters. In some embodiments, the solvent may contain a carbonate. In further embodiments, the carbonate may be selected from cyclic carbonates, such as, for example, ethylene carbonate (EC), propylene carbonate (PC), vinyl vinyl carbonate (VEC), vinylene carbonate (VC), vinyl fluorocarbonate (FEC), and combinations thereof, or acyclic carbonates, such as, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), and combinations thereof. In some embodiments, the electrolyte may contain LiPF6 and one or more carbonates.

[0068] In some embodiments, the active material comprises treated carbon material, wherein the treated carbon material includes a reduced number of hydrogen-containing functional groups, nitrogen-containing functional groups, and / or oxygen-containing functional groups, as described in U.S. Patent Publication No. 2014 / 0098464. For example, treated carbon particles may include a reduction in the number of one or more functional groups on one or more surfaces of the treated carbon, for example, a reduction of one or more functional groups of about 10% to about 60%, including about 20% to about 50%, compared to an untreated carbon surface. The treated carbon may include a reduced number of hydrogen-containing functional groups, nitrogen-containing functional groups, and / or oxygen-containing functional groups. In some embodiments, the treated carbon material contains functional groups containing less than about 1% hydrogen, including less than about 0.5%. In some embodiments, the treated carbon material contains functional groups containing less than about 0.5% nitrogen, including less than about 0.1%. In some embodiments, the treated carbon material contains functional groups containing less than about 5% oxygen, including less than about 3%. In another embodiment, the treated carbon material contains approximately 30% fewer hydrogen-containing functional groups than the untreated carbon material.

[0069] Elastic polymer adhesive

[0070] An electrode, such as an anode and / or cathode, is disclosed having one or more electrode films comprising an elastic polymer binder material. In some embodiments, the electrode film is PTFE-free. In some embodiments, the electrode film contains trace amounts of PTFE. In some embodiments, the elastic polymer binder may comprise one or more polyolefins and / or copolymers thereof. In some embodiments, the elastic polymer binder may comprise one or more of cellulose, polyolefins, polyethers, polyether precursors, polysiloxanes, copolymers thereof, and / or mixtures thereof. In some embodiments, one or more polyolefins may include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), copolymers thereof, and / or mixtures thereof. In some embodiments, the elastic polymer binder may include branched polyethers, polyethylene ethers, copolymers thereof, etc. The elastic polymer binder may include polysiloxanes and copolymers of polysiloxanes, and / or copolymers of polyether precursors. For example, the elastic polymer binder may include poly(ethylene oxide) (PEO), poly(phenylene ether) (PPO), polyethylene-block-poly(ethylene glycol), polydimethylsiloxane (PDMS), polydimethylsiloxane-co-alkylmethylsiloxane, copolymers thereof, and / or mixtures thereof. In some embodiments, one or more polyolefins may include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), copolymers thereof, and / or mixtures thereof. The binder may include cellulose, such as carboxymethyl cellulose (CMC). The polymer mixture may contain an interpenetrating network of the above polymers or copolymers. For example, in some embodiments, the elastic polymer binder may include a binder selected from at least one of PE, PVDF, and PEO. In some embodiments, the elastic polymer binder may be composed of PE or substantially composed of PE. In some embodiments, the elastic polymer binder may be composed of PVDF or substantially composed of PVDF. In some embodiments, the elastic polymer binder may be composed of PEO or substantially composed of PEO. In some embodiments, the elastic polymer binder may be composed of PE and PVDF or substantially composed of PE and PVDF. In some implementations, the elastic polymer adhesive may consist of PE, PVDF, and PEO, or be substantially composed of PE, PVDF, and PEO.

[0071] In some embodiments, the elastic polymer binder is in particulate form. In some embodiments, the elastic polymer binder particles have a Dm value that is or is within the range of 2 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, or 100 μm, or any value between therewith. 50 Average particle size distribution.

[0072] The electrode membrane may contain varying amounts of an elastic polymer binder. In some embodiments, the electrode membrane may contain or contain about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 8, or 10 wt.% or any value range thereof of an elastic polymer binder. In some embodiments, the electrode membrane may contain or contain about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 8, or 10 wt.% or any value range thereof of PE. In some embodiments, the electrode membrane may contain or contain about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 8, or 10 wt.% or any value range thereof of PVDF. In some embodiments, the electrode membrane may contain or contain PEO in any range of about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 6, 8 or 10 wt.% or between.

[0073] In some embodiments, the self-supporting and / or self-supporting electrode film comprising the elastic polymer as described herein may have a tensile strength of at least or at least about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 N, or any value range thereof. In further embodiments, the tensile strength may be or may be about 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, or 6 N, or a value range thereof.

[0074] Example

[0075] Electrode materials

[0076] SMG-A5 Graphite and LiNi 0.6 Mn 0.2 Co 0.2 The O2 (NMC622) powder was used as is without drying. Therefore, the powder may contain limited residual water due to atmospheric moisture. The elastic polymer binders include polyethylene (PE), polyethylene oxide (PEO), and polyvinylidene fluoride (PVDF) (with a wide range of molecular weights), homopolymers, and copolymers. In some embodiments, the particle size and distribution of the binder polymer can play a role in maintaining the mechanical stability of the self-supporting electrode membrane. Polytetrafluoroethylene (PTFE) binders were also used in the comparative examples. Table 1 shows the specifications of the active materials and binders tested below.

[0077] Table 1: Specifications of Active Materials and Binders

[0078] Dry-coated electrode formulations

[0079] Table 2 provides the electrode formulations under examination containing active materials and binders. A dry powdering process was performed following the following dry mixing process: (i) mixing graphite and binder at 60% intensity for 5 minutes using a resonant acoustic mixer; (ii) grinding the mixed powder using a micronizer at a feed rate of 9 at 40 psi pressure. PTFE-free formulations 4-6 were not included in step (ii) of the grinding process; they were processed only by the resonant acoustic mixer in step (i) without the jet milling in step (ii). Formulation 3 contains PTFE and is provided as a comparison. Figure 2A A photograph of a processed PTFE-free formulation powder is shown. Unlike processed powder formulations containing PTFE, it appears powdery and dusty. Figure 2B As shown, the processed dry powder is converted into a self-standing electrode film under the calendering process conditions shown in Table 3 to form film A and film B for each of electrode film formulations 1-6. Film A is directly converted from the processed powder into a film, while film B is obtained by recalendering the film prepared under the film A conditions until the target thickness and load are achieved. Figures 2C-2F Images of PTFE-free films A, produced by direct calendering of formulations 1, 4, 5, and 6 from mixed powders, are shown, demonstrating the production of self-standing graphite films without PTFE binder and jet milling processes. We note that formulations 1, 2, and 4-6 allow for the production of thinner graphite electrode films with lower material loads directly from the processed formulation powders via a single calendering process, compared to typical graphite electrode films using PTFE as the sole binder.

[0080] Table 2 Electrode Formulation Composition

[0081] Table 3 Calendering Processing Conditions

[0082] Mechanical properties

[0083] Figure 3A and Figure 3BThe tensile strength and elongation results of self-standing graphite electrode films of formulations 1-3, calendered to film specifications A and B, are shown. Unexpectedly and advantageously, it was found that the tensile strength of the self-standing graphite electrode films of formulations 1 and 2, without a PTFE binder, was comparable to or exceeded that of the film of formulation 3, which had a PTFE binder. Furthermore, formulations 1 and 2 showed significantly lower film elongation compared to the graphite electrode film of formulation 3, which had a PTFE binder. In addition, formulation 2, which added PVDF to a graphite electrode film with a PE binder, showed a significantly improved tensile strength while maintaining similar film elongation characteristics to formulation 1, which had a graphite electrode film with only a PE binder. We note that the graphite electrode film of formulation 2, using both PE and PVDF binders, produced a higher film density than the electrode film of formulation 3, which used only a PTFE binder, as shown in Table 4.

[0084] Table 4 Mechanical Strength Test

[0085] Electrochemical battery testing

[0086] Self-standing electrodes containing membranes A and B (formulations 1-3) were laminated onto copper foil using a calendering process at 185°C, vacuum-dried overnight at 110°C, and then assembled against a lithium metal electrode in a pouch containing electrolyte for electrochemical evaluation. Table 5 provides the coating weights of the graphite electrodes used for battery pack evaluation. Table 6 provides the electrolyte compositions for battery packs containing electrode films treated with membranes A and B.

[0087] Table 5: Coating Load

[0088] Table 6: Electrolyte Composition

[0089] Figures 4A-5B The first-cycle capacity and efficiency results for dry graphite electrode half-cells with electrolytes A and B, measured at 0.05C, are shown. Regardless of electrolyte composition, the PTFE-free graphite electrodes of formulations 1 and 2 provided significantly lower charge and discharge capacities compared to formulation 3, partly due to the higher electrode density. Furthermore, the PTFE-free graphite electrodes of formulations 1 and 2 exhibited reasonable capacities and significantly higher first-cycle efficiencies. Additionally, electrolyte B, with 1 wt.% VC, was observed to suppress charge and discharge capacity while maintaining first-cycle efficiency. Similar results were observed when using electrolyte A.

[0090] Figures 6A-7CExtended differential capacity curves of the lithiation process of half-cells with dry graphite electrodes in formulations 1-3, containing electrolytes A and B, are shown, exhibiting irreversible SEI formation behavior during the initial charging process, which is related to the first cycle efficiency. These results suggest that the electrochemical reduction of PTFE occurs at approximately 0.6 V, which is considered the reason for the lower first cycle efficiency of the graphite electrodes using PTFE binders. Furthermore, the graphite electrode in formulation 3, with a PTFE binder, exhibits additional peaks between 0.2 V and 0.6 V.

[0091] Figures 8A-9C The first cycle voltage curves of half-cells with dry graphite electrodes of formulations 1-3, containing electrolytes A and B, tested at a 0.05C rate are shown. Formulations 2 and 3, with PE and / or PVDF binders, exhibited shallower inflection points (knees) between 0 and 50 mAh / g during lithiation. A similar curve was observed during delithiation compared to formulation 3, with a PTFE binder used for both electrolytes A and B.

[0092] Figures 9A-9C The initial cycling performance of half-cells with electrolyte B from formulations 1-3 (dry graphite electrode) is shown at 0.1C rate. Compared to the formulation 3 graphite electrode cell, formulations 1 and 2 (PTFE-free graphite electrode cells) exhibited more stable initial cycling behavior, reflecting the influence of the PTFE binder forming a highly passivated interface and electrochemical instability between the graphite and lithium metal electrodes. The formulation 2 graphite electrode cell showed sustained stability and high capacity without capacity degradation at 0.1C rate, while the formulation 3 graphite electrode cell showed a relatively large capacity degradation at 0.1C rate, followed by a gradual increase in capacity. This indicates that the formulation 3 electrode cell with the PTFE binder suffers from high interfacial impedance caused by polarization overpotential.

[0093] Although certain embodiments have been described, these embodiments are presented by way of example only and are not intended to limit the scope of this disclosure. In fact, the novel methods and systems described herein can be implemented in many other forms. Furthermore, various omissions, substitutions, and changes can be made to the systems and methods described herein without departing from the spirit of this disclosure. The appended claims and their equivalents are intended to cover such forms or modifications that fall within the scope and spirit of this disclosure.

[0094] Features, materials, characteristics, or groups described in connection with a particular aspect, embodiment, or example shall be construed as applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless incompatible with it. All features disclosed in this specification (including any appended claims, abstract, and drawings) and / or all steps of any disclosed method or process may be combined in any combination, except that at least some of such features / steps are mutually exclusive combinations. Protection is not limited to the details of any of the foregoing embodiments. Protection extends to any novel feature or any novel combination of features disclosed in this specification (including any appended claims, abstract, and drawings), or any novel step or any novel combination of steps of any method or process so disclosed.

[0095] Furthermore, certain features described in the context of individual implementations in this disclosure may also be implemented in combination within a single implementation. Conversely, various features described in the context of a single implementation may also be implemented separately in multiple implementations or in any suitable sub-combination. Moreover, although features may be described above as functioning in certain combinations, in some cases, one or more features from the claimed combination may be removed from that combination, and that combination may be claimed as a sub-combination or a variation of the sub-combination.

[0096] Furthermore, although operations may be depicted in the accompanying drawings or described in the specification in a specific order, it is not necessary to perform such operations in the specific order or sequence shown, or to perform all operations to obtain the desired result. Other operations not depicted 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 any of the stated operations. Furthermore, in other implementations, operations may be rearranged or reordered. Those skilled in the art will understand that in some embodiments, the actual steps taken in the illustrated and / or disclosed process may differ from the steps shown in the figures. Depending on the implementation, some of the above steps may be removed, and other steps may be added. Furthermore, the features and attributes of the specific embodiments disclosed above may be combined in different ways to form other embodiments, all of which fall within the scope of this disclosure. Additionally, 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 can generally be integrated together in a single product or packaged into multiple products. For example, any components described herein for energy storage systems may be provided separately or integrated together (e.g., packaged together, or attached together) to form an energy storage system.

[0097] For the purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not all of these advantages may necessarily be achieved according to any particular embodiment. Therefore, for example, those skilled in the art will recognize that this disclosure may be implemented or practiced in a manner that achieves one or more advantages taught herein without necessarily achieving other advantages taught or suggested herein.

[0098] Unless otherwise explicitly stated or otherwise understood in the context in which they are used, conditional languages ​​such as “can,” “could,” “might,” or “may” are generally intended to convey that certain embodiments include, while other embodiments do not, certain features, elements, and / or steps. Therefore, such conditional languages ​​are generally not intended to imply that one or more embodiments require features, elements, and / or steps in any way, or that one or more embodiments must include logic for determining whether such features, elements, and / or steps are included or will be performed in any particular embodiment, with or without user input or prompts.

[0099] Unless otherwise specified, conjunctions such as “at least one of X, Y, and Z” are generally understood in context to convey that an item, term, etc., can be X, Y, or Z. Therefore, such conjunctions are generally not intended to imply that some implementation requires the presence of at least one of X, at least one of Y, and at least one of Z.

[0100] The degree language used herein, such as the terms “approximately,” “about,” “generally,” and “substantially,” refers to a value, quantity, or characteristic that is close to still being able to perform the desired function or achieve the desired result. For example, the terms “approximately,” “about,” “generally,” and “substantially” can refer to a quantity that, depending on the desired function or desired result, is within 10%, 5%, 1%, 0.1%, or 0.01% of the specified quantity.

[0101] The headings (if any) included in this document are for convenience only and do not necessarily affect the scope or meaning of the apparatus and methods disclosed herein.

[0102] The scope of this disclosure is not intended to be limited by the specific disclosure of preferred embodiments in this part or other parts of this specification, and may be defined by the claims as set forth in this part or other parts of this specification or hereafter. The language of the claims will be interpreted broadly based on the language used in the claims and is not limited to the instances described in this specification or during the execution of this application, which shall be interpreted as non-exclusive.

Claims

1. A dry electrode membrane for an energy storage device, comprising: Dry active materials containing dry particles; and Dry adhesives comprising an elastic polymer selected from the group consisting of polyethylene, poly(ethylene oxide), polyvinylidene fluoride, and mixtures thereof, wherein the elastic polymer comprises a D-value having a density of 10-100 µm. 50 Particles with average particle size distribution; The dry electrode membrane includes an adhesive matrix that provides structural support, such that the dry electrode membrane is self-supporting, free of polytetrafluoroethylene (PTFE), free of solvent residues, has a tensile strength of at least 2 N, contains at least 96 wt% dry active material, and contains 0.5-4 wt.% elastic polymer.

2. The dry electrode membrane according to claim 1, wherein the dry electrode membrane further comprises at least 3 wt% polyethylene.

3. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane further comprises at least 1 wt% polyvinylidene fluoride.

4. The dry electrode film according to claim 1 or 2, wherein the dry active material is graphite.

5. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane has a tensile strength of at least 3 N.

6. The dry electrode film according to claim 1 or 2, wherein the dry electrode film is defect-free.

7. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane comprises at least 97 wt% dry active material.

8. The dry electrode film according to claim 1 or 2, wherein the dry active material is the original dry active material.

9. The dry electrode membrane according to claim 1 or 2, wherein the elastic polymer comprises particles having a density of 10-50 µm. 50 Average particle size distribution.

10. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane comprises 96 wt% dry active material and at least 3 wt% polyethylene.

11. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane comprises 96 wt% dry active material and at least 1 wt% polyvinylidene fluoride.

12. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane has a thickness of at least 77 µm.

13. The dry electrode membrane according to claim 1 or 2, wherein the dry electrode membrane has a thickness of 100-300 µm.

14. An electrode comprising a current collector and a dry electrode membrane as claimed in claim 1 or 2.

15. A battery comprising the electrode of claim 14.

16. A method for manufacturing a dry electrode film, comprising: A dry active material comprising dry particles and a dry binder are mixed to form a dry first mixture, wherein the dry binder comprises D particles having a diameter of 10-100 µm. 50 Elastic polymers with particles of average size distribution; and The dry first mixture is rolled to form a dry electrode film; The dry electrode membrane includes an adhesive matrix that provides structural support, such that the dry electrode membrane is self-supporting, is free of polytetrafluoroethylene (PTFE), has a tensile strength of at least 2N, contains at least 96 wt% dry active material, and contains 0.5-4 wt% elastic polymer. The elastic polymer is selected from the group consisting of polyethylene, poly(ethylene oxide), polyvinylidene fluoride, and mixtures thereof; and The dry active material has a first particle size distribution before mixing and a second particle size distribution after mixing, wherein the first particle size distribution and the second particle size distribution are the same.

17. The method of claim 16, wherein the mixing is carried out by a non-destructive mixing process including resonant acoustic mixing.

18. The method of claim 16 or 17, wherein the mixing does not include high-shear mixing.

19. The method of claim 16 or 17, wherein the mixing is carried out at a temperature of at least room temperature.

20. The method according to claim 16 or 17, wherein the calendering is performed at a temperature of 150-250°C.

21. The method according to claim 16 or 17, further comprising rolling the dry electrode film.

22. The method of claim 16 or 17, wherein the dry electrode film comprises at least 97 wt% dry active material.

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