Compositions and methods for energy storage devices having improved performance

Abstract

To provide electrode films combining complimentary attributes of energy storage devices increasing the operating power and energy.SOLUTION: A single dry electrode film of an energy storage device comprises: a dry active material; and a dry binder; where the dry electrode film is self-supporting, and where the single dry electrode film is at least 110 μm in thickness.SELECTED DRAWING: Figure 14

Description

[Technical field]

[0001] [Field] The present invention relates generally to energy storage devices, and more specifically to materials and methods for dry electrode energy storage devices with improved performance.

[0002] [Incorporation by reference to the priority application] This application claims priority to U.S. Provisional Application No. 62 / 590110, filed November 22, 2017, the entire disclosure of which is incorporated herein by reference. [Background technology]

[0003] Description of Related Art Electrical energy storage batteries are widely used to power electrotechnical, electromechanical, electrochemical, and other useful devices. Such batteries include primary chemical batteries, secondary (rechargeable) batteries, fuel cells, and various types of capacitors, including ultracapacitors. Increasing the operating power and energy of energy storage devices, including capacitors and batteries, is desirable to increase energy storage, increase power capabilities, and expand real-world usage opportunities. Summary of the Invention [Problem to be solved by the invention]

[0004] Energy storage devices including electrode thin films that combine complementary attributes provide improved performance of energy storage devices in real-world applications. Furthermore, existing fabrication methods impose practical limits on electrode properties for various structures. Therefore, new electrode thin film formation and fabrication methods offer the potential for improved performance. Additionally, new combinations of electrode thin films will reveal combinations that can improve the performance of energy storage devices.

[0005] For purposes of summarizing the disclosure and the advantages that can be achieved over the prior art, certain objects and advantages of the disclosure are described herein. Not all such objects and advantages may be achieved in any particular embodiment. Thus, for example, one skilled in the art will appreciate that the invention may be embodied or performed in a manner that achieves or optimizes one or more advantages as taught herein, without necessarily achieving other objects or advantages as taught or suggested herein. [Means for solving the problem]

[0006] In a first aspect, a lithium ion battery is provided that includes at least one self-supporting dry thin electrode film and has improved performance, which may be improved electrode material loading, active material loading, specific capacity, specific capacity, areal energy density, energy density, specific energy density, or coulombic efficiency. In some embodiments, such a battery may have a specific energy density of at least 250 Wh / kg, or an energy density of at least 600 Wh / L.

[0007] In one embodiment, a single dry electrode film of 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 film further includes that the dry electrode film is self-supporting and that the thickness of the dry electrode film is about 110 μm or greater.

[0008] In another 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 film further includes a dry electrode film that is self-supporting and has an electrode film density of at least 1.4 g / cm. 3 This includes the fact that

[0009] In another aspect, a method for fabricating a single dry electrode film for an energy storage device is provided. The method includes providing a dry active material. The method further includes providing a dry binder. The method further includes combining the dry active material and the dry binder to provide an electrode film mixture. The method further includes forming a self-supporting dry electrode film having a thickness of about 110 μm or greater with the electrode film mixture.

[0010] In another aspect, a method for manufacturing a dry electrode film for an energy storage device is provided. The method includes providing a dry active material. The method further includes providing a dry binder. The method further includes combining the dry active material and the dry binder to provide an electrode film mixture. The method further includes providing a dry electrode film having an electrode film density of at least 1.4 g / cm. 3 The method includes forming a self-supporting dry electrode film.

[0011] All of these embodiments are intended to be encompassed within the scope of the invention disclosed herein. These and other embodiments will be readily understood by those of ordinary skill in the art based on the following detailed description of the preferred embodiments, which are described in conjunction with the accompanying drawings. The present invention is not limited by any of the disclosed preferred embodiments. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 illustrates one embodiment of an energy storage device. [Diagram 2] 2A-2D show various configurations of energy storage devices combining dry or wet anodes and cathodes. [Diagram 3]Figure 3A shows a bipolar electrode in which the anode and cathode are joined by a current collector, and Figures 3B-E show various configurations of bipolar electrodes including wet and / or dry electrode films joined by a current collector. [Figure 4] Figures 4(A) to (E) show various energy storage device cell configurations. [Figure 5A] 5A provides capacity data for lithium-ion batteries containing various combinations of dry or wet electrodes: Type 1 contains a dry cathode and a dry anode, Type 2 contains a dry cathode and a wet anode, Type 3 contains a wet cathode and a dry anode, and Type 4 contains a wet cathode and a wet anode. [Figure 5B] 5B provides efficiency data for lithium-ion cells containing various combinations of dry or wet electrodes: Type 1 contains a dry cathode and a dry anode, Type 2 contains a dry cathode and a wet anode, Type 3 contains a wet cathode and a dry anode, and Type 4 contains a wet cathode and a wet anode. [Figure 6] Figure 6 provides data showing the voltage vs. capacity relationship for lithium-ion batteries with various combinations of dry or wet electrodes: Type 1 includes a dry cathode and a dry anode, Type 2 includes a dry cathode and a wet anode, Type 3 includes a wet cathode and a dry anode, and Type 4 includes a wet cathode and a wet anode. [Figure 7] Figure 7 provides volumetric energy density (Wh / L) and gravimetric energy density (Wh / kg) data for lithium-ion batteries with various combinations of dry or wet electrodes: Type 1 includes a dry cathode and a dry anode, Type 2 includes a dry cathode and a wet anode, Type 3 includes a wet cathode and a dry anode, and Type 4 includes a wet cathode and a wet anode. [Figure 8A]FIG. 8A provides capacity data for dry lithium-ion battery anodes processed in multiple sequential steps ("Mix A") or in one step ("Mix B"). [Figure 8B] FIG. 8B provides efficiency data for dry lithium-ion battery anodes processed in multiple sequential steps ("Mix A") or in one step ("Mix B"). [Figure 9A] FIG. 9A provides capacity data for dry lithium-ion battery anodes treated with a blade mixer ("Mixer A") or an acoustic mixer ("Mixer B"). [Figure 9B] FIG. 9B provides efficiency data for dry lithium-ion battery anodes treated with a blade mixer ("Mixer A") or an acoustic mixer ("Mixer B"). [Figure 10A] FIG. 10A provides capacity data for dry lithium-ion battery anodes processed with a polymer binder that was not pre-ground ("Process A") or that was pre-ground using a jet mill prior to introducing the remaining electrode fabrication ingredients ("Process B"). [Figure 10B] FIG. 10B provides efficiency data for dry lithium-ion battery anodes processed with a polymer binder that was not pre-ground ("Process A") or that was pre-ground using a jet mill prior to introducing the remaining electrode fabrication ingredients ("Process B"). [Figure 11A]FIG. 11A provides capacity data for dry lithium-ion battery anodes processed with active material processed using a jet milling step and a binder also processed using a jet milling step ("Formula 1"), or with active material processed using mild powder processing and a binder processed using a jet milling step ("Formula 4"). [Figure 11B] FIG. 11B provides efficiency data for dry lithium-ion battery anodes processed with active material processed using a jet milling step and a binder also processed using a jet milling step ("Formula 1"), or with active material processed using mild powder processing and a binder processed using a jet milling step ("Formula 4"). [Figure 12] FIG. 12 shows the voltage vs. capacity data for the dry-coated thick NMC622 cathode half-cell. [Figure 13] FIG. 13 shows voltage vs. capacity data for a dry-coated thick graphite anode half-cell. [Figure 14] FIG. 14 provides the first cycle electrochemical results for the dry-coated thick NMC622 cathode half-cells with different electrode material loading weights. [Figure 15A] FIG. 15A provides the full cell discharge rate voltage profile for the dry coated thick electrode. [Figure 15B] FIG. 15B provides the full cell discharge rate voltage profile for the wet-coated thick electrode. [Figure 16] FIG. 16 provides the discharge capacity for the dry and wet coated thick electrodes in the full cells shown in FIGS. 15A and 15B at different current rates. [Figure 17A]FIG. 17A provides the full cell charge rate voltage profile for the dry coated thick electrode. [Figure 17B] FIG. 17B provides the full cell charge rate voltage profile for the wet-coated thick electrode. [Figure 18] FIG. 18 provides the charge capacity for the dry and wet coated thick electrodes in the full cells shown in FIGS. 17A and 17B at different current rates. [Figure 19A] FIG. 19A provides electrochemical impedance spectroscopy data of the dry-coated thick electrode in a pouched full cell before degradation. [Figure 19B] FIG. 19B provides electrochemical impedance spectroscopy data of the dry-coated thick electrode in a pouched full cell after aging. [Figure 19C] FIG. 19C provides electrochemical impedance spectroscopy data of the wet-coated thick electrode in a pouched full cell before degradation. [Figure 19D] FIG. 19D provides electrochemical impedance spectroscopy data of the wet-coated thick electrode in a pouched full cell after aging. [Figure 20] FIG. 20 provides the cell voltages of dry and wet coated thick electrodes in a pouched full cell before and after aging. [Figure 21] FIG. 21 provides the cell capacity conservation of dry and wet coated thick electrodes in a pouched full cell after aging. [Figure 22] FIG. 22 shows the relationship between electrode film density and loading amount for traditionally dried electrodes. [Figure 23] FIG. 23 shows the electrode film density versus loading for differently fabricated electrodes produced by the disclosed dry process versus the prior art wet coat process. [Figure 24A]FIG. 24A shows gravimetric energy density versus loading for graphite anodes made in accordance with the present disclosure. [Figure 24B] FIG. 24B shows the volumetric energy density versus loading for graphite anodes made according to the present disclosure. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Provided herein are various embodiments of energy storage devices with improved performance. In particular, in some specific embodiments, the energy storage devices disclosed herein include thin electrode films with high energy density. The energy storage devices incorporate thin electrode films manufactured using improved techniques and by a combination of various processes. The energy storage devices may be lithium-ion based batteries.

[0014] Lithium-ion batteries are used as power sources in many commercial and industrial applications, such as consumer devices, productivity devices, and battery-powered vehicles. However, the demand for energy storage devices is continuously and rapidly growing. For example, the automotive industry is developing vehicles that utilize small and efficient energy storage, in particular plug-in hybrids and fully electric vehicles. Although lithium-ion batteries are suitable to meet future demands, there is a demand for improved energy density to provide longer battery life so that vehicles can travel further on a single charge. Thus, there is a demand for energy storage devices in general, and lithium-ion batteries in particular, to be able to provide higher energy storage and energy density, for example, per unit size relative to the mass and / or volume of the device.

[0015] The key storage components of potential energy storage devices are the electrodes, and more specifically the electrode thin films that make up each electrode. The electrochemical performance of the electrodes, such as the capacity and efficiency of a battery electrode, is influenced by a variety of factors, including the distribution of active materials, binders, and additives, the physical properties of the materials, such as the particle size and surface area of ​​the active materials, the surface properties of the active materials, the physical properties of the electrode thin films, such as their adhesion, and the adhesion of the conductive elements.

[0016] In principle, a thicker electrode film is advantageous because the thicker the electrode film, the As the electrode thickness increases, there is more active material in the device compared to other materials that are not energy storage components. Thicker electrode films can be achieved by loading electrode material per unit area of ​​the current collector, or by increasing the capacity or energy density per unit area of ​​the electrode film. However, making the electrode film thicker tests the practical limits of the electrode film manufacturing technology.

[0017] In general, electrode thin films may degrade due to the mechanical properties of the components of the thin film and their interactions. For example, mechanical limitations may be due to poor adhesion between the active layer and the current collector, or weak bonds between the active material and the binder in the electrode thin film. Such processes may result in performance degradation in both power delivery and energy storage capacity. Performance degradation may be due to deactivation of the active material, for example, due to reduced ionic conductivity, reduced electrical conductivity, or a combination of both. For example, as adhesion between the active layer and the current collector decreases, the battery resistance increases. Reduced bonding between the active materials may also result in increased battery resistance, possibly impairing electrical contact, and removing some active material from the ionic and electrical transport cycle of the battery. Without being limited by theory, volumetric changes of the active material may affect such processes. For example, additional degradation may be observed in electrodes incorporating certain active materials, such as silicon-based materials, which undergo significant volumetric changes during battery cycling. In some systems, the process of lithium intercalation and deintercalation corresponds to such a change in volume. In general, such a mechanical degradation process is observed in any electrode, such as a cathode, anode, positive electrode, negative electrode, battery electrode, capacitor electrode, hybrid electrode, or other electrode of an energy storage device.

[0018] Classic wet battery electrodes coated with slurry can suffer from undesirable problems such as cracking, delamination, and poor flexibility. These problems are exacerbated as the electrode film becomes thicker. As the electrode film becomes thicker, a correspondingly larger electrode material load is typically observed, resulting in poor electrochemical performance and reliability in wet processed electrodes. Wet processing can suffer from limited material options, and the resulting wet processed electrode film can suffer from uneven distribution of constituents, e.g., active materials. As the film thickness and / or density increases, the adverse effects of unevenness also increase. This results in poor ionic and / or electrical conductivity. Wet processing also typically requires expensive and time-consuming drying processes, which become more difficult as the film becomes thicker. Thus, the thickness of electrode films produced by wet processing is also limited. Furthermore, wet, eg, slurry-based, thin film deposition processes, eg, spray, chemical bath deposition, slot die, jetting, and baking, limit the possible configurations of the electrode thin film.

[0019] Embodiments include batteries including electrodes produced by dry processing that have a specific energy density of at least 250 Wh / kg or an energy density of at least 600 Wh / L. Embodiments include wet electrode formation and manufacturing processes that can achieve electrode films with higher density active material, greater electrode film thickness, higher electrode film density, and / or higher electron density (e.g., energy density, specific energy density, areal energy density, specific capacity, and / or specific capacitance). A denser electrode film will generally contain more active material per smaller volume of electrode film. Specifically, dry electrode processing can achieve smaller particle sizes and more intimate contact of active material, binders, and additives. Dry electrode processing methods traditionally utilize high shear and / or high pressure processing steps to disperse and mix the electrode film materials. This step provides structural advantages. In some embodiments, such dry electrode processing can be used to improve the density of the compacted electrode (approximately 1.3 g / cm) compared to conventional wet slurry casting. 3 Sufficiently high electrode density (approximately 1.55 g / cm3) at higher loadings compared to the low electrode loading (approximately 1.55 g / cm3 or less) and porosity (approximately 37% or more). 3 ), and lower electrode porosity (about 26%). However, as shown in FIG. 22, electrodes produced by traditional wet electrode processing have electrode films that become less dense as more electrode material is loaded. This limits the energy and power density in high loaded electrode cells. Some embodiments of the present disclosure provide electrode film densities (about 1.79 g / cm) independent of electrode loading. 3Dry fabrication methods and formulations are provided to control the electrode material composition (e.g., by changing the active material, polymer binders, and additives) and porosity (approximately 16%). Formulations are modified to vary the electrode material composition, e.g., by changing the active material, polymer binders, and additives. Fabrication methods are modified to accommodate dry coating process parameters, e.g., rolling temperature, rolling pressure, rolling roll gap, number of passes, and the like. Embodiments utilizing such processes and compositions exhibit significantly improved electrode film density at high loads. In some embodiments, the rolling process may be performed at about ambient temperature. In some embodiments, high loads and high electrode film density are achieved without drawbacks such as electrode decomposition and / or delamination.

[0020] The wet or self-supporting thin electrode films provided herein provide improved properties compared to typical thin electrode films. For example, the wet or self-supporting thin electrode films provided herein provide one or more of improved material loading or electrode material loading (expressed as the amount of electrode film per unit area of ​​electrode film or current collector), improved active material loading (expressed as the amount of active material per unit area of ​​electrode film or current collector), improved areal volume (expressed as the volume per unit area of ​​electrode film or current collector), improved areal collector (expressed as the energy per unit area of ​​electrode film or current collector), improved specific energy density (expressed as the energy per unit area of ​​electrode film), or improved energy density (expressed as the energy per unit volume of electrode film). In yet another example, the wet or self-supporting thin electrode films provided herein may provide improved coulombic efficiency.

[0021] In some embodiments, energy storage devices are provided that exhibit improved coulombic efficiency compared to energy storage devices constructed using typical materials and manufacturing processes. In particular, the first cycle efficiency of lithium ion batteries that include at least one drying process and / or self-supporting electrodes provided herein can be improved. For example, the first cycle coulombic efficiency during electrochemical cycling can be improved.

[0022] The energy storage devices presented herein are advantageously characterized by a reduced rise in equivalent series resistance over the life of the device, which allows for increased power density over the life of the device. In some embodiments, the energy storage devices presented herein are characterized by reduced capacity loss over the life of the device. Further improvements realized in various embodiments include improved cycling performance, including improved storage stability upon cycling, and reduced capacity loss.

[0023] In some embodiments, dry battery electrodes are connected to conventional slurry coated wet battery electrodes, thereby providing improved performance of batteries containing dry electrodes. In particular, in some embodiments, improved performance of self-supporting dry cathode and wet anode pairs is realized.

[0024] In some embodiments, an energy storage device, such as a lithium ion battery, includes a cathode comprising a self-supporting dry electrode thin film and an anode comprising a self-supporting dry electrode thin film. The energy storage device has one or more additional features provided herein. In further embodiments, the energy storage device includes a cathode comprising a self-supporting dry electrode thin film, and the energy storage device has one or more other performance characteristics provided herein. In yet other embodiments, an energy storage device, such as a lithium ion battery, includes a cathode comprising a self-supporting dry electrode thin film and an anode comprising a wet processed electrode thin film. The energy storage device has one or more additional performance characteristics provided herein. Several combinations of wet or dry electrodes are envisioned, as shown in Table 1.

[0025] [Table 1]

[0026] In Table 1, "dry" refers to self-supporting electrode films (having anode or cathode composition as indicated) prepared by a dry process, and "wet" refers to electrode films (having anode or cathode composition as indicated) prepared by a slurry process.

[0027] Some embodiments relate to dry electrode processing techniques. In one embodiment, dry powder mixing conditions (i.e., sequence, intensity, and time), mixing methods such as grinding and milling, and formulation developments (i.e., active materials, additives, binders) have improved the electrochemical performance of the resulting dry battery electrodes. This improvement is achieved over conventional dry electrode manufacturing processes, such as those disclosed in one or more of U.S. Patent Application Publication No. 2006 / 0114643, U.S. Patent Application Publication No. 2006 / 0133013, U.S. Patent No. 9,525,168, or U.S. Patent No. 7,935,155, all of which are incorporated herein by reference.

[0028] In various embodiments, the dry powders can be mixed in a gentle process using, for example, convection, pneumatic, or diffusion mixers, such as tumblers, paddle mixers, blade mixers, or ultrasonic mixers with or without mixing media (e.g., glass beads, ceramic balls). The gentle mixing process may not destroy the active material in the mixture. Without limitation, graphite particles maintain their size through the gentle mixing process. In further embodiments, the order and conditions of mixing of the powders can be altered to promote uniform distribution of the active material, binder, and additional additives.

[0029] Embodiments include electrode films produced by various combinations of electrode film processing methods. Some examples of electrode formation consisting of processed active materials and binders are listed in Table 2. Process A includes gentle powder processing, such as tumbling, blending, or ultrasonic mixing. Process B includes aggressive powder processing, such as mixing in a Waring blender, by jet milling or grinding.

[0030] [Table 2]

[0031] The materials and methods provided herein can be implemented in a variety of energy storage devices. As provided herein, an energy storage device can be a capacitor, a lithium ion capacitor (LIC), an ultracapacitor, a battery, or any combination of two or more of the above. The above aspects may be combined into a hybrid energy storage device, which in a preferred embodiment is a battery.

[0032] The energy storage devices provided herein may be in any suitable configuration, such as planar, spirally wound, button-shaped, pouch-shaped, etc. The energy storage devices provided herein may be used in a variety of applications, such as power generation systems, uninterruptible power supply systems (UPS), solar power systems, and the like, for example, industrial and / or transportation applications. The energy storage device provided herein may be a component of a system, such as a hybrid electric vehicle (HEV), a plug-in hybrid electric vehicle (PHEV), and the like. The present invention is used to power a variety of electrical devices and / or motor vehicles, including powertrains and / or electric vehicles (HVs).

[0033] 1 shows an example of an energy storage device 100 having a high electrode film density and / or high electron density. The energy storage device 100 can be classified as, for example, a capacitor, a battery, a capacitor-battery hybrid, or a fuel cell. In some embodiments, the device 100 is a lithium ion battery.

[0034] The device includes a first electrode 102, a second electrode 104, and a first electrode 102 and a second electrode 104. and a separator 106 disposed between the electrodes 102 and 104. The first electrode 102 and the second electrode 104 are adjacent to opposing surfaces of the separator 106. The energy storage device 100 is configured to facilitate ionic exchange between the electrodes 102, 104 of the energy storage device 100. The energy storage device includes an electrolyte 118 for charging the first electrode 102, the second electrode 104, and the separator 106. 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.

[0035] One or more of the first electrode 102, the second electrode 104, and the separator 106, or compositions thereof, may include a porous material. The pores of the porous material may confine the electrolyte 118 within the housing 120 and / or increase the surface area in contact with the electrolyte 118. The energy storage device housing 120 may be sealed around the first electrode 102, the second electrode 104, and the separator 106, respectively, and thus physically isolate them from the outside environment.

[0036] 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 isolate two adjacent electrodes, e.g., the first electrode 102 and the second electrode 104, on opposing sides of the separator 106, while allowing ionic exchange between the two adjacent electrodes. The separator 106 can be made of any suitable material that is porous and electrically insulating. For example, the separator 106 can be made of a cellulosic material (e.g., paper), a polyethylene (PE)-based material, a polypropylene (PP)-based material, and / or a polyethylene- and polypropylene-based material.

[0037] Generally, the first electrode 102 and the second electrode 104 each comprise a current collector and an electrode thin film. The electrodes 102, 104 each comprise a high density and / or electron-dense electrode thin film. The electrodes 102, 104 each comprise a single electrode film 112, 114 as shown, although other combinations of two or more electrode films may be included with each electrode 102, 104. Although the device 100 is shown as having a single electrode 102 and a single electrode 104, other combinations are possible. The dense electrode films 112, 114 each may be of any suitable shape, size, and thickness. For example, each of the electrode films may be about 30 microns (μm) to about 250 μm. The electrode thin film 112 and / or the electrode thin film 114 may have a thickness of, for example, 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 a range of values ​​therebetween. Throughout this disclosure, electrode thin film thicknesses are further provided for single electrode thin films. An electrode thin film generally comprises one or more active materials, i.e., an anode active material or a cathode active material, for example, as provided herein. The electrode thin film 112 and / or the electrode thin film 114 are dry and / or self-supporting electrode thin films, as provided herein, and have advantageous properties, such as, for example, thickness, increased electrode thin film density, energy density, specific energy density, energy density per area, capacity per area, or specific capacity, as provided herein. The first electrode thin film 112 and / or the second electrode thin film 114 may include one or more binders, as provided herein. The first electrode film 112 and / or the second electrode film 114 are prepared by processes as described herein. The first electrode film 112 and / or the second electrode film 114 may be wet or self-forming dry electrodes as described herein.

[0038] As shown in FIG. 1, the first electrode 102 and the second electrode 104 each include a first current collector 108 in contact with a first dense electrode film 112 and a second current collector 110 in contact with a second dense electrode film 114. The first current collector 108 and the second current collector 110 facilitate electrical coupling between the respective electrode film and an external electrical circuit (not shown). The first current collector 108 and / or the second current collector 110 may be comprised of one or more conductive materials and may be of any suitable shape and size selected to facilitate transfer of charge between the respective electrode and the external circuit. For example, the current collector may include metallic materials such as aluminum, nickel, copper, rhenium, niobium, tantalum, and may also include precious metals such as silver, gold, platinum, palladium, rhodium, osmium, iridium, alloys, and combinations of the above. For example, the first current collector 108 and / or the second current collector 110 may be made of aluminum foil, copper foil, etc. The first current collector 108 and / or the second current collector 110 may have a rectangular or generally rectangular shape sized to allow transfer of charge between the corresponding electrode and an external circuit.

[0039] Various embodiments of electrode configurations for example energy storage device 100 are shown in Figures 2A-2D. Figure 2A illustrates an energy storage device including a dry anode and a dry cathode. Figure 2B illustrates an energy storage device including a wet anode and a dry cathode. Figure 2C illustrates an energy storage device including a dry anode and a wet cathode. Figure 2D illustrates a comparative energy storage device including a wet anode and a wet cathode. Figure 3A illustrates a generic bipolar electrode. Figures 3B-3E illustrate various bipolar electrode configurations including dry and / or wet electrode films for use in energy storage devices. Figure 3B illustrates a cell with a dry anode combined with a dry cathode. Figure 3C illustrates a cell with a wet anode combined with a dry cathode. Figure 3D illustrates a cell with a dry anode combined with a wet cathode. FIG. 3E depicts a comparative cell configuration in which a wet anode is bonded to a wet cathode.

[0040] Various battery configurations are depicted in Figures 4A-4E. For example, Figure 4A depicts a cell in which the cathode and anode share a single contact area. Figure 4B depicts a cell configuration in which the cathode shares two contact areas with a single anode. In Figure 4B, the cathode is a double-sided cathode and is coated on opposing surfaces with a material suitable for a current collector or separator. In Figure 4C, a cell configuration in which a single anode shares two contact areas with each of two separate cathodes is depicted. In Figure 4C, each of the two cathodes is a double-sided cathode and each cathode is coated on opposing surfaces with a material suitable for a current collector or separator. In Figure 4D, two anodes share two contact areas with each of two separate cathodes, and a third separate cathode provides a contact area with each of the two anodes. FIG. 4E depicts a cell configuration in which a single anode shares a single contact area with a single cathode, but the electrode pair is folded over itself. In some embodiments, an energy storage device may have the configuration depicted in any one of FIGS. 4A-4E. In further embodiments, an energy storage device may have any combination of the aspects depicted in FIGS. 4A-4E. For example, an energy storage device may have at least one of the cells having the configuration depicted in any one of FIGS. 4A-4E and at least one of the other cells having the configuration depicted in another of FIGS. 4A-4E. Additionally, an energy storage device may have an electrode of any one of FIGS. 4A-4E in ionic contact (e.g., separated by a separator impregnated with a suitable electrolyte as shown) or electrical contact (e.g., coupled by a current collector) with an electrode having another configuration of FIGS. 4A-4E.

[0041] In some embodiments, at least one active material comprises a treated carbon material, where the treated carbon material comprises a reduced number of hydrogen-containing, nitrogen-containing, and / or oxygen-containing functional groups, as described in U.S. Patent Application Publication No. 2014 / 0098464. For example, the treated carbon particles may comprise a reduced number of one or more functional groups on one or more surfaces of the treated carbon, where the reduced number is from about 10% to about 60% in one or more functional groups, as compared to about 20% to about 50% on an untreated carbon surface. The treated carbon may comprise a reduced number of hydrogen-containing, nitrogen-containing, and / or oxygen-containing functional groups. In some embodiments, the treated carbon material comprises less than about 1% (including less than about 0.5%) of the functional groups that contain hydrogen. In some embodiments, the treated carbon material comprises less than about 5% (including less than about 3%) of the functional groups that contain oxygen. In a further embodiment, the treated carbon material has about 30% fewer hydrogen-containing functional groups compared to the untreated carbon material.

[0042] In some embodiments, the energy storage device 100 can be a lithium ion battery. In some embodiments, the electrode film of the lithium ion battery electrode includes one or more active materials and a fiberized binder matrix provided herein.

[0043] In further embodiments, the energy storage device 100 is loaded with a suitable lithium-containing electrolyte. For example, the device 100 may include a lithium salt and a solvent, such as a non-aqueous or organic solvent. Typically, the lithium salt includes a redox stable anion. In some embodiments, the anion is monovalent. In some embodiments, the lithium salt is selected from among hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), bis(trifluoromethanesulfonyl)imide (LiN(SO2CF3)2), lithium trifluoromethanesulfonate (LiSO3CF3), 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 may be about 0.1 mol / L (M) to about 5 M, about 0.2 M to about 3 M, or about 0.3 M to about 2 M. In further embodiments, the salt concentration of the electrolyte is about 0.7 M 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 between these values.

[0044] In some embodiments, the electrolyte of the energy storage device provided herein may include a liquid solvent. As provided herein, the solvent need not dissolve all components, and need not completely dissolve any of the electrolyte components. In further embodiments, the solvent may be an organic solvent. In some embodiments, the solvent may include one or more functional groups selected from carbonates, ethers, and / or esters. In some embodiments, the solvent comprises a carbonate. In further embodiments, the carbonate may 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 some embodiments, the electrolyte may include LiPF6 and one or more carbonates. It can be said that it is included.

[0045] In some embodiments, the lithium ion battery is configured to operate between 2.5 V and 4.5 V, or between 3.0 V and 4.2 V. In further embodiments, the lithium ion battery is configured to have a minimum operating voltage between about 2.5 V and about 3 V, respectively. In further embodiments, the lithium ion battery is configured to have a maximum operating voltage between about 4.1 V and about 4.4 V, respectively.

[0046] In some embodiments, a method of manufacturing an energy storage device is provided. In further embodiments, the method includes selecting an anode and a cathode. In some embodiments, selecting an anode includes selecting a dry, self-supporting anode or a wet anode. Selecting a dry anode can include selecting a method for treating the active material and selecting a method for treating the binder.

[0047] In some embodiments, the electrode thin film provided herein includes at least one active material and at least one binder. The at least one active material may be any active material known in the art. The at least one active material may be a material suitable for use in a battery anode or cathode. The anode active material may include, for example, an intercalation material (e.g., carbon, graphite, and / or graphene), an alloying or dealloying material (e.g., silicon, silicon oxide, tin, tin oxide), a metal alloy or composite (e.g., Si-Al, and / or Si-Sn), and / or a conversion material (e.g., manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anode active material may be used alone or in the form of a multiphasic 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).

[0048] 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 include, for example, a layered transition metal oxide (e.g., LiCoO2 (LCO), Li(NiMnCo)O2 (MNC), and / or LiNi 0.8 Co 0.15 Al 0.05 O2(NCA)), spinel manganese oxides (e.g., LiMn 2O4(LMO) and / or LiMn 1.5 Ni 0.5The cathode active material may include lithium oxynitride (LiFePO4), lithium oxynitride (Li2S), or olivine (e.g., LiFePO4). The cathode active material may include sulfur or a sulfur-containing material, such as lithium sulfate (Li2S) or other sulfur-based materials or mixtures thereof. In some embodiments, the cathode thin film includes a material containing sulfur or sulfur active material at a concentration of at least 50 wt %. In some embodiments, the cathode thin film including sulfur or sulfur active material has a capacity of at least 6 mAh / cm 2 In some embodiments, the cathode thin film comprising sulfur or sulfur active material has a specific capacity of 1 g / cm 3 In some embodiments, the cathode thin film containing sulfur or sulfur active material further comprises a binder. In some embodiments, the binder of the cathode thin film containing sulfur or sulfur active material is selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyethylene (PE), other thermoplastics, or any combination thereof.

[0049] At least one active material may include one or more carbon materials. The carbon materials may be selected from, for example, graphitized materials, graphite, graphene-containing materials, hard carbon, soft carbon, carbon nanotubes, porous carbon, conductive carbon, or combinations thereof. The activated carbon may be derived from a steam treatment or an acid / etch treatment. In some embodiments, the graphitized 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 a surface treated carbon.

[0050] In some embodiments, the cathode electrode thin film of the lithium ion battery or hybrid energy storage device can include about 70% to about 98% by weight of at least one active material. This range includes about 70% to about 92% by weight, or about 70% to about 96% by weight. In some embodiments, the cathode electrode thin film includes about 70% or more, about 90% or more, about 92% or more, about 94% or more, about 95% or more, about 96% or more, or about 98% or more by weight of at least one active material, or a range between any of the above values. In some embodiments, the cathode electrode thin film of the lithium ion battery or hybrid energy storage device can include about 40% to about 60% by weight of at least one active material. In some embodiments, the cathode electrode thin film includes up to about 10% by weight of a porous carbon material. This range also includes up to about 5 wt%, or from about 1 wt% to about 5 wt%. In some embodiments, the cathode electrode thin film includes about 10 wt% or more, about 5 wt% or more, about 1 wt% or more, about 0.5 wt% or more of the porous carbon material, or ranges between any of the values ​​recited above. In some embodiments, the cathode electrode thin film includes about 5 wt%, including from about 1 wt% to about 3 wt%, of the conductive additive. In some embodiments, the cathode electrode thin film includes about 10 wt% or more, 5 wt%, about 3 wt% or more, or about 1 wt% or more of the conductive additive, or ranges between any of the values ​​recited above. In some embodiments, the cathode electrode thin film includes up to about 20 wt% (e.g., from about 1.5 wt% to 10 wt%, from about 1.5 wt% to 5 wt%, or from about 1.5 wt% to 3 wt%) of the binder. In some embodiments, the cathode electrode film includes about 1.5% to about 3% by weight of a binder. In some embodiments, the cathode electrode film includes up to about 20% by weight, up to about 15% by weight, up to about 10% by weight, up to about 5% by weight, up to about 3% by weight, up to about 1.5% by weight, up to about 1% by weight. or a range between any of the values ​​recited above.

[0051] In some embodiments, the anode electrode thin film includes at least one active material, a binder, and optionally includes a conductive additive. In some embodiments, the conductive additive may include a conductive carbon additive, such as carbon black. In some embodiments, the at least one active material of the anode may include synthetic graphite, natural graphite, hard carbon, soft carbon, graphene, mesoporous carbon, silicon, silicon oxide, tin, tin oxide, germanium, lithium, titanate, mixtures, or mixtures of the above materials. In some embodiments, the anode electrode thin film may include about 80% to about 98% by weight of the at least one active material. This range includes about 80% to about 98% by weight, or about 94% to about 97% by weight. In some embodiments, the at least one active material may include about 80% to about 98% by weight, or about 94% to about 97% by weight. In some embodiments, the anode electrode thin film may include 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 a range between any of the above values, of at least one active material. In some embodiments, the anode electrode thin film includes up to about 5 wt%, including about 1 wt% to about 3 wt%, of a conductive additive. In some embodiments, the anode electrode thin film includes about 5 wt% or more, about 3 wt% or more, about 1 wt% or more, about 0.5 wt% or more, or a range between any of the above values, of a conductive additive. In some embodiments, the anode electrode thin film includes up to about 20 wt% of a binder. This range includes 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 includes about 20% by weight or more, about 15% by weight or more, about 10% by weight or more, about 5% by weight or more, about 3% by weight or more, about 1.5% by weight or more, about 1% by weight or more, or a range between any of the above values, of a binder. In some embodiments, the anode electrode film can be free of conductive additives.

[0052] Some embodiments include an electrode film, such as an anode and / or a cathode, having one or more active layers that include a polymeric binder material. The binder may include polytetrafluoroethylene (PTFE), polyolefins, polyalkylenes, polyethers, styrene-butadiene, polysiloxane and polysiloxane copolymers, branched polyethers, polyvinyl ethers, copolymers thereof, and / or mixtures thereof. The binder may include a 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 thermoplastic. In some embodiments, the binder may include a fiberizable polymer. In some embodiments, the binder includes, consists essentially of, or consists of PTFE.

[0053] In some embodiments, the binder may include PTFE and additionally 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 celluloses, polyolefins, polyethers, precursors of polyethers, polysiloxanes, polymers thereof, and / or mixtures thereof. The mixture of polymers may include an interpenetrating network of the above-mentioned polymers or copolymers.

[0054] The binder may include various suitable ratios of polymeric components. For example, PTFE may comprise 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. Ranges include 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, PTFE may comprise about 99% or more by weight, about 98% or more by weight, about 95% or more by weight, about 90% or more by weight, about 80% or more by weight, about 70% or more by weight, about 60% or more by weight of the binder. % or more, about 50% or more, about 40% or more, about 30% or more, about 20% or more, or a range between any of the recited values. In some embodiments, the binder can consist essentially of or consist of PTFE.

[0055] In some embodiments, the electrode film mixture may include binder particles having a selected size, in some embodiments, the binder particles are 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 a range between any of the above values.

[0056] As used herein, dry fabrication processes refer to processes in which no or substantially no solvents are used in forming the electrode film. For example, the components of the active layer or electrode film, including the carbon material and binder, may include dry particles. The dry particles for forming the active layer or electrode film may be combined to provide a dry particle active layer mixture. In some embodiments, the 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 are substantially the same as the weight percentages of the components of the dry particle active layer mixture. In some embodiments, the active layer or electrode film formed from the dry particle active layer mixture using a dry fabrication process is free or substantially free of processing additives, such as, for example, solvents and solvent residues. In some embodiments, the resulting active layer or electrode film is a self-forming thin film formed from the dry particle mixture using a dry process. In some embodiments, the resulting active layer or electrode film is a free-standing thin film formed from the dry particle mixture using a dry process. The process for forming the active layer or electrode film may include fiberizing a fiberizable binder component such that the film includes a fiberized binder. In a further embodiment, the free-standing active layer or film is formed in an environment free of a current collector. In a further embodiment, the active layer or electrode film may include a fiberized polymer matrix such that the film is self-supporting. It is believed that a matrix, lattice, or web of fibrils may be formed to provide mechanical structure to the electrode film.

[0057] In some embodiments, the electrode film of the energy storage device, such as when the electrode film is dry and / or self-forming, has a thickness of about 12 mg / cm 2 , about 13mg / cm 2 , about 14mg / cm 2 , about 15mg / cm 2 , about 16mg / cm 2 , about 17mg / cm2 , 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 , about 100mg / cm 2 A high electrode material loading or high active material loading (expressed as the amount of electrode film per unit area of ​​electrode film or current collector) of at least about 12 mg / cm or a range between any of the above values ​​may be provided. In some embodiments, the electrode film of the energy storage device may have a high active material loading (expressed as the amount of electrode film per unit area of ​​electrode film or current collector) of at least about 12 mg / cm, where the electrode film is dry and / or self-forming. 2 of at least about 13 mg / cm 2 of at least about 14 mg / cm 2 of at least about 15 mg / cm 2 of at least about 16 mg / cm 2 of at least about 17 mg / cm 2 of at least about 18 mg / cm 2 of at least about 19 mg / cm 2 of at least about 20 mg / cm 2 of at least about 21 mg / cm 2 of at least about 22 mg / cm 2 of at least about 23 mg / c m 2 of at least about 24 mg / cm 2of at least about 25 mg / cm 2 of at least about 26 mg / cm 2 of at least about 27 mg / cm 2 of at least about 28 mg / cm 2 of at least about 29 mg / cm 2 of at least about 30 mg / cm 2 of at least about 40 mg / cm 2 of at least about 50 mg / cm 2 of at least about 60 mg / cm 2 of at least about 70 mg / cm 2 of at least about 80 mg / cm 2 of at least about 90 mg / cm 2 of at least about 100 mg / cm 2 A high electrode material loading or high active material loading (expressed as the amount of electrode film per unit area of ​​electrode film or current collector) of, or ranging between any of the above values ​​may be provided.

[0058] The electrode thin film may have a selected thickness suitable for a given application. The thickness of the electrode thin film provided herein may be greater than the thickness of electrode thin films prepared by conventional processes. In some embodiments, the electrode thin film may have a thickness of about 110 microns, 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 greater, or may have a thickness within any range between the aforementioned values. The thickness of the electrode thin film may be selected to correspond to a desired specific capacitance, specific capacitance, areal energy density, energy density, or specific energy density.

[0059] In some embodiments, the electrode thin films provided herein may have a greater electrode thin film porosity than electrode thin films prepared by conventional processes. In some embodiments, the electrode thin films provided herein may have a lesser electrode thin film porosity than electrode thin films prepared by conventional processes. In some embodiments, the electrode thin films may have an electrode thin film porosity (expressed as a percentage of the volume of the electrode thin film that is occupied by pores) of about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, or any range between the aforementioned values. In some embodiments, the electrode thin films may have an electrode thin film porosity (expressed as a percentage of the volume of the electrode thin film that is occupied by pores) of up to about 10%, up to about 12%, up to about 14%, up to about 16%, up to about 18%, up to about 20%, or any range between the aforementioned values.

[0060] In some embodiments, the electrode films provided herein may have an electrode film density 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 density of electrode films prepared by conventional processes. In some embodiments, the electrode film may have a density less than about 0.8 g / cm 3 , 1.0g / cm 3 , 1.4g / 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 / cm 3 , about 3.0g / cm 3 , about 3.3g / cm 3 , about 3.4g / cm 3 , about 3.5g / cm 3 , about 3.6g / cm 3 , about 3.7g / cm 3 , about 3.8g / cm 3, or any range between the aforementioned values. In some embodiments, the electrode film has a density of about 0.8 g / cm 3 Up to 1.0g / cm 3 , 1.4g / cm 3 of about 1.5g / cm 3 Up to approx. 1.6g / cm 3 Up to approx. 1.7g / cm 3 Up to approx. 1.8g / cm 3 Up to approx. 1.9g / cm 3 Up to approx. 2.0g / cm 3 In some embodiments, the electrode film can have 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 of at least about 1.6 g / cm 3 of at least about 1.7 g / cm 3 A few At most about 1.8g / cm 3 of at least about 1.9 g / cm 3 of at least about 2.0 g / cm 3 of at least about 2.5 g / cm 3 of at least about 3.0 g / cm 3 of at least about 3.3 g / cm 3 of at least about 3.4 g / cm 3 of at least about 3.5 g / cm 3 The electrode film density may be within a range of any of the above values.

[0061] The formed electrodes are laminated to the electrode films provided herein at temperatures lower than those of conventional processes. In some embodiments, the formed electrodes are laminated at temperatures of about 20° C., about 23° C., about 25° C., about 30° C., about 35° C., about 40° C., about 50° C., about 60° C., about 65° C., about 90° C., about 120° C., about 150° C., about 170° C., about 200° C., or any range between the aforementioned values. In some embodiments, the formed electrodes are laminated at about ambient or room temperature.

[0062] In some embodiments, the electrode film of the energy storage device, in a dry and / or self-supporting state, has a capacity of about 3.5 mAh / cm 2 or more, approximately 3.8mAh / cm 2 of approximately 4mAh / cm 2 of approximately 4.3mAh / cm 2 of approximately 4.5mAh / cm 2 of approximately 4.8mAh / cm 2 of about 5mAh / cm 2 of approximately 5.5mAh / cm 2 of approximately 6mAh / cm 2 of approximately 8mAh / cm 2 of about 10mAh / cm 2 In a further embodiment, the electrode film of the energy storage device, in a dry and / or self-supporting state, may provide a specific capacity (expressed as capacity per unit area of ​​electrode film or current collector) of at least about 8 mAh / cm or within any range between the aforementioned values. 2 For example, about 8mAh / cm 2 of about 10mAh / cm 2 of approximately 12mAh / cm 2 of approximately 14mAh / cm 2 of approximately 16mAh / cm 2 of approximately 18mAh / cm 2 of about 20mAh / cm 2The specific capacity may provide a specific capacity (expressed as capacity per unit area of ​​electrode film or current collector) of or within any range between the above values. In some embodiments, the specific capacity is a charge capacity. In further embodiments, the specific capacity is a discharge capacity.

[0063] In some embodiments, the dry and / or self-supporting graphite battery anode electrode thin film has a capacity of about 3.5 mAh / cm 2 of approximately 4mAh / cm 2 of approximately 4.5mAh / cm 2 of about 5mAh / cm 2 of approximately 5.5mAh / cm 2 of approximately 6mAh / cm 2 of approximately 6.5mAh / cm 2 of approximately 7mAh / cm 2 of approximately 7.5mAh / cm 2 of approximately 8mAh / cm 2 of approximately 8.5mAh / cm 2 of approximately 9mAh / cm 2 of about 10mAh / cm 2 or within any range between the aforementioned values. In some embodiments, the specific capacity is a charge capacity. In further embodiments, the specific capacity is a discharge capacity.

[0064] In some embodiments, the electrode film of the energy storage device, in a dry state and / or self-forming, may provide a specific capacity (expressed as capacity per amount of 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, about 400 mAh / g, or within any range between the aforementioned values. In further embodiments, the electrode film of the energy storage device, in a dry state and / or self-forming, may provide a specific capacity (expressed as capacity per amount of electrode film or current collector) of at least about 170 mAh / g, at least about 250 mAh / g, or within any of the ranges of values ​​mentioned above. In some embodiments, the specific capacity is a charge capacity. In further embodiments, the specific capacity is a discharge capacity. In some embodiments, In some embodiments, the specific capacity is the first charge and / or discharge capacity. In further embodiments, the specific capacity is the charge and / or discharge capacity measured after the first charge and / or discharge.

[0065] In some embodiments, the self-supporting dry electrode thin films provided herein advantageously exhibit improved performance compared to typical electrode thin films. Performance may be, for example, tensile strength, elasticity (stretch), bendability, coulombic efficiency, capacity, or electrical conductivity. In some embodiments, the dry and / or self-forming energy storage device electrode thin films may provide a coulombic efficiency (expressed as a percentage of discharge capacity divided by charge capacity) of approximately at least about 85%, 86%, 87%, about 88%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%. Alternatively, the coulombic efficiency may be within a range between any of the values ​​set forth above, such as, for example, 90.1%, 90.5%, and 91.9%, or may be within a range between any of the values ​​set forth above.

[0066] In some embodiments, an electrode film or electrode of an energy storage device, such as where the electrode film or electrode comprises a dry and / or self-supporting film, may provide a charge capacity retention (expressed as the discharge capacity at a given rate divided by the discharge capacity measured at C / 10) of about 10% or at least about 10%, about 20% or at least about 20%, about 30% or at least about 30%, about 40% or at least about 40%, about 50% or at least about 50%, about 60% or at least about 60%, about 70% or at least about 70%, about 80% or at least about 80%, about 90% or at least about 90%, about 98% or at least about 98%, about 99% or at least about 99%, about 99.9% or at least about 99.9%, about 100% or at least about 100%, or a range between any of the above-mentioned values. In some embodiments, the discharge rate of charge capacity retention is about C / 10 or at least about C / 10, about C / 5 or at least about C / 5, about C / 3 or at least about C / 3, about C / 2 or at least about C / 2, about 1C or at least about 1C, about 1.5C or at least about 1.5C, about 2C or at least about 2C, or within a range between any of these values.

[0067] In some embodiments, an electrode film or electrode of an energy storage device, such as where the electrode film or electrode comprises a dry and / or self-supporting film, may provide a charge capacity production rate (expressed as charge capacity measured at a given constant current rate divided by discharge capacity measured at C / 10) of about or at least about 10%, about 20% or at least about 20%, about 30% or at least about 30%, about 40% or at least about 40%, about 50% or at least about 50%, about 60% or at least about 60%, about 70% or at least about 70%, about 80% or at least about 80%, about 90% or at least about 90%, about 98% or at least about 98%, about 99% or at least about 99%, about 99.9% or at least about 99.9%, about 100% or at least about 100%, or a range between any of the above-mentioned values. In some embodiments, the charge rate of the charge capacity production rate is about C / 10 or at least about C / 10, about C / 5 or at least about C / 5, about C / 3 or at least about C / 3, about C / 2 or at least about C / 2, about 1C or at least about 1C, about 1.5C or at least about 1.5C, about 2C or at least about 2C, or within a range between any of these values.

[0068] In some embodiments, the dry and / or self-forming electrode thin film of the energy storage device has a capacity 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 3 In some embodiments, the electrode thin film may provide a specific energy density or gravimetric energy density (expressed as energy per volume of electrode thin film) of 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, about 900 Wh / kg, or a range between any of these values.

[0069] In some embodiments, the electrode film of the energy storage device in a dry and / or self-forming form has an energy density or volumetric energy density (expressed as energy per unit volume of the final or as-assembled 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, about 1550 Wh / L, or a range between any of these values.

[0070] In some embodiments, a self-supporting dry battery cathode can provide reduced ohmic resistance and / or improved polarization voltage characteristics compared to a wet battery cathode. In further embodiments, a lithium ion battery incorporating a self-supporting dry cathode can advantageously provide reduced ohmic resistance and / or improved polarization voltage characteristics compared to a lithium ion battery having a wet cathode and a wet anode. In further embodiments, a lithium ion battery incorporating a self-supporting dry cathode can demonstrate improved energy density and / or specific energy density compared to a lithium ion battery having a wet cathode.

[0071] In some embodiments, the aged self-supporting dry battery electrodes can achieve reduced ohmic resistance, improved division voltage characteristics, and / or improved capacity compared to aged wet battery electrodes. In some embodiments, the aged dry battery electrodes exhibit a reduction in ohmic resistance of about 5 times, about 10 times, about 15 times, or about 20 times, or a factor between any of these values, compared to the reduction in ohmic resistance of a similarly aged wet battery electrode. In some embodiments, the aged dry battery electrodes exhibit a reduction in voltage of about 1.5 times, about 2 times, about 3 times, or about 5 times, or a factor between any of these values, compared to the reduction in voltage of a similarly aged wet battery electrode. In some embodiments, aged dry battery electrodes exhibit a reduction in capacity that is about 1.5 times, about 2 times, about 3 times, or about 5 times less than the degree of capacity reduction in similarly aged wet battery electrodes, or by any factor within any range of these values.

[0072] In the specific examples below, battery electrodes were produced that have high energy density, high specific energy density, high thickness, and / or high electrode film density.

[0073] [Definition] As used herein, the terms "battery" and "capacitor" are to be given their ordinary and accustomed meaning to those of ordinary skill in the art. The terms "battery" and "capacitor" are non-exclusive of each other. A capacitor or battery may refer to a single electrochemical cell operated alone or as a component of a multi-cell system.

[0074] As used herein, the voltage of an energy storage device is the operating voltage of a single battery or capacitor cell. The voltage may be above the rated voltage, below the rated voltage under load, or due to manufacturing tolerances.

[0075] As provided herein, a "self-supporting" electrode film is an electrode film that incorporates a binder matrix structure sufficient to support and maintain the shape of the film or layer, thereby allowing the electrode film or layer to be self-supporting. When incorporated into an energy storage device, a self-supporting electrode film or active layer is one that includes a binder matrix structure as described above. Typically, and depending on the method employed, such an electrode film or active layer has sufficient strength to be used in the energy storage device manufacturing process without the need for any external support elements (e.g., current collectors or other films). For example, a "self-supporting" electrode may have sufficient strength to be rolled, handled, and unrolled in the electrode manufacturing process without the need for other support elements. A dry electrode film, such as a cathode electrode film or an anode electrode film, may be self-supporting.

[0076] As provided herein, a "solvent-free" electrode film refers to an electrode film that does not contain detectable process solvent, process solvent residues, or process solvent impurities. Dry electrode films, such as cathode and anode electrode films, may be solvent-free.

[0077] A "wet" electrode, "wet processed" electrode, or slurry electrode refers to an electrode that is prepared by at least one process of slurrying active material, binder, and additional additives. A wet electrode may contain processing solvent, processing solvent residues, and / or processing solvent impurities.

[0078] [Example 1: Thick electrode] The dry cell anode was fabricated with 96% graphite and 4% binder by weight. The binder included 2% PTFE, 1% CMC, and 1% PVDF, totaling 4% by weight. The cathode was also fabricated by dry processing. The cathode included 94% NMC622, 3% conductive charge, and 3% polymer binder by weight. In addition, wet electrodes were fabricated with the following composition: the wet anode included 95.7% graphite, 1% conductive additive, and 3.3% polymer binder by weight. The wet cathode included 91.5% active component, 4.4% conductive additive, and 4.1% polymer binder by weight. Other compositions for the electrode thin films may be created and prepared, and the disclosure herein is not intended to be limited to the specific compositions disclosed.

[0079] Four lithium-ion cells were assembled according to the scheme in Table 1. Each lithium-ion cell in Table 1 was tested for specific capacity (see FIG. 5A), coulombic efficiency (see FIG. 5B), polarization during charge and discharge (see FIG. 6), and energy density / specific energy density (see FIG. 7).

[0080] As shown in Figures 5A and 5B, the performance of the cells incorporating dry electrodes was better than that of the cells including wet cathodes and wet anodes. In Figure 5A, the specific capacity measured for the cells with dry cathodes ("Type 1" and "Type 2") was the best. In Figure 5B, the coulombic efficiency measured for the cells with dry cathodes (again, "Type 1" and "Type 2") was the best. For the cells tested in Figures 5A and 5B, the electrode material loading was 20.9 mg / cm for Type 1. 2 , and type 2, 24.3 mg / cm 2 , type 3, 22.8 mg / c m 2 , and type 4, 24.1 mg / cm 2 It was.

[0081] FIG. 6 shows the polarization behavior of all lithium-ion battery cells with electrode pairs paired according to Table 1. Lithium-ion cells containing wet anode and wet cathode pairs ("wet-wet", type 4 in Table 1) exhibited steeper voltage polarization during charging and a faster voltage drop during discharging than those containing dry anode and dry cathode pairs ("dry-dry", type 1 in Table 1). This supports the higher ohmic resistance in cells with wet-wet pairs. Without being limited by theory, it is believed that under similar applied current conditions, the slower diffusion of lithium ions increases the resistance in wet-wet cells. In the example shown, replacing the wet cathode with a dry cathode ("dry-wet", corresponding to type 2 in Table 1) significantly improved the voltage profile. This suggests that the incorporation of dry electrodes reduces the ohmic impedance seen in wet-wet cells. In the battery tested in Figure 6, the electrode material loading was 20.9 mg / cm for type 1. 2 , and type 2, 23.9 mg / cm 2 , and type 3, 23.0 mg / cm 2 , and type 4, 23.8 mg / cm 2 It was.

[0082] As shown in Figure 7, lithium ion batteries incorporating a self-supporting dry cathode exhibited significantly improved energy density and specific energy density compared to wet-wet battery cells. In the embodiment of Figure 7, the energy density and specific energy of the cells incorporating a dry cathode ("Type 1" and "Type 2") were significantly higher than those having a wet cathode ("Type 3" and "Type 4").

[0083] As shown, dry battery electrodes can, in some embodiments, improve the electrochemical performance of energy storage devices. For example, it has been found that dry battery electrodes can improve the performance of energy storage devices incorporating one wet processed electrode compared to energy storage devices incorporating only wet processed electrodes. In particular, it has been found that the use of self-supporting dry cathodes can improve the performance of lithium ion batteries.

[0084] 8A and 8B show the results of specific capacity and coulombic efficiency of graphite anodes prepared by two different dry mixing processes using the same anode manufacturing method. The first anode thin film containing graphite, binder, and additives was prepared by mixing in multiple successive steps ("Mix A"), and the second anode thin film was prepared by mixing all materials in one step ("Mix B"). Mix A was made according to the following procedure: graphite was combined with a first binder (CMC) to form a first mixture, the first mixture was combined with a second binder (PVDF) to form a second mixture, and the second mixture was combined with a third binder (PTFE) to form a third mixture. The mixing conditions in each step were the same. The anode made with Mix A showed higher specific charge and discharge capacity. Both the anodes made with Mix A and Mix B showed similar coulombic efficiency. Without being limited by theory, it is believed that the coulombic efficiency depends in part on the amount of surface area of ​​the active material. Thus, it can be hypothesized that the improved electrochemical performance in Mix A is due to the uniform spreading of the powder components in the Mix A electrode. The electrode material loading was 23.1 mg / cm for the Mix A electrode. 2 , and 23.4 mg / cm for the electrode of Mix B. 2 It was.

[0085] 9A and 9B show the specific capacity and coulombic efficiency results for graphite anodes prepared using two different mixer techniques used in the same anode fabrication process. , provided. The first anode, containing graphite, binder, and additives, was combined by a blade blender ("Mixer A"), and the second anode was produced by combining the materials in an acoustic resonance mixer ("Mixer B"). The electrochemical performance of the anode produced by Mixer B was higher, both in terms of specific charge / discharge capacity and coulombic efficiency. It can be assumed that the powder components are better spread in the Mixer B electrode, and conversely, the active material particles are less damaged. The electrode material loading was 16 mg / cm for the Mixer A electrode. 2 , and 17.8 mg / cm for the electrode of mixer B. 2 It was.

[0086] 10A and 10B provide the specific capacity and coulombic efficiency results for graphite anodes of the same material composition prepared using a non-pre-ground polymer binder (relative "Treatment A") and a pre-ground polymer binder that was processed using a jet mill prior to the introduction of the remaining electrode fabrication ingredients. After the introduction of the remaining electrode fabrication ingredients, the next processing step ("Treatment B") is performed. In both specific charge / discharge capacity and coulombic efficiency, the electrodes of Treatment B were superior to those of Treatment A. The electrode material loading was 17.8 mg / cm for the electrodes of Treatment A. 2 , and 19.5 mg / cm for the electrode of treatment B. 2 It was.

[0087] Two additional anodes were fabricated and tested. A first dry cell graphite anode was prepared with active material that had been processed using a jet milling step and a binder that had also been processed using a jet milling step ("Formula 1"). A second dry cell graphite anode was prepared with active material that had been processed using a gentle powder process such as a tumble blender, but not jet milling, and a binder that had been processed using a jet milling step ("Formula 4"). Specific capacity and coulombic efficiency results are shown in Figures 11A and 11B. The electrode from Formulation 4, which has non-destructively processed active material and a jet milled binder, exhibited better specific capacity and efficiency performance than Formulation 1. The electrode material loading was 20.2 mg / cm for Formulation 1 electrodes. 2 , and 19.5 mg / cm for the electrode made using method 4. 2 It was.

[0088] [Specific capacitance in thick dry electrodes] Table 3 provides electrode details for the thick NMC622 cathode and thick graphite anode. The NMC622 cathode is composed of 94 wt% NMC622, 2 wt% porous carbon, 1 wt% conductive carbon, and 3 wt% PTFE. The graphite anode is composed of 96 wt% graphite, 1.5 wt% CMC, 0.5 wt% PVDF, and 2 wt% PTFE. The half-cell first cycle results for the dry NMC622 and graphite electrodes, respectively, are shown in Figures 12 and 13. The half-cell in Figure 12 was charged at room temperature at a constant current of C / 20 to a cutoff at 4.3 V, then a constant voltage was maintained to a cutoff at C / 40, and then discharged at room temperature at a constant current of C / 20 to a cutoff at 2.7 V. The half-cells of FIG. 13 were charged at room temperature at a constant current of C / 20 to a cutoff at 5 mV, then a constant voltage was maintained to a cutoff at C / 40, and then discharged at a constant current of C / 20 to a cutoff at 2 V at room temperature. The first cycle specific discharge capacity in both polarities exceeds the manufacturer's specific target capacity (175 mAh / g for NMC622 and 350 mAh / g as recorded in Table 4). The electrochemical results of these half-cells suggest that thick, dry, coated lithium-ion battery electrodes have improved functionality.

[0089] [Table 3]

[0090] [Table 4]

[0091] FIG. 14 shows that the electrode material loading is approximately 29 mg / cm 2 , about 38mg / cm 2 , and about 46 mg / cm 2Electrochemical half-cell results for the first cycle of dry-coated NMC electrodes of 117 μm, 137 μm, and 169 μm are presented. The corresponding electrode thicknesses are proportional to the three loadings, i.e., 117 μm, 137 μm, and 169 μm, respectively. The specific charge capacity for all three cathodes is 196 mAh / g. The specific discharge capacity for all three cathodes exceeds the manufacturer's target of 175 mAh / g for NMC622. Thus, their efficiencies are greater than 90% (discharge capacity divided by charge capacity). As a comparison, a wet-coated NMC622 cathode of about 80 μm thickness provides an efficiency of about 87.5%, with a similar specific At higher thicknesses, wet-coated electrodes typically suffer degradation in energy density, first charge capacity, cycle life, and high temperature storage (supporting data provided below). These results suggest that the dry-coated thick NMC622 cathode can provide faster charging and higher energy density compared to traditional wet-coated electrodes.

[0092] [Example 3: Charge and discharge performance in thick electrodes] Figures 15A and 15B provide the discharge rate voltage profiles for the dry and wet coated electrodes, respectively. The active materials used for both coating techniques are NMC622 for the cathode and graphite for the anode. The wet NMC622 cathode is approximately 92% by weight NMC622, 4% by weight conductive carbon, and 4% by weight of PVDF. The wet NMC622 cathode is 41.0 mg / cm 2 loading, resulting in a film thickness of 155 μm, porosity of 36%, and a weight of 2.66 g / cm 3The wet graphite anode is composed of approximately 96% graphite, 1% conductive carbon, and 3% CMC / styrene-butadiene binder by weight. The wet graphite anode has an electrode film density of 24.5 mg / cm. 2 loading, resulting in a film thickness of 182 μm, a porosity of 37.5%, and a weight of 1.35 g / cm 3 An electrode thin film density of

[0093] The dried NMC622 cathode is composed of about 95% by weight NMC622, 2% by weight porous carbon, 1% by weight conductive carbon, and 2% by weight PTFE. The dried graphite anode is composed of about 96% by weight graphite, 1% by weight CMC, 1% by weight PVDF, and 2% by weight PTFE. Further properties of the dried NMC622 cathode and dried graphite anode are shown below in Table 5.

[0094] [Table 5]

[0095] The specific capacity of the designed electrode is approximately 6.6 mAh / cm 2 and the cell format used to compare both coating technologies is the same. The charge rate used to establish the cell capacity was measured under C / 10 rate, which resulted in about 0.14 Ah for both dry and wet coated electrodes. As seen in FIG. 16, the charge capacity retention, defined as the charge capacity at a given rate divided by the discharge capacity measured at C / 10, decreased more rapidly for the wet coated electrode as the discharge rate increased from C / 10 to 1.5C. These results suggest that for a given battery operated at a discharge rate of 1.5C, the wet coated electrode provides more than three times the runtime.

[0096] Figures 17A and 17B provide the charge rate voltage profiles for the dry and wet coated electrodes, respectively. Both electrodes shown in Figures 17A and 17B were charged under constant current. The active materials used in both coating techniques were NMC622 for the cathode and graphite for the anode. The specific capacity of the designed electrodes was 6.6 mAh / cm. 2 The cell format used to compare both coating technologies is the same. The charge rate used to establish the cell capacity was measured at a rate of C / 10, resulting in about 0.16 Ah for both dry and wet coated electrodes. As shown in FIG. 18, the charge capacity production rate, defined as the charge capacity measured under a given constant current rate divided by the discharge capacity measured at C / 10, decreases more rapidly for the wet coated electrodes as the charge rate increases from C / 5 to 2C, compared to the dry coated thick electrodes. These results are consistent with the results shown in FIG. 18, where the charge rate is measured at a rate of C / 5 to 2C, and the cell format used to compare both coating technologies is the same. The charge rate used to establish the cell capacity was measured at a rate of C / 10, resulting in about 0.16 Ah for both dry and wet coated electrodes. As shown in FIG. 18, the charge capacity production rate, defined as the charge capacity measured under a given constant current rate divided by the discharge capacity measured at C / 10, decreases more rapidly for the wet coated electrodes as the charge rate increases from C / 5 to 2C, compared to the dry coated thick electrodes. These results suggest that in a given battery at 1000 Hz (~2000 Hz), the dry-coated thick electrode provides more than five times the capacity compared to the wet-coated electrode.

[0097] [Example 4: Storage of thick electrodes at high temperatures] Table 6 provides electrode details for the thick NMC622 cathode and thick graphite anode produced by the drying process. The dried NMC622 cathode is composed of about 95 wt% NMC622, 2 wt% porous carbon, 1 wt% conductive carbon, and 2 wt% PTFE. The dried graphite anode is composed of about 96 wt% graphite, 1 wt% CMC, 1 wt% PVDF, and 2 wt% PTFE.

[0098] [Table 6]

[0099] Table 7 provides electrode details for thick NMC622 cathode and thick graphite anode produced by wet processing. The wet NMC622 cathode is composed of about 92 wt% NMC622, 4 wt% conductive carbon, and 4 wt% PVDF. The wet graphite anode is composed of about 96 wt% graphite, 1 wt% conductive carbon, and 3 wt% CMC / styrene-butadiene binder. The cell format used to compare the coating techniques in Tables 5 and 6 is the same.

[0100] [Table 7]

[0101] 19A and 19B provide electrochemical impedance spectroscopy data for the dry-coated thick electrodes shown in Table 6, before and after aging, respectively. FIG. 19C and 19D provide electrochemical impedance spectroscopy data for the wet-coated thick electrodes shown in Table 7, before and after aging, respectively. Measurements were recorded under 100% state of charge (SOC) both before and after aging. The active materials used in both coating techniques were NMC622 for the cathode and graphite for the anode. As can be seen by comparing FIG. 19A with FIG. 19C, the resistance of the dry-coated electrode cells before storage at elevated temperature is consistently lower than that of the wet-coated electrode cells. As can be seen by comparing FIG. 19B with FIG. 19D, after storing the cells for 6 weeks at 65 degrees Celsius and 100% SOC, the resistance of the wet-coated electrode cells increased by about 10 times compared to the minimal change observed in the dry-coated electrode cells.

[0102] As can be seen in Figure 20, after 6 weeks of storage at 65 degrees Celsius and 100% SOC, the cell voltage of the wet coated electrode was more severely affected than that of the dry coated electrode. The voltage drop in the wet coated electrode was about three times higher than that of the dry coated electrode, 255 millivolts and about 108 millivolts, respectively.

[0103] As shown in Figure 21, after 6 weeks of aging, high temperature storage conditions significantly reduced the wet coating After six weeks at 65 degrees Celsius and 100% SOC, the wet-coated electrode cell lost approximately twice as much capacity as the dry-coated electrode cell (37% vs. 17.7%).

[0104] The set of comparative tests shown in Figures 19A through 21 suggest that in many applications, such as electric vehicle batteries, dry coated electrodes provide a greater range under high performance driving conditions, faster charge times, and longer life than wet coated thick electrodes.

[0105] [Example 5: High-density electrodes and thin electrode films] Electrode formulations and thin film rolling processes have been developed to improve the density of the electrode thin film while maintaining the physical properties and electrochemical performance of the electrode, thereby overcoming the problem of high loading of the electrode material by wet casting. Two electrode preparation methods include 94 wt% graphite active material and 6 wt% polymer binder, which are rolled at temperatures ranging from 37°C to about 150°C. Preparation 1 is 94 wt% graphite, 3 wt% CMC, and 3 wt% PTFE, and Preparation 2 is 94 wt% graphite, 2 wt% CMC, 1 wt% PVDF, and 3 wt% PTFE. It is suggested that by optimizing the preparation method and by rolling the graphite electrode at a low temperature, the density of the electrode thin film can be significantly improved. The densities of the electrode thin films for Preparations 1 and 2 rolled at various temperatures are shown in Table 8 below.

[0106] [Table 8]

[0107] In addition, in the preparation of 94% active material, the electrode material loading of the graphite anode and cathode was 40 mg / cm2. 2 ~50mg / cm 2 A significant increase in the electrode material loading and electrode film density suggests that dry electrode processing at temperatures as low as 35°C produces a 6% binder, and thus a reversible capacity delivery over a wide range of electrode film densities compared to conventional low film density wet electrodes (see Benchmark). In addition, Figures 24A and 24B show that the energy density of electrodes prepared with such high electrode material loading and high electrode film density is 24.7 mg / cm at the electrode level. 2 A 52% increase in gravimetric density and a 198% increase in volumetric density were observed compared to conventional wet-coated graphite anodes. In addition, the electrode density increased by 36% compared to conventional wet-slurry electrodes. was seen.

[0108] [Solid state] In some examples, a solid-state energy storage device is disclosed that includes the electrode thin film described herein. In some embodiments, the solid-state energy storage device is a solid-state battery. The solid-state battery has improved safety by employing non-flammable elements. In addition, the solid-state battery can safely utilize elemental lithium metal since the problem of protrusion formation is less severe compared to typical liquid-based lithium-ion batteries. Lithium metal offers a significantly higher theoretical specific capacity compared to graphite. Therefore, lithium metal can improve the energy density compared to typical lithium-ion batteries. Furthermore, the dry electrode processing method is expected to be cheaper and safer than conventional methods. Typically, a solid-state lithium battery comprises an ionically and / or electrically conductive cathode, a solid electrolyte, and a lithium metal anode. In some embodiments, at least one of the electrolytes includes a solid electrolyte salt. In some embodiments, the solid electrolyte particles are an ionically conductive inorganic solid electrolyte. In some embodiments, the solid electrolyte particles are a dry-processed mixed solid polymer electrolyte (SPE).

[0109] In some embodiments, the solid electrolyte salt is a lithium salt. In some embodiments, the lithium salt is at least one selected from lithium hexafluorophosphate, bis(trifluoromethanesulfonyl)imide, lithium tetrafluoroborate, trifluoromethanesulfonate, lithium bis(glycolosulfonyl)imide, lithium bis(pentafluoroethanesulfonyl)imide, lithium bis(oxalato)borate, and lithium perchlorate. In some embodiments, the electrode salt is, for example, Li 6.5 La3Zn 1.5 Ta 0.5 O 12 , Li6La3SnMO 12 (M=Sb, Nb, Ta, Zr), Li5La3Ta2O 12In some embodiments, the electrode salt is a sulfur-based electrode salt, such as Li2S-P2S5 and Li2S-P2S5-Li3PO4. In some embodiments, the electrode salt is Li 0.5 La 0.5 TiO3(LLTO) and / or Li7La3Zr2O 12 In some embodiments, the electrode salt is Lithium Super Ionic Conductor (LISCON). (2+2X) Zinc (1-X) It may have the molecular formula GeO4.

[0110] In some embodiments, the mixture, a solid polymer electrolyte (SPE), comprises at least one ionically conductive polymer. In some embodiments, the SPE comprises at least one lithium ion salt. In some embodiments, the SPE comprises at least one supporting polymer binder. In some embodiments, the SPE comprises at least one filler. In some embodiments, the SPE comprises at least one ionically conductive polymer and at least one lithium ion salt. In some embodiments, the SPE comprises at least one ionically conductive polymer, at least one lithium ion salt, and at least one supporting polymer. In some embodiments, the SPE comprises at least one ionically conductive polymer, at least one lithium ion salt, at least one supporting polymer, and at least one filler.

[0111] In some embodiments, the ion-conducting polymer is polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), poly(methylene oxide), polyoxymethylene, poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone) (PVP), poly(methyl methacrylate), poly(vinyl acetate), poly(vinyl chloride), poly(vinyl acetate), poly(oxyethylene) 9 methacrylate, poly(ethylene oxide) methyl ether methacrylates, and poly(propylene imines).

[0112] In some embodiments, the lithium salt is lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(fluorosulfonyl)imide, lithium bis(pentafluoroethanesulfonyl)imide, lithium perchlorate (LiClO4 ), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (Li(C2F5 SO2)2N), lithium bis(oxalato)borate (LiB(C2O4)2), lithium trifluoromethanesulfonate (LiCF3SO3), Li 6.4 La3Zn4Ta 0.6 O 12 , Li7La3Zr2O 12 , Li 10 SnP2S 12 , Li 3X La 2 / 3-X TiO3, Li 0.8 La 0.6 Zr2(PO4)3, Li 1+X Ti 2-X A l X (PO4)3, Li 1+X+y Ti 2―X Al X S y (PO4) 3-y , and LiTi X Zr 2-X(PO4)3. In some embodiments, the lithium salt may be a lithium salt as previously described herein.

[0113] Although several embodiments have been shown, 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 presented herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions, and changes may be made to the systems and methods presented herein without departing from the spirit of the present disclosure. The appended claims and their equivalents are intended to cover such forms or modifications as fall within the scope and spirit of the present disclosure.

[0114] Unless a contradiction occurs, features, materials, properties, or groups described herein in conjunction with a particular aspect, embodiment, or example should be understood to be applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification. All features disclosed in this specification (including any of the accompanying claims, abstract, and drawings) and / or any steps of any method or process disclosed may be combined in any combination, except combinations in which at least some of such features and / or methods are mutually exclusive. Protection is not limited by the details of any of the preceding embodiments. Protection extends to any new one or new combination of features disclosed in this specification (including any of the accompanying claims, abstract, and drawings). Alternatively, protection extends to any new one or new combination of any steps of any method or process disclosed.

[0115] Moreover, features that are shown in this disclosure as separate implementations in the context may be implemented in combination in a single implementation. Conversely, various features that are shown in the context as a single implementation may also be implemented in multiple implementations separately or in any suitable subcombination. Furthermore, even if certain features are shown above as operating in a certain combination, in some cases, one or more features may be isolated from the claimed combination and the isolated features may be claimed as a subcombination or a variant of the subcombination.

[0116] Moreover, although certain operations may be illustrated in the figures or described in the specification as being in a particular order, such operations do not necessarily have to be performed in the particular order or sequence shown, or all operations need not be performed, to achieve desirable results. In some implementations, the steps may be combined in a single step or in a single step. For example, one or more additional operations may be performed before, after, simultaneously with, or between the operations described above. Additionally, operations may be rearranged or resequenced in other implementations. Those skilled in the art will recognize that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may differ from those shown in the figures. Depending on the embodiment, certain steps described above may be omitted and other steps may be added. Additionally, features and attributes of specific embodiments disclosed above may be combined in other manners to form additional embodiments, all such embodiments being within the scope of the present disclosure. Additionally, the separation of the various system elements in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described elements and systems may generally be combined to form a single product or packaged into multiple products. For example, the elements of the energy storage device shown herein may be provided alone or integrated (e.g., packaged or combined together) together to form an energy storage system.

[0117] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. It is not necessary that all such advantages be achieved in any particular embodiment. Thus, for example, one skilled in the art will recognize that the disclosure can be embodied or carried out in a manner that achieves one advantage or a group of advantages as taught herein, without necessarily achieving other advantages as taught or suggested herein.

[0118] Conditional language such as "can," "could," "would," or "may" is typically intended to convey that certain features, elements, and / or steps are included in particular embodiments and not included in other embodiments, unless specifically stated otherwise and unless otherwise understood in the context in which it is used. As such, such conditional language is typically not intended to imply that certain features, elements, and / or steps are required in any way in one or more embodiments, nor is it intended to imply that one or more embodiments require logic for determining, with or without user input or prompting, whether those features, elements, and / or steps are included or performed in any particular embodiment.

[0119] Linked language, such as the phrase "at least one of X, Y, and Z," unless specifically stated otherwise, is to be understood in its ordinary context, i.e., to convey that an item, term, etc. is either X, Y, or Z. As such, such linking language is generally not intended to imply that the presence of at least one X, at least one Y, and at least one Z is required in an embodiment.

[0120] For example, words indicating degree, such as "approximately," "about," "typically," and "substantially," as used herein, refer to a value, amount, or characteristic that is close to the stated value, amount, or characteristic and that would still perform a desired function or achieve a desired result if that value, amount, or characteristic were adopted. For example, terms such as "approximately," "about," "typically," and "substantially" refer to an amount within a 10% difference, within a 5% difference, within a 1% difference, within a 0.1% difference, and within a 0.01% difference from the stated amount, where the ranges vary depending on the desired function or result.

[0121] The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the apparatus and methods disclosed herein.

[0122] The scope of the disclosure is not intended to be limited by the specific disclosures in the preferred embodiments here or elsewhere in this specification, but rather as defined by the claims here or elsewhere in this specification, or as set forth in the future. Claim language is to be interpreted broadly based on the language employed in the claims, and not limited by examples set forth in the present specification or prosecution history of the application. Examples are to be construed in a non-limiting manner.

Claims

1. A dry electrode thin film for an energy storage device, comprising: A dried active material; A dried binder; Equipped with the dry electrode film is self-supporting, substantially free of solvent residue, has a porosity of up to 40%, and is at least 110 μm thick; The dry electrode thin film, wherein the dry binder comprises polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC).

2. A dry electrode thin film as described in claim 1, wherein the porosity of the dry electrode thin film is up to 20%.

3. The dry electrode thin film of claim 1, wherein the density of the electrode thin film is at least 0.8 g / cm 3 .

4. A dry electrode thin film for an energy storage device, comprising: A dried active material; A dried binder; Equipped with the dry electrode film is self-supporting, substantially free of solvent residues, and has a density of at least 1.4 g / cm ; The dry electrode thin film, wherein the dry binder comprises polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC).

5. A dry electrode thin film as described in claim 4, having a thickness of at least 110 μm.

6. A dry electrode thin film as described in claim 4, having a thickness of at least 155 μm.

7. The dry electrode thin film of claim 1 or 4, wherein the electrode material loading of the dry electrode thin film is at least 20 mg / cm 2 .

8. A dry electrode thin film as described in claim 1 or 4, wherein the dry electrode thin film contains at least 90% by weight of the dry active material.

9. A dry electrode thin film as described in claim 1 or 4, wherein the dry active material includes an anode active material.

10. A dry electrode thin film as described in claim 9, wherein the anode active material includes a carbon active material.

11. A dry electrode thin film as described in claim 10, wherein the carbon active material includes graphite.

12. A dry electrode thin film as described in claim 1 or 4, wherein the dry active material includes a cathode active material.

13. The dry electrode thin film of claim 12, wherein the cathode active material comprises lithium nickel manganese cobalt oxide (NMC).

14. A dry electrode thin film as described in claim 12, wherein the cathode active material includes a sulfur-based material.

15. A dry electrode thin film as described in claim 1 or 4, wherein the dried binder includes a fibrous binder.

16. A dry electrode thin film as described in claim 1 or 4, wherein the dry binder comprises polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC) in a 1:1 ratio by weight.

17. A dry electrode thin film as described in claim 1 or 4, wherein the dry binder comprises polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), and polyvinylidene fluoride (PVDF) in a ratio of 2:1:1 or 3:2:1 by weight.

18. A dry electrode thin film as described in claim 1 or 4, wherein the dry electrode thin film contains 20% by weight or less of the dry binder.

19. A dry electrode thin film according to claim 1 or 4, further comprising a conductive additive.

20. A dry electrode thin film as described in claim 19, wherein the dry electrode thin film contains 5 wt% or less of the conductive additive.

21. A dry electrode thin film as described in claim 1 or 4, further comprising a porous material.

22. A dry electrode thin film as described in claim 21, wherein the dry electrode thin film contains 10% by weight or less of the porous material.

23. An electrode comprising the dry electrode thin film described in claim 1 or 4, wherein the dry electrode thin film is in contact with a current collecting material.

24. An electrode as described in claim 23, wherein the volumetric energy density of the electrode is at least 550 Wh.

25. An electrode as described in claim 23, wherein the specific energy density of the electrode is at least 200 Wh / kg.

26. An electrode as described in claim 23, wherein the specific capacity of the electrode is at least 150 mAh / g.

27. The electrode of claim 23, wherein the specific capacity of the electrode is at least 3.5 mAh / cm 2 .

28. An electrode as described in claim 27, wherein the specific capacity is a discharge capacity.

29. An electrode as described in claim 23, wherein the charge capacity retention rate at a discharge rate of 1.5C is at least 20%.

30. An electrode as described in claim 23, wherein the charge capacity production rate at a charge rate of 2C is at least 10%.

31. An electrode as described in claim 23, having a coulombic efficiency of at least 85%.

32. A lithium ion battery comprising the electrode described in claim 23.

33. A solid-state lithium-ion battery comprising the electrode of claim 23.

34. A dry electrode thin film as described in claim 1, wherein the dry electrode thin film contains 4 wt% or less of the dry binder.

35. A dry electrode thin film as described in claim 1, wherein the porosity of the dry electrode thin film is 36% or less.

36. The dry electrode thin film of claim 1, wherein the dry electrode thin film comprises at least 94 to 98 weight percent dry active material.

37. The dry electrode thin film of claim 4, wherein the density of the dry electrode thin film is at least 1.9 g / cm 3 .

38. A method for producing a dry electrode thin film for an energy storage device, comprising: mixing a dry active material with a dry binder to form an electrode film mixture; forming a self-supporting dry electrode film from the electrode film mixture; the dry electrode film has a thickness of at least 110 μm and a density of at least 1.4 g / cm 3 ; The method is a dry manufacturing process, The method, wherein mixing the dry active material with the dry binder comprises mixing the dry active material with polytetrafluoroethylene (PTFE) and carboxymethyl cellulose (CMC).

39. The method described in claim 38, wherein forming the dry electrode thin film is carried out at a temperature of 20°C to 200°C.

40. The method of claim 38, wherein forming the dry electrode thin film includes compressing the electrode thin film mixture.

41. A method as described in claim 40, wherein compressing the electrode thin film mixture includes rolling.

42. The method of claim 38, wherein the dried active material is further processed to form a processed dried active material.

43. The method of claim 42, wherein the dried active material after the treatment is treated by a mild powder treatment method.

44. The method of claim 42, wherein the dried active material after the treatment is treated by a vigorous powder treatment method.

45. The method of claim 38, wherein the dried binder is further processed to form a processed dried binder.

46. ​​The method of claim 45, wherein the dried binder after said treatment is treated by a mild powder treatment method.

47. The method of claim 45, wherein the dried binder after said treatment is treated by a vigorous powder treatment method.

48. A method according to claim 43 or 46, wherein the gentle powder processing method is selected from tumbling, blending and ultrasonic mixing.

49. A method according to claim 44 or 47, wherein the vigorous powder processing method is selected from milling and grinding.

50. The method of claim 38, wherein combining the dried active material and the dried binder comprises mixing the dried active material with carboxymethyl cellulose to form a first mixture, mixing the first mixture with polyvinylidene fluoride (PVDF) to form a second mixture, and mixing the second mixture with polytetrafluoroethylene (PTFE) to form a third mixture.

51. A dry electrode thin film as described in claim 1, wherein the dry electrode thin film contains 1.5 to 3 weight percent of the dry binder.

52. The dry electrode film of claim 1, wherein the electrode material loading of the dry electrode film is at least 15 mg / cm 2 .

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