Compositions and methods for multilayer electrode films

Abstract

To provide energy storage device electrode films comprising multiple active layers, and methods of forming such multiple active layer energy storage device electrode films.SOLUTION: In a film structure having multiple (from one to n) active layers, each active layer may be a self-supporting active layer comprising a binder and an active material. The binder and / or active material may be the same as or different from any other active layer. The active layers may be stacked to form an electrode film, and the electrode film may be laminated to a current collector to form an electrode.SELECTED DRAWING: Figure 2A

Description

Technical Field

[0001] This application claims the benefit of priority based on U.S. Provisional Application No. 62 / 580,956, filed on November 2, 2017, entitled "Compositions and Methods for Multilayer Electrode Films", the disclosure of which is incorporated herein by reference in its entirety. and the disclosure of said application is incorporated herein by reference in its entirety. The present invention generally relates to energy storage devices, and more particularly to materials and methods for multilayer electrode films.

[0002] The present invention generally relates to energy storage devices, and more particularly to materials and methods for multilayer electrode films. materials and methods.

Background Art

[0003] Electrical energy storage batteries are widely used to power electronics, electromechanical, electrochemical, and other useful devices. Such batteries include various types of capacitors, including primary chemical batteries and secondary ( rechargeable) batteries, fuel cells, and ultracapacitors. Increasing the operating power and energy of energy storage devices such as capacitors and batteries is desirable to improve energy storage performance, improve power performance, and expand practical applications. rechargeable) batteries, fuel cells, and ultracapacitors. Increasing the operating power and energy of energy storage devices such as capacitors and batteries is desirable to improve energy storage performance, improve power performance, and expand practical applications. performance, and expand practical applications. is desirable.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Electrode films that combine complementary attributes can improve the performance of energy storage devices in practical applications. Furthermore, existing manufacturing methods may impose practical limitations on various structural electrode characteristics. Therefore, there is a need for new methods for manufacturing electrode films with improved mechanical properties and performance. Electrode films that combine complementary attributes can improve the performance of energy storage devices in practical applications. Furthermore, existing manufacturing methods may impose practical limitations on various structural electrode characteristics. Therefore, there is a need for new methods for manufacturing electrode films with improved mechanical properties and performance. Therefore, there is a need for new methods for manufacturing electrode films with improved mechanical properties and performance. are desired.

Means for Solving the Problems

[0005] For the purpose of summarizing the present invention achieved beyond the prior art and its advantages, in this specification the specific objectives and advantages of the present invention will be described. Not all of such objectives or advantages will be achieved in a specific embodiment of the present invention. Thus, for example, those skilled in the art do not necessarily have to achieve other objectives or advantages taught or suggested in this specification, and it should be recognized that the present invention can be embodied or implemented by a method of achieving or optimizing one or a group of advantages taught in this specification.

[0006] In a first aspect, a self-supporting electrode film is provided, and the electrode film comprises a plurality of stacked active layers of two or more. In some embodiments, the self-supporting electrode film comprises a first active layer and a second active layer, and the first active layer and the second active layer have different compositions with respect to each other. In further embodiments, the first active layer and the second active layer are each a self-supporting film. In still further embodiments, the first active layer and the aforesaid second active layer comprise different active material compositions and / or binder material compositions. In some embodiments, the electrode film is adhered to a current collector to form an electrode. In some embodiments, no separate adhesive layer is provided between the active layers of the multilayer electrode film and / or between the multilayer electrode film and the current collector.

[0007] In another aspect, a multilayer electrode film is provided. In some embodiments, the multilayer electrode film comprises a first active layer having a first active material and a first binder. In some embodiments the multilayer electrode film comprises a second active layer having a second active material and a second binder. . In some embodiments, the first and second active layers are laminated to form the multilayer electrode film. In some embodiments, the multilayer electrode film is a self-supporting film.

[0008] In another aspect, a multilayer electrode is provided. In some embodiments, the multilayer electrode comprises a current collector having a first surface and a second surface. In some embodiments, the multilayer electrode comprises a first multilayer electrode film laminated to the first surface of the current collector.

[0009] In another aspect, a double-sided multilayer electrode is provided. In some embodiments, the double-sided multilayer electrode comprises a first multilayer electrode film. In some embodiments, the double-sided multilayer electrode comprises a second multilayer electrode film laminated to the second surface of the current collector.

[0010] In another aspect, a method of manufacturing a multilayer electrode is provided. In some embodiments, the method includes providing a first active layer having a first active material and a first binder, wherein the first active layer is a self-supporting film. In some embodiments, the method includes providing a second active layer having a second active material and a second binder, wherein the second active layer is a self-supporting film. In some embodiments, the method includes laminating the first active layer to the second active layer to form a multilayer electrode film, wherein the multilayer electrode film is a self-supporting film.

[0011] In another aspect, a method of manufacturing a multilayer electrode is provided. In some embodiments, the method includes manufacturing a first multilayer electrode film. In some embodiments, the method includes providing a current collector having a first surface and a second surface. In some embodiments, the method includes forming a multilayer electrode by laminating the first multilayer electrode film to the first surface of the current collector. ​ including the following.

[0012] In another aspect, a method of manufacturing a multilayer electrode is provided. In some embodiments, the method includes providing a first active layer having a first active material and a second binder, the first active layer being a self-supporting film. In some embodiments, the method includes providing a second active layer having a second active material and a second binder, the first active layer being a self-supporting film. In some embodiments, the method includes providing a current collector. In some embodiments, the method includes laminating the first active layer onto the second active layer. In some embodiments, the method includes laminating the first active layer onto the current collector.

[0013] All of these embodiments are shown within the scope of the invention disclosed herein. These and other embodiments of the invention will be readily apparent to those skilled in the art from the following detailed description of the preferred embodiments with reference to the accompanying drawings, and the invention is not limited to the specific preferred embodiments disclosed.

Brief Description of the Drawings

[0014]

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Mode for Carrying Out the Invention

[0015] As used herein, the terms "battery" and "capacitor" are given their general and customary meanings to those skilled in the art. The terms "battery" and "capacitor" are not mutually exclusive. A capacitor or a battery is a single electrochemical cell that operates either alone or as a component of a multi-cell system.

[0016] As used herein, the voltage of an energy storage device is the operating voltage of a single battery or capacitor cell. The voltage may exceed the rated voltage, drop below the rated voltage under load, or vary due to manufacturing tolerances.

[0017] As described herein, a "self-supporting" electrode film or active layer is an electrode film or layer that incorporates a binder matrix structure sufficient to support the film or layer and maintain its shape so that the film or layer can stand on its own. When incorporated into an energy storage device, the self-supporting electrode film or active layer incorporates such a binder matrix structure. Generally, and depending on the method of use, such an electrode film or active layer has sufficient strength to be used in the manufacturing process of an energy storage device without using external support elements such as current collectors or other films. For example, a "self-supporting" electrode film has sufficient strength to be wound, handled, and unwound during the electrode manufacturing process without other support elements. strength for it to be wound, handled, and unwound during the electrode manufacturing process without other support elements. ​​​​It can have strength.

[0018] As described herein, a "solvent-free" electrode film is an electrode film that does not contain detectable processing solvents, processing solvent residues, or processing solvent impurities. Processing solvents or conventional solvents include organic solvents. Dry electrode films such as cathode electrode films or anode electrode films can be solvent-free.

[0019] A "wet" electrode or "wet process" electrode is an electrode manufactured by at least one process that includes a slurry of active material, binder, and processing solvent, processing solvent residues, and / or processing solvent impurities. The wet electrode may optionally contain additives.

[0020] Various embodiments incorporating electrode films formed from multiple active layers are provided herein. The electrode films used in energy storage devices may be manufactured from multiple active layers, as provided herein. Further, the energy storage devices may be configured by a method of laminating multiple active layers to form the electrode films, as provided herein.

[0021] The performance of the electrode film may be degraded by the mechanical properties of the film components and their interactions. For example, mechanical limitations are thought to be caused by insufficient adhesion between the active layer and the current collector, and insufficient bonding between the active layer and the binder. Such effects can lead to a decrease in performance in both power supply and energy storage capacity. Although not wishing to be limited by theory, the decrease in performance is caused by, for example, the deactivation of the active material due to a loss of ion conductivity, electrical conductivity, or a combination thereof. ​ is considered to be. For example, if the adhesion between the active layer and the current collector decreases, the cell resistance may increase. A decrease in the bond between active substances may lead to an increase in cell resistance, and in some cases, electrical contact may be lost, and some active substances may be removed from the ion and electrical conduction cycles within the cell. Although not wishing to be limited by theory, it is considered that the volume change of the active substance contributes to such an effect. For example, it may further decrease in an electrode incorporating a specific active material such as a silicon-based material that undergoes significant volume change during the cell cycle. The lithium intercalation / deintercalation process may correspond to such a volume change in some systems. Generally, these mechanical degradation processes may be observed in any electrode, for example, the positive electrode or the negative electrode, or the battery electrode, the capacitor electrode, the hybrid electrode or the energy storage device. In wet film formation processes such as spraying, slot die, extrusion and printing, the substrate may, depending on the situation, limit the possible combinations of the active layer. Furthermore, the wet process may limit the material selection, and as a result, the resulting wet-treated electrode film may also have a non-uniform dispersion of constituent materials such as the active material. The non-uniformity deteriorates as the film density increases, and the ionic conductivity and / or the electrical conductivity may become insufficient. Also, the wet process generally requires an effective and time-consuming drying process, which becomes difficult as the film gets thicker. Therefore, there is also a thickness limit for the electrode film manufactured by the wet process.

[0022]

[0023] ​​​​​​​​​This specification provides a multilayer electrode film incorporating two or more active layers. The active film forms a single electrode film by laminating two or more active layers and is laminated to a current collector to form an electrode and may be a self-supporting film that can be individually handled. Such multilayer electrode films and the associated processing techniques have been found to address some of the above problems. For example, the order of the active layers may be selected such that the film with higher adhesion is adjacent to the current collector. As a further example, the active layer with lower adhesion may be sandwiched between the active layers with higher adhesion, and as a result, for example, the influence of low adhesion to the current collector is reduced. In some embodiments, for example, the performance of the electrode film such as power and / or energy performance can be adjusted by combining a plurality of active layers with selected characteristics. Advantageously, the multilayer film provided in this specification is cost-effective to manufacture. For example, unlike wet processes, each active layer can be designed and manufactured in parallel before assembling the final electrode film from the plurality of active layers. Advantageously, electrode films with various active layers can be easily assembled and tested to find combinations with the desired characteristics. In some cases, by laminating the active layers in a selected combination, it is possible to meet the demand for cost-effective order-made applications.

[0024] The active films combined in the electrode film may be the same or different from each other. Advantageously, an example where a plurality of active layers with the same composition are laminated can enable the manufacture of a thicker electrode film than in the case of using the prior art. Advantageously, defects can be reduced in the manufactured active layer in terms of thickness, and in order to reduce defects such as non-uniformity, for an electrode film​ It is better to form a laminated electrode film than one formed in such a manner. Furthermore, three identical Some examples of the multilayer electrode film with active membranes will result in a more highly dense electrode film as compared with a conventional single-layer electrode having the same material. In some embodiments, the multilayer electrode has an improved pore structure on the surface of the electrode film as compared with a conventional electrode film having a similar composition and density. In some examples, laminating active layers of the same composition onto a single electrode film is more cost-effective as compared with forming the electrode film as a single layer. A thick electrode film is used, for example, in medical devices. Therefore, the multilayer electrode film provided herein is suitable for use in medical devices.

[0025] Furthermore, the multilayer electrode film provided herein has been found to be superior to typical electrode films, for example, those having only a single layer or having a generally homogeneous composition throughout. For example, active layers of different compositions are expected to have different electrical conductivity and ionic conductivity. Therefore, the overall performance of the electrode film is improved by selecting a specific active layer depending on its proximity to the current collector. Furthermore, active layers of different compositions are expected to have different energy and power performance characteristics. By combining high-output and high-energy active layers in a single electrode film, it is expected to provide each type of active layer.

[0026] A multilayer electrode film incorporating two or more active layers is generally manufactured by laminating at least one self-supporting dry type electrode active layer onto another active layer. In some embodiments, the active layers provided herein are not structurally and / or functionally distinguishable from the electrode film. Thus, each active layer may comprise an electrode active material and a binder. In some embodiments each active layer is a self-supporting dry electrode active layer. The self-supporting active layer is manufactured using dry electrode manufacturing techniques. Generally, the active electrode material and the binder are combined, pulverized mixed, or otherwise processed to form an active layer mixture, which is calendared or pressed to form a self-supporting active layer. In some embodiments, the binder is a fibrillatable polymer binder. In further embodiments, the binder comprises PTF E or has PTFE as a main component. In further embodiments, no solvent is used at any stage of the electrode film manufacturing process.

[0027] Dry electrode manufacturing is effective for manufacturing multilayer electrode films. Dry electrode manufacturing enables self supporting, for example, forming a self-standing active layer. Generally, these active layers can be combined as needed to achieve a series of desired operating characteristics . Thus, as a method of manufacturing individual active layers, self-supporting active layers can be laminated without limitation .

[0028] When the energy storage device comprises a current collector having electrode films on both sides, i.e., a double-sided electrode the two electrode films may have the same or different compositions from each other.

[0029] Generally, there is no limitation on the active layers combinable with the electrode film. Thus, each active layer can comprise, for example the same or different active materials, the same or different binders, the same or different thicknesses, the same or different dimensions, as another active layer within the same electrode film. In general, the number of active layers that can be combined in a single electrode film depends on the compressibility, ionic and and / or the properties of the energy storage device, without being limited to fundamental physical properties such as electrical conductivity. Limited by the number of active layers in the electrode film.

[0030] In some embodiments, each active layer of the multilayer electrode film provided herein comprises at least In a further embodiment, the present invention comprises an active material and at least one binder. Each active layer of the multilayer electrode film provided herein is a self-supporting layer. The material can be any active material known in the art. The active materials include, for example, graphite materials, graphite, graphene-containing materials, activated carbon, hard carbon, The material may include carbon materials such as polycarbonate, soft carbon, and / or carbon nanotubes. The at least one active material may be, for example, a metal oxide, a metal sulfide, or lithium metal. The battery may include an active material such as a lithium metal oxide. For example, the active material may be a lithium metal oxide. The zeolite may include, for example, a layered transition metal oxide, a spinel manganese oxide, or an olivine. Lithium metal oxides include lithium nickel manganese cobalt oxide (NMC), lithium Manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium iron Lithium phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate and / or or lithium nickel cobalt aluminum oxide (NCA). The binder may be carbon, graphite, conductive carbon or a combination thereof. , PTFE, polyolefins, poly(ethylene oxide) (PEO), styrene-butadiene Polyvinylidene chloride (PVDC), Polyvinyl chloride (PVC ) Poly(phenylene oxide) (PPO), polyethylene block-poly(ethylene glycol), polydimethylsiloxane (PDMS), polydimethylsiloxane-core alkylmethylsiloxane, their copolymers and / or their mixtures may also be used. In some embodiments, one or more polyolefins may include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), their copolymers and / or their mixtures. The binder may include, for example, cellulose such as carboxymethyl cellulose (CMC). In certain embodiments, the binder includes PTFE or is mainly composed of PTFE. In some embodiments, the binder includes a fibrillatable polymer.

[0031] A multi-layer electrode film incorporating two or more active layers described herein can advantageously exhibit improved performance compared to those having only a single active layer. Performance includes, for example, Coulomb efficiency, capacity, or conductivity.

[0032] The materials and methods provided herein can be implemented in various energy storage devices. As provided herein, the energy storage device can be a capacitor, a lithium-ion capacitor (LIC), an ultracapacitor, a battery, or a hybrid energy storage device combining two or more of the foregoing. In some embodiments, the device is a battery. The energy storage device can be characterized by its operating voltage. In some embodiments, the energy storage device described herein , can have an operating voltage from about 2.2V to about 3.8V. In further embodiments, the operating voltage is from about 2.7V to about 3V, from about 3.6V to about 3.7V, from about 2.7V to about 4. 2V, from about 2.7V to about 4.3V, from about 2.7V to about 4.4V or any value optionally selected therebetween. In some embodiments, the operating voltage is about 2.7V, about 3V, about 3.6V, about 3.7V, about 4.2V, about 4.3V, about 4.4V or about 4. 5V, or any value within any range therebetween.

[0033] The energy storage device provided herein comprises one or more electrodes. The electrodes generally comprise an electrode film and a current collector. The electrode film can be composed of stacked active layers and each active layer can be formed from an active layer mixture of one or more binders and one or more active electrode materials. The electrode binders and electrodes provided herein have been found to be usable with any of a number of energy storage devices and systems, such as one or more batteries, capacitors, capacitor-battery hybrids, fuel cells or other energy storage systems or devices, and combinations thereof. In some embodiments, the active layer mixture and electrodes manufactured from the active layer mixture described herein may be components of a lithium ion capacitor, a lithium ion battery, an ultracapacitor, or a hybrid energy storage device combining two or more of the foregoing aspects.

[0034] The energy storage device provided herein can be, for example, planar, wound in a helical shape ​​, or any suitable shape such as a button shape or a bag shape. The energy storage device provided by the present invention The energy storage device may be, for example, a component of a power generation system, an uninterruptible power supply system (UPS), a solar power generation system, such as an energy recovery system for use in industrial machinery and / or transportation system. The energy storage device provided herein The device may be classified as, for example, a capacitor, a battery, a capacitor-battery hybrid, or a fuel cell. The energy storage device provided herein can be used to supply power to various electronic devices and / or vehicles, including hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHE

[0035] The energy storage device described herein has the advantageous feature that the increase in equivalent series resistance is reduced until the end of the life of the device, thereby providing a device with an increasing power density until the end of the life of the device. The energy storage device described herein is advantageously characterized in that the increase in equivalent series resistance is reduced over the life of the device, and a device with an increasing power density over the life of the device can be provided. In some embodiments, the energy storage device described herein is characterized in that the loss of capacity is reduced until the end of the life of the device. Further improvements that can be realized in various embodiments include improvements in cycle performance, including improved storage stability during cycling and reduced capacity degradation. is characterized in that the loss of capacity is reduced until the end of the life of the device. The energy storage device described herein is advantageously characterized in that the increase in equivalent series resistance is reduced over the life of the device, and a device with an increasing power density over the life of the device can be provided. In some embodiments, the energy storage device described herein is advantageously characterized in that the rise in equivalent series resistance is reduced over the life of the device, and a device with an increasing power density over the life of the device can be provided. In some embodiments, the energy storage device described herein is characterized in that the loss of capacity is reduced until the end of the life of the device. Further improvements that can be realized in various embodiments include improvements in cycle performance, including improved storage stability during cycling and reduced capacity degradation. is characterized in that the loss of capacity is reduced until the end of the life of the device. Further improvements that can be realized in various embodiments include improvements in cycle performance, including improved storage stability during cycling and reduced capacity degradation. Included are improvements in cycle performance, including improved storage stability during cycling and reduced capacity degradation, which are further improvements that can be realized in various embodiments. Included are improvements in cycle performance, including improved storage stability during cycling and reduced capacity degradation, which are further improvements that can be realized in various embodiments.

[0036] FIG. 1 shows a schematic side cross-sectional view of an example of an energy storage device 100. The energy storage device 1 00 may be classified, for example, as a capacitor, a battery, a capacitor-battery hybrid, or a fuel cell.

[0037] The device can have a first electrode 102, a second electrode 104, and a separator 106 disposed between the first electrode 102 and the second electrode 104. The first electrode 102 and the second electrode 104 may be disposed adjacent to opposite surfaces of the separator 106. The energy storage device 100 may include an electrolyte 118 to facilitate ion transfer between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 118 may be in contact with the first electrode 10 2, the second electrode 104, and the separator 106. The electrolyte 118, the first electrode 102, the second electrode 104, and the separator 106 may be placed within a housing 120 of the energy storage device. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. ー storage device 100 may include an electrolyte 118 to facilitate ion transfer between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 118 may be in contact with the first electrode 10 2, the second electrode 104, and the separator 106. The electrolyte 118, the first electrode 102, the second electrode 104, and the separator 106 may be placed within a housing 120 of the energy storage device. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. 2, the second electrode 104, and the separator 106 may be in contact. The electrolyte 118, the first electrode 102, the second electrode 104, and the separator 106 may be placed within a housing 120 of the energy storage device. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. 1 electrode 102, the second electrode 104, and the separator 106 may be placed within a housing 120 of the energy storage device. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. The first electrode 102, the second electrode 104, and the separator 106 may be placed within a housing 120 of the energy storage device. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. One or more of the first electrode 102, the second electrode 104, and the separator 106, or components thereof, may include a porous material. The pores within the porous material can provide suppression and / or an increased surface area for reactivity with the electrolyte 118 within the housing 120. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment. The housing 120 of the energy storage device can be sealed around the first electrode 102, the second electrode 104, and the separator 106 and may be physically sealed from the surrounding environment.

[0038] In some embodiments, the first electrode 102 can be an anode (negative electrode), and the second electrode 104 can be a cathode (positive electrode). The separator 106 can be configured to electrically insulate two adjacent electrodes, such as the first electrode 102 and the second electrode 104, on opposite sides of the separator 106 from each other, while simultaneously allowing ion transfer between the two adjacent electrodes. The separator 106 can include a suitable porous electrical insulating material. The second electrode 104 can be a cathode (positive electrode). The separator 106 can be configured to electrically insulate two adjacent electrodes, such as the first electrode 102 and the second electrode 104, on opposite sides of the separator 106 from each other, while simultaneously allowing ion transfer between the two adjacent electrodes. The separator 106 can include a suitable porous electrical insulating material. The second electrode 104 can be a cathode (positive electrode). The separator 106 can be configured to electrically insulate two adjacent electrodes, such as the first electrode 102 and the second electrode 104, on opposite sides of the separator 106 from each other, while simultaneously allowing ion transfer between the two adjacent electrodes. The separator 106 can include a suitable porous electrical insulating material. The second electrode 104 can be a cathode (positive electrode). The separator 106 can be configured to electrically insulate two adjacent electrodes, such as the first electrode 102 and the second electrode 104, on opposite sides of the separator 106 from each other, while simultaneously allowing ion transfer between the two adjacent electrodes. The separator 106 can include a suitable porous electrical insulating material. The second electrode 104 can be a cathode (positive electrode). The separator 106 can be configured to electrically insulate two adjacent electrodes, such as the first electrode 102 and the second electrode 104, on opposite sides of the separator 106 from each other, while simultaneously allowing ion transfer between the two adjacent electrodes. The separator 106 can include a suitable porous electrical insulating material. In some embodiments, separator 106 can include a polymeric material. For example , separator 106 can include a cellulose-based material (e.g., paper), a polyethylene (PE) material, a polypropylene (PP) material, and / or a polyethylene and polypropylene material .

[0039] Generally, first electrode 102 and second electrode 104 each include a current collector and an electrode film . Electrodes 102 and 104 each include electrode films 112 and 114. Electrode films 11 2 and 114 can have any suitable shape, size, and thickness. For example , the electrode film can have a thickness ranging from about 30 microns (μm) to about 250 microns, such as about 50 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, or any value in between . The electrode film generally includes one or more active materials. In some embodiments, electrode films 112 and 114 can include an active layer including a binder material and at least one active material. In some embodiments , at least one active material can include a carbon-based material or a battery material. In some embodiments, the battery active material can include a lithium metal oxide and / or lithium sulfide . In some embodiments, the battery active material can include lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium iron phosphate (LFP), lithium cobalt oxide ( LCO), lithium titanate, and / or lithium nickel cobalt cobalt oxide (NCA). Electrode films 112 and / or 114 are provided herein The electrode may be a multi-layer electrode film as described above, and may have beneficial thicknesses, such as those provided herein. The first electrode 102 and / or the second electrode 104 may have any of the beneficial properties provided herein. The electrodes may be double-sided electrodes as illustrated, with each electrode including an electrode film on either side of a current collector.

[0040] Carbon-based materials include graphite carbon, porous carbon, activated carbon, carbon black, and conductive carbon. , graphene-containing carbon, graphite, and combinations thereof. Activated carbon can be obtained from a steam process or an acid / etching process. In some forms, the graphitic carbon may be a surface treated carbon.

[0041] In some embodiments, the porous carbon may include activated carbon. In some embodiments, the porous carbon may comprise hierarchical carbon. Porous carbon may be structured carbon nanotubes, structured carbon nanowires and / or may comprise structured carbon nanosheets. In some embodiments, the porous carbon may comprise graphene sheets. In some embodiments, the porous carbon may be surface-treated It may be carbon that has been bonded to the surface.

[0042] The first electrode film 112 and / or the second electrode film 114 may be any one or more of the electrode films provided herein. The binder may also include an active layer that includes a plurality of binders. In some embodiments, the binder may include one or more polymers. The binder component may contain the above-mentioned fibrillizable binder component. The fibrils may be polymerized to provide a large number of fibrils, which may be desirably coupled to one or more other components of the membrane. Provide mechanical support. The fibrils form a matrix, lattice, or web and are thought to be able to provide a mechanical structure to the electrode film. In some embodiments, the binder component may include one or more of various suitable fibrillatable polymer materials.

[0043] Generally, the active layers and / or electrode films described herein can be manufactured using modified dry manufacturing processes. For example, some of the steps provided herein may be as described in U.S. Patent Publication No. 2005 / 0266298 and U.S. Patent Publication No. 2006 / 0 146479. These, and other external documents described herein are hereby incorporated by reference in their entirety. As used herein, the dry manufacturing process can refer to a process in which no solvent or substantially no solvent is used in the formation of the electrode film. For example, the components of the active layer or electrode film, including carbon materials and binders, may include dry particles. Dry particles for forming the active layer or electrode film can be combined to provide a dry particle active layer mixture. In some embodiments, the active layer or electrode film may be formed from the dry particle active layer mixture such that the weight percentages of the components of the active layer or electrode film and the weight percentages of the components of the dry particle active layer mixture are substantially the same. In some embodiments, the active layer or electrode film formed from the dry particle active layer mixture using a dry manufacturing process does not contain, or substantially does not contain, processing additives such as solvents and solvent residues that result therefrom. In some embodiments, the resulting active layer or electrode film is formed from a dry sub-mixture using a dry process It is a self-supporting film formed by use. In some embodiments, the resulting active layer or the electrode film is a self-standing film formed from a dry particle mixture using a dry process. The active layer or the process for forming the electrode film may include fibrillating a fibrillatable binder component such that the film includes a fibrillating binder. In further embodiments, the self-standing active layer or electrode film may be formed in the absence of a current collector. Further, in another embodiment, the active layer or electrode film may include a fibrillated polymer matrix such that the film is self-supporting. As shown in FIG. 1, the first electrode 102 and the second electrode 104 each include a first current collector 108 in contact with the first electrode film 112 and a second current collector 110 in contact with the second electrode film 114. The first current collector 108 and the second current collector 110 can facilitate the electrical connection between the respective electrode films and an external electrical circuit (not shown). The first current collector 108 and / or

[0044] the second current collector 110 includes one or more conductive materials and can have any suitable shape and size selected to facilitate the movement of charge between the corresponding electrode and the external electrical circuit. For example, the current collector can include a metal material such as a material including a noble metal such as aluminum, nickel, copper, rhenium, niobium, tantalum, as well as silver, gold, platinum, palladium, rhodium, osmium, iridium, and alloys and combinations thereof. For example, the first current collector 108 and / or the second current collector 110 can include aluminum foil. The aluminum foil can have a rectangular or substantially rectangular shape of a size that provides for the movement of charge between the corresponding electrode and the external electrical circuit. The first current collector 108 and / or the second current collector 110 includes one or more conductive materials and can have any suitable shape and size selected to facilitate the movement of charge between the corresponding electrode and the external electrical circuit. The first current collector 108 and / or the second current collector 110 can have any suitable shape and size selected to facilitate the movement of charge between the corresponding electrode and the external electrical circuit. For example, the current collector can include a metal material such as a material including a noble metal such as aluminum, nickel, copper, rhenium, niobium, tantalum, as well as silver, gold, platinum, palladium, rhodium, osmium, iridium, and alloys and combinations thereof. For example, the first current collector 108 and / or the second current collector 110 can include aluminum foil. The aluminum foil can have a rectangular or substantially rectangular shape of a size that provides for the movement of charge between the corresponding electrode and the external electrical circuit. For example, the first current collector 108 and / or the second current collector 110 can include aluminum foil. The aluminum foil can have a rectangular or substantially rectangular shape of a size that provides for the movement of charge between the corresponding electrode and the external electrical circuit. The aluminum foil can have a rectangular or substantially rectangular shape of a size that provides for the movement of charge between the corresponding electrode and the external electrical circuit. The aluminum foil can have a rectangular or substantially rectangular shape of a size that provides for the movement of charge between the corresponding electrode and the external electrical circuit.

[0045] In some embodiments, the cathode electrode film of a lithium-ion battery or a hybrid energy storage device contains at least one active material in an amount of from about 70 wt% to about 92 wt%, or from about 70 wt% to about 88 wt%, and may contain from about 70 wt% to about 95 wt%. In some embodiments, the cathode electrode film may contain a porous carbon material in an amount of up to about 10 wt%, or from about 1 wt% to about 5 wt%. In some embodiments, the cathode electrode film contains a conductive additive in an amount of up to about 5 wt% containing from about 1 wt% to about 3 wt%. In some embodiments, the cathode electrode film contains a binder in an amount of, for example, 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% and up to about 20 wt%. In some embodiments, the cathode electrode film contains a binder in an amount of from about 1.5 wt% to about 3 wt%.

[0046] In some embodiments, the anode electrode film can contain at least one active material, a binder, and any conductive additive. In some embodiments, the conductive additive can include a conductive carbon additive such as carbon black. In some embodiments at least one active material of the anode includes synthetic graphite, natural graphite, hard carbon, soft carbon, graphene, mesoporous carbon, silicon, silicon oxide, tin, tin oxide, germanium, lithium titanate, a mixture, or a composite of said materials. In some embodiments, the anode electrode film contains at least one active material in an amount of from about 80 wt% to about 92 wt%, or from about 80 wt% to about 90 wt% ​can contain from about 80% to about 94% by weight, inclusive. In some embodiments, A node electrode film contains a conductive additive in an amount of up to about 5% by weight, from about 1% to about 3% by weight. In some embodiments, the anode electrode film contains a binder in an amount of from about 1.5% to 10% by weight, from about 1.5% to 5% by weight, or from about 1.5% to 3% by weight, up to about 20 % by weight. In some embodiments, the anode electrode film contains from about 1.5% to about 3 % binder. In some embodiments, the anode electrode film may not contain a conductive additive.

[0047] Some embodiments include electrode films such as anodes and / or cathodes having one or more active layers containing a polymeric binder material. In some embodiments, the binder can include PTFE and any one or more additional binder components. In some embodiments, the binder can include one or more polyolefins and / or their co polymers, as well as PTFE. In some embodiments, the binder can include PTFE and one or more celluloses, polyolefins, polyethers, polyether precursors, polysiloxanes, their copolymers, and / or mixtures thereof. In some embodiments, the binder can include branched polyethers, polyvinyl ethers, their copolymers, and / or homologues thereof. The binder can include polysiloxanes and copolymers of polysiloxanes, and / or copolymers of polyether precursors. For example, the binder can be poly(ethylene oxide) (PEO), poly(phenylene oxide) (PPO), polyethylene block po lymers, and the like. The binder can include polysiloxanes and copolymers of polysiloxanes, and / or copolymers of polyether precursors. For example, the binder can be poly(ethylene oxide) (PEO), poly(phenylene oxide) (PPO), polyethylene block po lymers, and the like. Ethylene glycol, polydimethylsiloxane (PDMS), polydimethylsiloxane-core alkylmethylsiloxane, their copolymers, and / or their mixtures can be included. In some embodiments, one or more polyolefins can include polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), their copolymers, and / or their mixtures. The binder can include cellulose, for example, carboxymethyl cellulose (CMC). The mixture of polymers can include an interpenetrating network of the aforementioned polymers or copolymers. The binder can contain various suitable ratios of polymer components. For example, PTFE can contain the binder from about 20 wt% to about 80 wt%, from about 30 wt% to about 70 wt%, or from about 30 wt% to about 50 wt% up to about 98 wt%, for example, from about 20 wt% to about 95 wt%, from about 20 wt% to about 90 wt%. In some embodiments, at least one active material includes a treated carbon material, and the treated carbon material includes a reduction in the number of hydrogen-containing functional groups, nitrogen-containing functional groups, and / or oxygen-containing functional groups as described in U.S. Patent Publication No. 2014 / 0098464. For example, the treated carbon particles can include a reduction in many of the one or more functional groups on one or more surfaces of the treated carbon, for example, one or more functional groups can be reduced by about 10% to about 60% including from about 20% to about 50% compared to the untreated carbon surface. The treated carbon contains a reduced number of hydrogen-containing functional groups, nitrogen-containing functional groups, and / or oxygen-containing functional groups.

[0048]

[0049] ​​​​​​​​​​​​​​​can be achieved. The treated carbon can include a reduced number of hydrogen-containing functional groups, nitrogen-containing functional groups, and / or oxygen-containing functional groups. In some embodiments, the treated carbon material contains less than about 1% of functional groups containing hydrogen, including less than about 0.5%. In some embodiments the treated carbon material contains less than about 0.5% of functional groups containing nitrogen, including less than about 0.1% In some embodiments, the treated carbon material contains less than about 5% of functional groups containing oxygen, including less than about 3% In a further embodiment, the treated carbon material contains about 30% fewer hydrogen-containing functional groups than the untreated carbon material.

[0050] The multi-layer electrodes described herein can be used separately or in combination in an energy storage device to enable operation under selected conditions.

[0051] Lithium-ion energy storage device In some embodiments, the energy storage device 100 can be a lithium-ion energy storage device such as a lithium-ion capacitor or a lithium-ion battery. In some embodiments, the electrode film of the electrode of the lithium-ion energy storage device can include one or more carbon materials and the fibrillated binder matrix provided herein.

[0052] In some embodiments, the electrode film of the anode of a lithium-ion battery or a hybrid energy storage device can include an anode active material. The anode active material can be, for example, an insertion material (such as carbon, graphite, and / or graphene), an alloy / non-alloy material (such as silicon, silicon oxide, tin, and / or tin oxide), a metal alloy, or Compounds (such as Si-Al and / or Si-Sn), and / or conversion materials (such as manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide, etc.) can be included. The anode active material can be used alone or mixed to form a multiphase material (such as Si-C, Sn-C, SiO x-C, SnOx-C, Si-Sn, Si-SiOx, Sn-SnOx, Si-SiOx -C, Sn-SnOx-C, Si-Sn-C, SiOx-SnOx-C, Si-SiOx -Sn, or Sn-SiOx-SnOx, etc.).

[0053] In some embodiments, the electrode film of the cathode of a lithium-ion battery or a hybrid energy storage device can include a cathode active material, a binder, optionally a porous carbon material, and optionally a conductive additive. In some embodiments, the conductive additive can include a conductive carbon additive such as carbon black. In some embodiments, the porous carbon material can include activated carbon. In some embodiments, the cathode active material can include a lithium metal oxide and / or lithium sulfide. In some embodiments, the cathode active material can include lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium nickel manganese oxide (LNMO), lithium iron phosphate (LFP), lithium cobalt oxide (LCO), lithium titanate, and / or lithium nickel cobalt aluminum oxide (NCA). The cathode active material can include a material containing sulfur such as sulfur or lithium sulfide (Li2S), or other sulfur-based materials, or mixtures thereof. In some embodiments, ​In an embodiment, the cathode film contains sulfur or a sulfur active material at a concentration of at least 50% by weight. It contains a material containing sulfur or a sulfur active material. In some embodiments, the cathode film containing a material containing sulfur or a sulfur active material has an areal capacity of at least 10 mAh / cm 2 . In some embodiments , the cathode film containing a material containing sulfur or a sulfur active material has an electrode film density of 1 g / cm 3 . In some embodiments, the cathode film containing a material containing sulfur or a sulfur active material further contains a binder. In some embodiments, the binder of the cathode film containing a material containing sulfur or a sulfur active material is selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), poly(ethylene oxide) (PEO), polyethylene (PE ), polyacrylic acid (PAA), gelatin, other thermoplastic resins, or any combination thereof .

[0054] In some embodiments, the electrode film of the electrode of the lithium-ion energy storage device contains an active material configured to reversibly insert lithium ions. In some embodiments , the lithium insertion active material is graphite, hard carbon and / or soft carbon . For example, the electrode film of the electrode can contain a binder material, one or more graphites, graphite -containing carbon, hard carbon and soft carbon, as well as an electric conduction promoting material . In some embodiments, the electrode is pre-doped with lithium ions .

[0055] In a further embodiment, the energy storage device 100 is charged with a suitable lithium-containing electrolyte . For example, the device 100 can contain a lithium salt and a solvent such as a non-aqueous or organic solvent It can include. Generally, the lithium salt includes an anion that is redox stable. In some embodiments, the anion may be monovalent. In some embodiments, the lith ium salt is hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium bis(trifluorometh anesulfonyl)imide (LiN(SO2CF3)2), lithium trifluoromethanesulf honate (LiSO3CF3), lithium bis(pentafluoroethanesulfonyl)imi de (C4F 10 LiNO4S2)(LiBETI) lithium bis(fluorosulfonyl) imide (F2LiNO4S2)(LiFSI), and combinations thereof. In some embodiments, the electrolyte is a quaternary ammonium cation as well as an anion selected from the group consisting of hexafluorophosphate, tetrafluoroborate and iodide. In some embodiments, the salt concentration is from about 0.1 m ol / L (M) to about 5 M, from about 0.2 M to about 3 M, or from about 0.3 M to about 2 M. In further embodiments, the salt concentration of the electrolyte may be from about 0.7 M to about 1 M. In certain embodiments, the salt concentration of the electrolyte is 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, about 1.3 M, about 1.4 M, about 1.5 M, or any value in the range therebetween. In some embodiments, the energy storage device provided herein includes a liquid solvent. In some embodiments, the energy storage device provided herein includes a liquid solvent. It may be.

[0056] In some embodiments, the energy storage device provided herein includes a liquid solvent. It is possible. The solvent provided in this specification does not need to dissolve all components of the electrolyte, nor does it need to completely dissolve any component. In a further embodiment, 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 may include carbonates. In a further embodiment, the carbonate may be, for example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), vinylethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof, or non-cyclic carbonates such as, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and combinations thereof. In a particular embodiment, the electrolyte may include LiPF6 and one or more carbonates. Nor does it need to completely dissolve any component. In a further embodiment, 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 may include carbonates. In a further embodiment, the carbonate may be, for example, ethylene carbonate (EC), propylene carbonate (PC), vinylethylene carbonate (VEC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof, or non-cyclic carbonates such as, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and combinations thereof. In a particular embodiment, the electrolyte may include LiPF6 and one or more carbonates.

[0057] In some embodiments, the energy storage device 100 is a lithium-ion battery or a hybrid energy storage device including a cathode including at least one cathode active material. In some embodiments, the lithium-ion battery is configured to operate at about 2 to 4.5V, about 3 to 4V, or about 3.6 to 3.7V.

[0058] In some embodiments, the energy storage device is as described herein and operates from -30 °C to about 70°C, for example, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30 ​​Operation at values of 0 °C, 40 °C, 50 °C, 60 °C, 70 °C, or any range therebetween A battery including one or more multi-layer electrodes configured for it. In some embodiments

[0059] Ultra-capacitor In some embodiments, the energy storage device 100 may be an ultra-capacitor configured to operate at about 2.7V, 2.8V, 2 .9V, 3V, or 3V or more, or any range of values therebetween .

[0060] The energy storage device 100 can be charged with any suitable electrolyte. For example the device 100 can include a solvent and salts including cations and anions. The cation may be a quaternary ammonium cation. In some embodiments, the quaternary ammonium cation can be selected from tetraalkylammonium. In some embodiments, the tetraalkylammonium cation can be, for example, a cyclic ammonium such as spiro-(1,1’) -bipyrrolidinium, and, for example, a non-cyclic ammonium such as triethylmethylammonium , triethylbenzylammonium, and tetraethylammonium . The quaternary ammonium salt can include an anion selected from the group consisting of hexafluorophosphate , tetrafluoroborate, and iodide. The cation of the electrolyte salt can include, for example, a symmetric cation such as cationic spiro-(1,1 ’)-bipyrrolidinium. In some embodiments the cation of the electrolyte salt can include, for example, an asymmetric cation such as triethylmethylammonium . It can contain thion. In some embodiments, the salt can contain, for example, spiro compounds such as symmetric or asymmetric spiro compounds. For example, the spiro compound may be an N-spiro bicyclic compound containing one or more 4, 5, 6 or 7-membered rings. The symmetric spiro cation may be spiro-(1,1’)-bipyrrolidinium tetrafluoroborate . In some embodiments, the salt can contain an asymmetric spiro compound with rings of unequal size or different substitutions on rings of equal size. In some embodiments . In some embodiments, the salt concentration can be from about 0.1 mol / L (M) to about 5 M, from about 0.2 M to about 3 M, or from about 0.3 M to about 2 M. In further embodiments, the salt concentration of the electrolyte can be from about 0 .7 M to about 1 M. In certain embodiments, the salt concentration of the electrolyte is 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 value within the range between them may be.

[0061] In some embodiments, the energy storage device provided herein can contain a liquid solvent. The solvent provided herein does not need to dissolve all components of the electrolyte, nor does it need to completely dissolve any component. In further embodiments, the solvent may be an organic solvent. In some embodiments, the solvent can contain one or more functional groups selected from nitriles, carbonates, ethers and / or esters. In some embodiments, the solvent can contain a nitrile such as acetonitrile, for example. In some embodiments, the solvent can contain a carbonate. In further embodiments . In some embodiments, the solvent can contain a nitrile such as, for example, acetonitrile. In some embodiments, the solvent can contain a carbonate. In an embodiment, the carbonate may be, for example, cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC), vinylene carbonate (VC), and combinations thereof, or non-cyclic carbonates such as, for example, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and combinations thereof. In a particular embodiment, the electrolyte can include a quaternary ammonium salt and acetonitrile. In a further embodiment, the ultracapacitor includes an electrolyte containing a quaternary ammonium salt at a concentration of less than 1 molar (M), as described in U.S. Patent Publication No. 2014 / 0104752, the entire contents of which are incorporated herein by reference. In yet another embodiment, the ultracapacitor includes a protective coating disposed on the inner surface of the housing, as described in U.S. Patent Publication No. 2014 / 0098463, the entire contents of which are incorporated herein by reference. In yet another embodiment, the ultracapacitor includes a positive or negative electrode including a carbon-based layer having a porosity selected, for example, to be mesoporous or microporous, as described in U.S. Patent Publication No. 2014 / 0098465, the entire contents of which are incorporated herein by reference. In some embodiments, the ultracapacitor includes an amount of electrolyte selected to correspond to the saturation amount of the components of the ultracapacitor, as described in U.S. Patent Publication No. 2014 / 0368973, the entire contents of which are incorporated herein by reference.

[0062] In a further embodiment, the ultracapacitor As described in U.S. Patent Publication No. 2014 / 0104752, it contains an electrolyte with a quaternary ammonium salt concentration of less than 1 molar (M), and the entire content is incorporated herein by reference. In yet another embodiment, the ultracapacitor As described in U.S. Patent Publication No. 2014 / 0098463, it includes a protective coating disposed on the inner surface of the housing, and the entire content Is incorporated herein by reference. In yet another embodiment, the ultracapacitor As described in U.S. Patent Publication No. 2014 / 0098465, for example, it includes a positive or negative electrode containing a carbon-based layer having a selected porosity such as mesoporous Or microporous, and the entire content is incorporated herein by reference. In some embodiments, the ultracapacitor As described in U.S. Patent Publication No. 2014 / 0368973, it contains an amount of electrolyte selected to correspond to the saturation amount of the components of the ultracapacitor, and the entire content Is incorporated herein by reference.

[0063] In some embodiments, the energy storage device is configured to operate at 3 volts or more and is an ultracapacitor including one or more multilayer electrodes described herein. In further embodiments, the ultracapacitor is configured to operate at 2.7 volts or more. In some embodiments, the ultracapacitor is configured to operate under selected conditions of voltage and temperature. For example, the ultracapacitor may be configured to operate at 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C , or higher temperatures, or any value in between. The ultracapacitor is configured for continuous operation at 2.7V (60 to 85°C), 2.8V (60 to 85°C ), 2.9V (60 to 85°C), or 3V (60 to 85°C), or any selected temperature value in between. In some embodiments, the conditions of voltage and temperature are about 2.7V and about 85°C, about 2.8V and about 80°C, about 2.9V and about 75 °C, about 3V and about 70°C, or about 3.1V and about 65°C. In some embodiments, the ultracapacitor is configured for an operating voltage of about 2.7 to 3 volts at a temperature of at least about 65°C for at least about 500k cycles. In some embodiments the ultracapacitor does not exhibit significant degradation of the electrodes after about 1500 hours of operation and / or at least 500k cycles, and significance is determined by the intervention of a harmful effect that requires operation of the device below its rated conditions.

[0064] As described herein, the ultracapacitor has an initial static A capacitance exceeding about 80% of the capacitance, and / or less than 200% of the initial equivalent series resistance The capacitance is operated at a voltage of about 2.7 to 3 volts for about 1500 hours, and / or can be maintained for at least 500k cycles and at a temperature of at least about 65°C To achieve this, it may include one or more multilayer electrodes. In other embodiments, the ultracapacitor maintains at least 75%, 85%, 90%, 95% or 99% of the initial capacitance at about 65 °C or higher for at least 1500 hours and / or during at least 500k cycles of operation when configured to do so.

[0065] Multilayer electrode film Compositions and methods are provided herein for electrode films composed of multiple active layers are provided.

[0066] Various embodiments of the multilayer electrode films provided herein are presented in FIGS. 2A through 2B and FIGS. 3A through 3B. FIGS. 2A and 2B show a multilayer (layer 1 through layer n ) film structure incorporated into an electrode. FIG. 2A shows a single-sided electrode including at least three layers of active layers in the electrode film, and FIG 2B shows a double-sided electrode including at least three layers of active layers in each electrode film. In FIG. 2B, the active layers on both sides of the current collector have the same composition and order. FIG. 2B shows a symmetric double-sided electrode including a multilayer electrode film . FIG. 3A and 3B show a multilayer (layer 1 through layer n) film structure incorporated into an electrode. FIG. 3A

[0067] shows a double-sided electrode including n layers, at least three layers of active layers in each electrode film. In FIG. 3A, the order of the active layers of the multilayer films on both sides of the current collector is different from each other. For example, the active layers directly adjacent to the corresponding sides of the current collector of each corresponding multilayer film can have different compositions relative to each other and the active layers directly adjacent to the corresponding sides of the current collector of each corresponding multilayer film can have different compositions relative to each other This is shown. FIG. 3B shows a double-sided electrode including an n-1 layer, at least two active layers in the electrode film on one side of the current collector, and an n layer, at least three active layers in the electrode film on the opposite side. Therefore, FIG. 3B shows a double-sided multilayer electrode having a first multilayer electrode film including a different number of layers from the second multilayer electrode film. FIGS. 3A and 3B show asymmetric double-sided electrodes including multilayer electrode films. It can be understood from the drawings that FIGS. 2B, 3 A and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It will be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It can be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It can be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It can be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It can be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It can be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's positive electrode and the other side is the negative electrode of the other cell. It can be understood from the drawings that FIGS. 2B, 3A, and 3B can be modified to include different numbers of layers. For example, a multilayer electrode film shown as having three or more layers may have two or more layers. Some embodiments may have only a single (non-multilayer) active film on one side of the current collector and a multilayer film on the opposite side. Furthermore, any of the shown layers may have the same or different compositions relative to each other. For example, as shown in FIG. 2B, "layer 1" is adjacent to the current collector and is represented as showing different layers on each side of the current collector, and the chemical composition of each layer 1 may be the same as or different from the others. Also, as in the embodiments shown from FIG. 2B to 3B, a bipolar multilayer configuration for use in a bipolar energy storage device configuration is also within the scope of the present invention. For example, layers 1, 2, and n shown above the current collector in FIG. 2B can be made positive, while layers 1, 2, and 2 shown below the current collector in FIG. 2B can be made negative, and vice versa, and the same applies to FIGS. 3A and 3B. In a bipolar energy storage device configuration, since the cells are stacked in a sandwich structure, the negative current collector of one cell is also used as the positive current collector of the next cell. In this way, the double-sided electrode is shared by two serially connected electrochemical cells, and one side of the double-sided electrode is one cell's functions as an anode, and the opposite side of the double-sided electrode functions as the cathode of the next cell. The double-sided anode and cathode polarities of the electrode are separated by a current collector that functions as an electron conductive film and a series connection and functions as a partition that prevents the flow of ions between the cells.

[0068] Generally, the active layer may include one active material or may be a composite active layer including two or more active materials. For example, the composite active layer may include a high-energy active material such as silicon together with carbon, which is a high-output material such as graphite. For example, silicon may have about 4000 mA-h / g, or up to about 4200 mA- h / g, and graphite may have about 300 mA-h / g, or up to about 370 mA- h / g. These materials can be used in the multilayer electrode film at different ratios for two different active layers, as will be further described herein. For example, the first layer may increase silicon compared to the second layer to increase energy, and the second layer may increase graphite compared to the first layer to increase power.

[0069] Generally, the multilayer electrode film is fabricated by stacking and / or laminating a plurality of active layers to form the electrode film, and the electrode film can be laminated on the current collector. The self-supporting electrode film may be assembled from the stacked active layers, for example, before being laminated on the current collector, or the active layers may be laminated on the current collector individually, in groups, and / or in sequence. For example, two active layers may be stacked to form a self-supporting electrode film, and the electrode film may be laminated on the current collector to form an electrode. Alternatively, or further , laminate a single first active layer on a current collector, and stack a second active layer on the first active layer and form an electrode film in contact with the current collector. Generally, the assembly processes described herein can be performed on a current collector with both-sided electrodes or single-sided electrodes. Therefore , the lamination process can be performed on a current collector in contact with one or more active layers or electrode films . The active layer or electrode film may be on the same side or the opposite side of the current collector.

[0070] The multilayer electrode film can have a selected thickness suitable for a particular application. The thickness of the operable multilayer electrode film may be thicker than the thickness of an electrode film prepared by conventional processes. In some embodiments, the multilayer electrode film can have a thickness of about 250 microns, about 300 microns, about 350 microns, about 400 microns, about 450 microns, about 500 microns, about 750 microns , or about 1 mm, or at least these values, or any range of values therebetween . An electrode including one or more multilayer electrode films can have a thickness of about 500 microns, about 750 microns, or about 1 mm, or about 2 mm, or at least these values, or any range of values therebetween.

[0071] The active layers provided herein can be manufactured from two or more stacked identical or substantially identical active pre-layers. In some embodiments, the active pre-layer may be a self-supporting self-supported film as provided in this specification.

[0072] The multilayer electrode film can include, for example, a high-output active layer, a high-energy active layer, a high-load active layer, a hybrid active layer, or a combination thereof. The high-energy active layer has a ratio It can include an active material characterized by a relatively large capacity. The high-output active layer is relatively large It can include an active material characterized by relatively large ejection performance. The high-load active layer has a high content of active material in the active layer and / or can include a high-load active layer in the electrode film as compared with an electrode film prepared using conventional materials and methods. The hybrid active layer can include two or more materials selected from high energy ergy, high output, or high load. The high output active material can include, for example, hard carbon. The high-energy active material can include, for example, Si or Si-C. The hybrid layer can include, for example, Sn, S n-C, Si, or Si-C.

[0073] Generally, the stacking order of the active layers in the electrode film is not particularly limited, and the composition of any active layer can be the same as or different from the composition of other active layers in the electrode film. Thus, a two-layer film of a current collector and two active layers A and B can have the following order. Current collector - A - B, or Current collector - B - A. Further, active layers A and B can have the same or different compositions from each other. A three-layer film of a current collector and three active layers A, B, and C can have the following order. Current collector - A - B - C, Current collector - A - C - B, Current collector - B - C - A, Current collector - B - A - C, Current collector - C - B - A, or Current collector - C - A - B. Further, in each of the above orders of the active layers, A can have the same or different composition as B or C, B can have the same or different composition as C or A, and C can have the same or different composition as A or B. In a specific embodiment, A, B, and / or C are high-output active layers, high-energy active layers, high-load active layers ​It may be selected from an active layer, a hybrid active layer, or a combination thereof.

[0074] Generally, each lamination and / or laminating process may be performed at different temperatures. . Generally, the compression ratio, the number of repetitions of lamination, and the lamination temperature also affect the characteristics of the final electrode film. For example, the adhesion between layers is considered to be affected by the lamination temperature.

[0075] The active layer mixture can be processed by a high shear and / or high pressure process. High shear and / or high pressure processes may include jet milling, blending, etc. The processing time and / or the feed rate generally affect the final particle sizes of the binder and / or the active material. In some embodiments, the active layer and / or the electrode film thus formed are self-supporting active layers and / or electrode films.

[0076] In some embodiments, the active layer mixture can include binder particles having a selected size. In some embodiments, the binder particles are about 50 nm, about 100 n m, about 150 nm, about 200 nm, about 250 nm, about 300 nm, about 350 nm, about 40 0 nm, about 450 nm, about 500 nm, about 1 μm, about 5 μm, about 10 μm, about 50 μm, or any value in the range therebetween.

[0077] In some embodiments, the number of layers of the multilayer electrode film may be selected from the desired thickness of the electrode film and the thickness of each active layer.

[0078] In some embodiments, the active layer mixture is described in U.S. Patent Publication No. 2015 / 0072234 One or more dry electrode processes are performed as described in . In some embodiments a dry electrode is provided, which is not treated by contaminants such as solvents, and thus the dry electrode is prepared by the methods and materials provided herein.

[0079] In some embodiments, electrodes manufactured using the materials and methods described herein can be characterized by improved performance. In further embodiments, the capacitance of a multi-layer electrode film comprising a first active layer and a second active layer is greater than either the first active layer or the second active layer. In further embodiments, the Coulomb efficiency of a multi-layer electrode film comprising a first active layer and a second active layer exceeds either the first active layer or the second active layer.

[0080] In some embodiments, a method of manufacturing an energy storage device comprising a multi-layer electrode film is provided. In further embodiments, the method includes stacking a first self-supporting active layer and a second self-supporting active layer to form a laminate, pressing or calendaring the laminate to form a multi-layer electrode film, and, optionally, laminating the multi-layer electrode film to a current collector to form an electrode. Methods of calendaring or pressing stacked active layers to form an electrode film, and methods of laminating stacked active layers to a current collector are generally known in the art.

[0081] FIG. 4A shows a rolling process, such as a calendaring process, for stacking active layers on top of each other. FIG. 4B shows a rolling process such as a calendaring process for laminating a multi-layer film to a current collector.

[0082] Figure 5A shows a pressing process for stacking active layers on top of each other. Figure 5B shows a pressing process for laminating a multilayer film onto a collector.

[0083] Generally, the process for manufacturing the active layer is no different from the process for manufacturing the electrode film using dry electrode manufacturing technology. For example, such technology may be of the kind described in U.S. Patent Publication No. 2005 / 0266298 and / or U.S. Patent Publication No. 2006 / 0146479. These, and other references to external documents in this specification, are hereby incorporated by reference in their entirety into this specification.

[0084] In some embodiments, a self-supporting electrode film is provided, and the electrode film includes a stacked active layer as provided herein. In further embodiments, the first active layer and the second active layer are self-supporting films. In some further embodiments, the self-supporting electrode film includes a first active layer and a second active layer, and the first active layer and the second active layer have different compositions. In yet another embodiment, the first active layer and the second active layer include different active material compositions and / or binder material compositions.

[0085] Figure 6 is a flowchart showing a method 200 for manufacturing a multilayer electrode film provided herein. In block 205, a first self-supporting active layer is manufactured. The first self-supporting active layer may be manufactured by any suitable method. Generally, the manufacturing method may be a dry electrode manufacturing process. Generally, the manufacturing method of the self-supporting dry active layer is similar to the manufacturing method of the self-supporting dry electrode film. In some embodiments, the first self-supporting active layer is the high energy provided herein. ​​​​​​​​​​​​​​It may be a rugged layer, a high-output layer, a high-load layer, or a hybrid layer.

[0086] In box 210, a second self-supporting active layer is manufactured. The second self-supporting active layer may be manufactured by any suitable method. Generally, the manufacturing method may be a dry electrode manufacturing process . The second self-supporting active layer may have the same or different composition as the first self-supporting active layer. In some embodiments, the second self-supporting active layer may be the high-energy layer, high-output layer, high-load layer, or hybrid layer provided herein.

[0087] In box 220, the first and second self-supporting active layers are laminated. Laminating the first layer to the second layer means adhering the layers to each other with no intervening layer between them on the same side of the current collector of the electrode. Laminating may include laminating the first layer and the second layer to each other . Laminating may include laminating one of the two layers to the other two layers without a current collector, or in another step, laminating the first layer to the second layer that has been pre-laminated to the current collector . The lamination of the first and second self-supporting active layers may include a calendaring process or a pressing process for adhering the two layers to each other. The combined multilayer film may have a thickness that is approximately the sum of the thicknesses of the two layers before lamination, or thinner than the sum of the thicknesses of the two layers .

[0088] In box 230, electrodes are formed from the laminated active layers. Forming the electrodes may include laminating the laminated active layer formed in box 220 to a current collector. In some embodiments, forming the electrodes from the laminated active layers includes laminating the laminated active layer to a current collector including an adhesive layer . The method may include laminating the current collector, for example, by adhesion. Further embodiments In the case of forming an electrode from the laminated active layer, it may include laminating the laminated active layer to the current collector without using an adhesive In a further embodiment, forming an electrode from the laminated active layer may include laminating the laminated active layer to the current collector using an adhesive In a further embodiment, forming an electrode from the laminated active layer may include laminating the laminated active layer to the current collector using an adhesive The method 200 may include additional steps of forming third or more self-supporting layers (such as in steps 205 and 210), or additional steps of laminating third or more additional self-supporting active layers (such as in step 220). The final multilayer electrode film may be formed upon completion of step 220, or, in the case of an electrode film having two or more layers, after an additional self-supporting active layer is laminated on top of the first and second layers The method 200 may include additional steps of forming third or more self-supporting layers (such as in steps 205 and 210), or additional steps of laminating third or more additional self-supporting active layers (such as in step 220). The final multilayer electrode film may be formed upon completion of step 220, or, in the case of an electrode film having two or more layers, after an additional self-supporting active layer is laminated on top of the first and second layers In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230 In some embodiments, steps 220 and 230 can be completed simultaneously. For example, the first and second self-supporting active layers can be formed in steps 205 and 210, and one of these two layers can be attached to the current collector before performing the lamination step 220. Subsequently, the first layer, the second layer, and the current collector attached to one of the two layers can be laminated simultaneously to complete the lamination step 220 and the electrode film forming step 230

[0089] Example 1 The first self-supporting single-layer electrode film has a thickness of 120 μm and contains graphite as an active material, and is manufactured by typical dry electrode technology as a comparative sample. The second self-supporting multilayer electrode film has a thickness of 120 μm each and contains three identical active layers containing graphite active material, and is manufactured according to the present disclosure. As shown in FIG. 7A The first self-supporting single-layer electrode film has a thickness of 120 μm and contains graphite as an active material, and is manufactured by typical dry electrode technology as a comparative sample. The second self-supporting multilayer electrode film has a thickness of 120 μm each and contains three identical active layers containing graphite active material, and is manufactured according to the present disclosure. As shown in FIG. 7A The first self-supporting single-layer electrode film has a thickness of 120 μm and contains graphite as an active material, and is manufactured by typical dry electrode technology as a comparative sample. The second self-supporting multilayer electrode film has a thickness of 120 μm each and contains three identical active layers containing graphite active material, and is manufactured according to the present disclosure. As shown in FIG. 7A The first self-supporting single-layer electrode film has a thickness of 120 μm and contains graphite as an active material, and is manufactured by typical dry electrode technology as a comparative sample. The second self-supporting multilayer electrode film has a thickness of 120 μm each and contains three identical active layers containing graphite active material, and is manufactured according to the present disclosure. As shown in FIG. 7A , the first electrode film, as shown in Fig. 7B, an SEM image of the second electrode film was taken, showing a uniform surface morphology. As shown in Figs. 7A and 7B, the multilayer electrode (Fig. 7B) shows open pores on the surface of the electrode film, and the open pores are important for wetting with the liquid electrolyte, and an improvement in electrode performance is expected. The conventional single-layer electrode (Fig. 7A) had few pores on the surface, so it was expected to limit the diffusion of the electrolyte into the intermediate layer of the electrode film. Although the multilayer electrode film in Fig. 7B showed a desirable pore structure, its density was maintained.

[0090] Example 2 Three graphite electrode films were prepared as follows. The first electrode film contained graphite, 3 wt% CMC and 3 wt% PTFE ("Layer 1"), and the second electrode film contained graphite, 3 wt% polyvinyl chloride (PVC) and 3 wt% PTFE ("Layer 2"). The third multilayer electrode film was prepared with a three-layer active layer, Layer 1 - Layer 2 - Layer 1 (" Layer 121") having the following composition. The film thicknesses of Layer 1, Layer 2, and Layer 121, which are electrode films, were 132 μm, 132 μm, and 256 μm, respectively. Figs. 8A and 8B provide data on the capacitance and efficiency measured for the electrode films of Layer 1, Layer 2, and Layer 121.

[0091] As seen in Fig. 8A, Layer 1 had a charge capacity of approximately 325 mAh / g and a discharge capacity of approximately 27 5 mAh / g, Layer 2 had a charge capacity of approximately 350 mAh / g and a discharge capacity of approximately 300 mA h / g, and Layer 121 had a charge capacity of approximately 400 mAh / g and a discharge capacity of approximately 350 mAh / g. As shown in Fig. 8B, the efficiency of Layer 1 was approximately 81.5%, the efficiency of Layer 2 was approximately 83%, and the efficiency of Layer 121 was approximately 85%.

[0092] Example 3 A self-supporting self-standing electrode film was manufactured according to the present disclosure. The Si-C3 layer electrode film was fabricated by creating two active layers, a first active layer and a second active layer. The first active layer ( A) contained 94% graphite and 6% binder, and the second active layer (B) contained 8 9.5% graphite, 4.5% nano-sized silicon, and 6% binder. The binder for each electrode film contained 3 wt% CMC and 3 wt% PTFE . Three identical pre-layers were laminated and calendared to form the first active layer. The electrode film was formed by laminating the second active layer (B) between two first active layers (A) with a thickness of 120 μm . Thus, the order of the active layers was A-B-A. The resulting laminated active layer was calendared to form the electrode film. Figures 9A and 9B provide the capacity and efficiency data of the A-B-A three-layer laminated electrode film of Example 3. As shown in Figure 9A, the charge capacity of layer 1 was approximately 250 mAh / g and the discharge capacity was approximately 200 mA h / g, the charge capacity of layer 2 was approximately 350 mAh / g and the discharge capacity was approximately 275 mAh / g

[0093] , and the charge capacity of layer 121 was approximately 375 mAh / g and the discharge capacity was approximately 300 mAh / g . As shown in Figure 9B, the efficiency of layer 1 was approximately 83.5%, the efficiency of layer 2 was approximately 77.5%, and the efficiency of layer 121 was approximately 82%. Although specific embodiments of the present invention have been described, these embodiments are presented by way of example only and are not intended to limit the scope of the present disclosure. In fact, the novel methods and systems described herein

[0094] can be embodied in various other forms. Furthermore In the various omissions, substitutions, and changes in the systems and methods described in this specification, they can be made without departing from the gist disclosed herein. The appended claims and their equivalents are intended to include forms or improvements such as those that are within the scope and gist of this disclosure. Therefore, the scope of the present invention is defined only by referring to the appended claims.

[0095] Features, materials, properties, or groups described in connection with a particular aspect, embodiment, or example are to be understood as applicable to any other aspect, embodiment, or example described in this section or elsewhere in this specification, unless incompatible. All features (including the appended claims, abstract, and drawings) disclosed herein, and / or all steps of the methods or processes disclosed as such, can be combined in any combination, except combinations where at least some of such functions and / or steps are mutually exclusive. The protection is not limited to the details of the foregoing embodiments. The protection extends to new ones, or new combinations, of the functions (including the appended claims, abstract, and drawings) disclosed herein, or new ones, or new combinations, of the steps of the methods or processes.

[0096] Furthermore, specific functions described in the context of separate implementations in this disclosure can also be implemented in combination in a single implementation. Conversely, various functions described in the context of a single implementation can also be implemented individually in multiple implementations, or implemented in appropriate sub - combinations. Additionally, features have been described above as acting in a particular combination. ​​​​​​​​​​​​​​However, one or more features from the claimed combination may, in some cases, be removed from the combination, and the combination may be claimed as a sub - combination or a variation of a sub - combination. Moreover, operations are shown in the drawings or described in the specification in a particular order, but such operations may be performed in a particular order shown or in a sequential order to achieve the desired result, or not all operations need to be performed. Other operations not shown or described can be incorporated into the exemplary methods and processes. For example, one or more additional operations can be performed before, after, simultaneously with, or in between any of the described operations.

[0097] Furthermore, in other implementations, the operations can be rearranged or re - ordered. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may be different from those shown in the figures. Depending on the embodiment, the specific steps described above may be deleted, and other steps may be added. Additionally, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which are included within the scope of this disclosure. Also, the separation of the various system components in the above implementations should not be understood to be necessary in all implementations, and it should be understood that the components and systems described can generally be integrated into a single product or packaged into multiple products. For example, the components of the energy storage system described herein However, one or more features from the claimed combination may, in some cases, be removed from the combination, and the combination may be claimed as a sub - combination or a variation of a sub - combination. Moreover, operations are shown in the drawings or described in the specification in a particular order, but such operations may be performed in a particular order shown or in a sequential order to achieve the desired result, or not all operations need to be performed. Other operations not shown or described can be incorporated into the exemplary methods and processes. For example, one or more additional operations can be performed before, after, simultaneously with, or in between any of the described operations. Furthermore, in other implementations, the operations can be rearranged or re - ordered. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may be different from those shown in the figures. Depending on the embodiment, the specific steps described above may be deleted, and other steps may be added. Additionally, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which are included within the scope of this disclosure. Also, the separation of the various system components in the above implementations should not be understood to be necessary in all implementations, and it should be understood that the components and systems described can generally be integrated into a single product or packaged into multiple products. For example, the components of the energy storage system described herein Furthermore, in other implementations, the operations can be rearranged or re - ordered. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may be different from those shown in the figures. Depending on the embodiment, the specific steps described above may be deleted, and other steps may be added. Additionally, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which are included within the scope of this disclosure. Also, the separation of the various system components in the above implementations should not be understood to be necessary in all implementations, and it should be understood that the components and systems described can generally be integrated into a single product or packaged into multiple products. For example, the components of the energy storage system described herein However, one or more features from the claimed combination may, in some cases, be removed from the combination, and the combination may be claimed as a sub - combination or a variation of a sub - combination. Moreover, operations are shown in the drawings or described in the specification in a particular order, but such operations may be performed in a particular order shown or in a sequential order to achieve the desired result, or not all operations need to be performed. Other operations not shown or described can be incorporated into the exemplary methods and processes. For example, one or more additional operations can be performed before, after, simultaneously with, or in between any of the described operations. Furthermore, in other implementations, the operations can be rearranged or re - ordered. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may be different from those shown in the figures. Depending on the embodiment, the specific steps described above may be deleted, and other steps may be added. Additionally, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which are included within the scope of this disclosure. Also, the separation of the various system components in the above implementations should not be understood to be necessary in all implementations, and it should be understood that the components and systems described can generally be integrated into a single product or packaged into multiple products. For example, the components of the energy storage system described herein However, one or more features from the claimed combination may, in some cases, be removed from the combination, and the combination may be claimed as a sub - combination or a variation of a sub - combination. Moreover, operations are shown in the drawings or described in the specification in a particular order, but such operations may be performed in a particular order shown or in a sequential order to achieve the desired result, or not all operations need to be performed. Other operations not shown or described can be incorporated into the exemplary methods and processes. For example, one or more additional operations can be performed before, after, simultaneously with, or in between any of the described operations. Furthermore, in other implementations, the operations can be rearranged or re - ordered. Those skilled in the art will understand that in some embodiments, the actual steps performed in the illustrated and / or disclosed processes may be different from those shown in the figures. Depending on the embodiment, the specific steps described above may be deleted, and other steps may be added. Additionally, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which are included within the scope of this disclosure. Also, the separation of the various system components in the above implementations should not be understood to be necessary in all implementations, and it should be understood that the components and systems described can generally be integrated into a single product or packaged into multiple products. For example, the components of the energy storage system described herein However, one or more features from the claimed combination may, in some cases, be removed from the combination, and the combination may be claimed as a sub - combination or a variation of a sub - combination. Either may be provided separately or may be integrated together (e.g., packaged together). The electrodes may be coupled together (eg, coupled or attached together) to form an energy storage system.

[0098] For purposes of this disclosure, certain aspects, advantages, and novel features have been described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, one of ordinary skill in the art will appreciate that the present disclosure provides certain advantages over other advantages that may be taught or suggested herein. It is not necessary that all of the advantages or group of advantages taught herein be achieved. It will be appreciated that the present invention may be embodied or performed in any manner to achieve this.

[0099] Conditional phrases such as "can," "may," "can," and "may" generally Unless otherwise specified or understood otherwise within the context of use, Certain embodiments may include certain features, elements, and / or Therefore, such conditional language is intended to convey that Generally, features, elements, and / or steps are required for one or more embodiments. or one or more embodiments may be implemented with or without user input or prompting. The features, elements and / or steps of the present invention may be included or performed in a particular embodiment. It is not intended that the specification necessarily include the logic for determining whether or not a

[0100] Conjunctions such as "at least one of X, Y, and Z" are used unless otherwise noted. It is understood apart from the context in which it is commonly used to convey an item, term, etc., and is expressed as X, Y or Any of Z is the same. Therefore, such conjunctions generally do not intend to suggest that a particular embodiment requires the presence of at least one X, at least one Y, and at least one Z. Nor is it generally intended to suggest that. with at least one X, at least one Y, and at least one Z.

[0101] Terms such as "about," "approximately," "generally," and "substantially" as used herein indicate values, amounts, or characteristics that are close to the recited values, amounts, or characteristics and that still perform the desired function or achieve the desired result. which also perform the desired function or achieve the desired result. or achieve the desired result.

[0102] The scope of the present disclosure is not intended to be limited by the specific disclosure of the preferred embodiments in this section or elsewhere in this specification, but may be defined by the claims presented in this section or elsewhere in this specification or presented in the future. or elsewhere in this specification or presented in the future. or defined by the claims presented in this section or elsewhere in this specification or presented in the future. The language of the claims should be interpreted broadly based on the language used in the claims and not limited to the examples described in this specification, or during the examination of the application, the examples should be construed as non-limiting. or during the examination of the application, the examples should be construed as non-limiting. should be construed as non-limiting.

Claims

1. A first active layer having a first active material and a first binder, and a second active layer having a second active material and a second binder, wherein the first and second active layers are laminated to form a multilayer electrode film, and the multilayer electrode film is a self-supporting film. A multilayer electrode film characterized by this.

2. The multilayer electrode film according to Claim 1, characterized in that the multilayer electrode film has a thickness of at least about 200 μm.

3. The multilayer electrode film according to Claim 1, characterized in that at least one of the types and amounts of the first active material and the second active material is different between the first active layer and the second active layer.

4. The multilayer electrode film according to Claim 1, characterized in that at least one of the types and amounts of the first binder and the second binder is different between the first active layer and the second active layer.

5. The multilayer electrode film according to Claim 1, characterized in that the first active layer and the second active layer have substantially the same composition.

6. The multilayer electrode film according to Claim 1, further comprising a third active layer having a third active material and a third binder.

7. The multilayer electrode film according to Claim 1, characterized in that at least one of the first and second active materials comprises at least one of sulfur and a material containing sulfur.

8. A current collector having a first surface and a second surface, and a first multilayer electrode film which is the multilayer electrode film of Claim 1 laminated on the first surface of the current collector. A multilayer electrode comprising this.

9. The multilayer electrode according to Claim 8, characterized in that the first multilayer electrode film is directly laminated on the first surface of the current collector.

10. The multilayer electrode according to Claim 8, characterized in that no adhesive layer is provided between the multilayer electrode film and the current collector.

11. A multilayer electrode according to Claim 8, and a second multilayer electrode film laminated on the second surface of the current collector. A double-sided multilayer electrode comprising this.

12. The double-sided multilayer electrode according to Claim 11, characterized in that the first multilayer electrode film has a polarity opposite to that of the second multilayer electrode film.

13. The double-sided multilayer electrode according to Claim 11, characterized in that the first multilayer electrode film and the second multilayer electrode film are symmetric with respect to each other.

14. The double-sided multilayer electrode according to Claim 11, characterized in that the first multilayer electrode film and the second multilayer electrode film are asymmetric with respect to each other. ​ ​ ​ ​ ​ 。 ​ ​ ​ ​ ​ ​ ​ ​ ​

15. The first multilayer electrode film has a different number of layers from the second multilayer electrode film. The double-sided multilayer electrode according to claim 14, characterized in that.

16. The active layer of the first multilayer electrode film directly adjacent to the first surface of the current collector has a different composition from the active layer of the second multilayer electrode film directly adjacent to the second surface of the current collector. The double-sided multilayer electrode according to claim 14, characterized in that.

17. Providing a first active layer having a first active material and a first binder and being a self-supporting film; Providing a second active layer having a second active material and a second binder and being a self-supporting film; 、 Stacking the first active layer on the second active layer to form a multilayer electrode film that is a self-supporting film. 、 A method for manufacturing a multilayer electrode film, comprising:

18. The stacking of the first active layer on the second active layer is performed by a calendar processing step. The method according to claim 17, characterized in that.

19. The stacking of the first active layer on the second active layer is performed by a pressing step. The method according to claim 17, characterized in that.

20. Manufacturing a first multilayer electrode film according to the method of claim 17; Providing a current collector having a first surface and a second surface; Laminating the first multilayer electrode film onto the first surface of the current collector to form a multilayer electrode. A method for manufacturing a multilayer electrode, comprising:

21. The first multilayer electrode film is directly laminated onto the first surface of the current collector. The method according to claim 20, characterized in that.

22. No adhesive layer is provided between the multilayer electrode film and the current collector. The method according to claim 20, characterized in that.

23. Laminating the first multilayer electrode film onto the first surface of the current collector is performed by a calendar processing step. The method according to claim 20, characterized in that.

24. Laminating the first multilayer electrode film onto the first surface of the current collector is performed by a pressing step. The method according to claim 20, characterized in that.

25. Providing a second multilayer electrode film; and Laminating the second multilayer electrode film onto the second surface of the current collector to form a double-sided multilayer electrode. The method according to claim 20, further comprising:

26. Providing a first active layer having a first active material and a first binder and being a self-supporting film; ​ 、 Providing a second active layer having a second active material and a second binder and being a self-supporting film 、 Providing a current collector Laminating the first active layer on the second active layer Laminating the first active layer on the current collector, a method for manufacturing a multilayer electrode including the above 。

27. Prior to laminating the first active layer on the second active layer, laminating the first active layer on the current collector, the method according to claim 26, characterized in that

28. Prior to laminating the first active layer on the current collector, laminating the first active layer on the second active layer, the method according to claim 26, characterized in that

29. Providing a second multilayer electrode film Laminating the second multilayer electrode film on the second surface of the current collector to form a double-sided multilayer electrode The method according to claim 26, including the above

30. The first multilayer electrode film has a polarity opposite to that of the second multilayer electrode film, characterized in that the claim The method according to claim 29

31. The first multilayer electrode film and the second multilayer electrode film are symmetric with respect to each other, characterized in that The method according to claim 29

32. The first multilayer electrode film and the second multilayer electrode film are asymmetric with respect to each other, characterized in that The method according to claim 29

33. The first multilayer electrode film includes a different number of layers from the second multilayer electrode film, characterized in that The method according to claim 32

34. The active layer of the first multilayer electrode film directly adjacent to the first surface of the current collector has a composition different from that of the active layer of the second multilayer electrode film directly adjacent to the second surface of the current collector, characterized in that The method according to claim 32 The method according to claim 32

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