Compositions and methods for dry electrode films comprising particulate non-fibrillating binders

Abstract

To provide a dry electrode film showing improved mechanical characteristics and processing characteristics, an electrode, a lithium ion battery, and a manufacturing method of the dry electrode film.SOLUTION: There is provided a dry electrode-film for an energy storage device comprising a dry active material and a dry binder comprising a fibrillizable binder and a particulate non-fibrillated binder having a D50 particle size of 1-25 μ m, wherein the dry electrode-film is free-standing.SELECTED DRAWING: Figure 6

Description

[Technical Field]

[0001] This application is based on the application filed on March 30, 2018, entitled "Microparticulate non-fibrillating binder." U.S. Provisional Patent Application No. 62 / 600, entitled "Compositions and Methods for Dry Electrode Films Comprising No. 50,903, the entire disclosure of which is incorporated herein by reference. Included.

[0002] The present invention relates generally to energy storage devices, and more particularly to particulate non-fibrillated binders. This invention relates to materials and methods for dry electrode films containing DA. [Background technology]

[0003] Electrical energy storage cells are used in electronic, electromechanical, electrochemical, and other useful devices. They are widely used to provide electrical power. These batteries include primary chemical batteries and secondary ( Various types of capacitors, including batteries such as rechargeable batteries, fuel cells, and ultracapacitors The operating power and Increasing the amount of energy and power required will enhance energy storage, increase power capacity, and This is desirable to broaden the range of possible uses. Summary of the Invention [Problem to be solved by the invention]

[0004] Energy storage devices containing electrode films with a combination of complementary attributes are becoming increasingly popular for practical applications. Furthermore, the performance of the energy storage device can be improved in existing dry and Solvent-free manufacturing methods can impose practical limitations on the composition of the electrodes. New electrode film formulations and their manufacturing methods expand the possibilities of electrode film formulations. This can result in improved performance. [Means for solving the problem]

[0005] For purposes of summarizing the invention and the advantages achieved over the prior art, certain aspects of the invention are set forth below. All such objects or advantages are expressly incorporated herein by reference. This may not be achieved in any particular embodiment. does not necessarily achieve any other objectives or advantages that may be taught or suggested herein. without the need to achieve or optimize one or a group of advantages as taught herein. It will be appreciated that the present invention can be embodied or carried out in a variety of ways.

[0006] In a first embodiment, a particulate non-fibre composition having a particle size of about 0.5 μm to about 40 μm is used. A self-supporting dry electrode film is provided that includes an allylated binder.

[0007] In a second aspect, a dry electrode film for an energy storage device is provided. Dry electrode films consist of a dry active material, a fibrillated binder, and a D of approximately 0.5 to 40 μm. 50 a dry binder comprising a particulate non-fibrillating binder having a particle size of The dry electrode film is self-supporting.

[0008] In some embodiments, the particulate non-fibrillating binder has a D of about 1 to 25 μm. 50 In some embodiments, the dry binder comprises up to 50% by weight of particulate non-abrasive particles. Contains a fibrillating binder.

[0009] In some embodiments, the particulate non-fibrillating binder is a binder of cellulose and In some embodiments, the microparticles are selected from at least one of a cellulose derivative. The non-fibrillating binder may be cellulose, cellulose ester, cellulose ether, Cellulose nitrate, carboxyalkyl cellulose, cellulose salts and cellulose salt derivatives In some embodiments, the particulate non-fibrous The acrylate binder is cellulose, cellulose acetate, methyl cellulose, ethyl cellulose, cellulose, hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HE C), cellulose nitrate, carboxymethyl cellulose (CMC), carboxyethyl cellulose Rosin, carboxypropyl cellulose, carboxyisopropyl cellulose, sodium Sodium cellulose, sodium nitrate cellulose and sodium carboxyalkyl cellulose In some embodiments, the particulate non-fibrillar The acrylate binder is carboxymethyl cellulose (CMC) and polyvinylidene fluoride. (PVDF). In some embodiments, the polymer is selected from at least one of cellulose acetate, cellulose acetate diphosphate, and cellulose acetate phosphate dehydrate. The cellulose or cellulose derivative has a number average molecular weight of about 10,000 to about 500,000. In some embodiments, the cellulose derivative has a degree of substitution of about 0.7 to about 1.5. do.

[0010] In some embodiments, the fibrillating binder is polytetrafluoroethylene In some embodiments, the dry electrode film contains pores, cracks, and In some embodiments, the dry electrode film is substantially free of surface pits. Both have a tensile strength of about 1 N. In some embodiments, the dry active material comprises graphite.

[0011] In a third aspect, an electrode is provided that includes a dry electrode film in contact with a current collector. In an aspect, a lithium ion battery is provided that includes an electrode.

[0012] In a fifth aspect, a method for manufacturing a dry electrode film for an energy storage device is provided. This method involves treating a dry non-fibrillating binder with high shear to produce a dry particulate non-fibrillating binder. and forming a dry fibrillated binder, and converting the dry particulate non-fibrillated binder into a dry particulate non-fibrillated binder. and combining the dry electrode film mixture with a calender to form a dry electrode film mixture. and processing to form a free-standing dry electrode film.

[0013] In a sixth aspect, a method for manufacturing a dry electrode film for an energy storage device is provided. The method includes providing a dry particulate non-fibrillating binder, The fibrillated binder is mixed with the dry first active material by a first non-destructive mixing process to form a dry 2. A method for forming a bulk active material mixture, comprising: subjecting a dry fibrillated binder to a high shear mixing process; and mixing the dry binder with a second dry active material to form a dry structural binder mixture; The active material mixture and the dry structural binder mixture are mixed by a second non-destructive mixing process. forming a dry electrode film mixture; and forming a free-standing electrode film from the dry electrode film mixture. The method includes manufacturing a dry electrode film.

[0014] In some embodiments, the method comprises treating a dry non-fibrillating binder with high shear. , further comprising forming a dry particulate non-fibrillating binder.

[0015] All of these embodiments are intended to be within the scope of the invention(s) disclosed herein. These and other embodiments of the present invention are described in the following preferred embodiments with reference to the accompanying drawings. As will be readily apparent to those skilled in the art from the detailed description of the preferred embodiments, the present invention It is not limited to any particular preferred embodiment shown. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 shows an embodiment of an energy storage device. [Figure 2A] Figure 2A is a photograph of the inside of the grinding chamber of a jet mill with three jets pointing at the same point. [Figure 2B] FIG. 2B is an image of a classifier with a spinning wheel that selects the output size of the particles. [Figure 3A] FIG. 3A shows an SEM image of commercially available CMC particles. [Figure 3B] FIG. 3B shows jet-milled CMC particles processed according to Example 1. [Figure 4] FIG. 4 shows a chart providing the charge and discharge specific capacity of dry graphite anodes prepared according to Example 1, comparing anodes prepared from commercial CMC and milled CMC. [Figure 5A] FIG. 5A shows an image of an anode film prepared using commercially available CMC particles. [Figure 5B] FIG. 5B shows an image of an anode film prepared using jet-milled CMC particles according to the process of Example 1. [Figure 6] FIG. 6 provides a flow chart illustrating a method for producing a free-standing electrode film by combining a non-fibrillating binder with a fibrillating binder. [Figure 7] FIG. 7 provides a flow chart illustrating a method for parallel processing of electrode film binders. DETAILED DESCRIPTION OF THE INVENTION

[0017] Various embodiments of electrode films for use in energy storage devices are described herein. In particular, in certain embodiments, the energy storage devices disclosed herein comprise: The electrode film includes a particulate non-fibrillating binder having a particular particle size. The electrode films were found to exhibit improved mechanical and processing properties. Methods for treating such particulate non-fibrillating electrode film binders, and A method for incorporating the particulate non-fibrillating binder into an electrode film is also provided. The figures show that when the particle size of a particular component is within the ranges provided herein, It is evident that improved uniformity of material distribution can be achieved.

[0018] Lithium-ion batteries are used in, for example, consumer electronics, productivity equipment, and battery-powered vehicles. It has been trusted as a power source for many commercial and industrial applications in the The demands placed on energy storage devices are continually and rapidly increasing. The industry is focusing on compact and efficient electric vehicles such as plug-in hybrids and pure electric vehicles. They are developing vehicles that rely on energy storage.

[0019] Several components that affect the storage potential of an energy storage device are the electrodes, More specifically, the electrode film includes each electrode in the device. The electrochemical capabilities of the electrodes, e.g. For example, the capacity and efficiency of a battery electrode are governed by various factors, such as the active material. , binder, additive distribution, material properties such as particle size and surface area of ​​the active material, surface area of ​​the active material, Surface characteristics, or physical properties of the electrode film such as cohesion and adhesion to conductive elements. Methods have traditionally used high shear and / or high pressure processing steps to convert electrode film materials into The electrode film is ground and mixed, which is more structurally sound than electrode films produced using wet processes. This can contribute to structural advantages.

[0020] In principle, electrode fillers with a more uniform distribution of active material, binder, and other components are desirable. Generally, electrode films exhibit higher performance due to the mechanical properties of the film components and It is believed that the interactions between these factors may result in poor performance. For example, mechanical limitations can be due to poor adhesion between the active layer and the current collector, and to poor adhesion between the active material and the current collector. It is believed that this may be due to poor cohesion in the electrode film, such as with the binder. Such a process results in a loss of performance in both power supply and energy storage capacity. The degradation of performance may be due to, for example, a decrease in ionic conductivity, a decrease in electrical conductivity, etc. This may be due to inactivation of the active material by, for example, As the adhesion between the active layer and the current collector decreases, the cell resistance can increase. Decreased aggregation can also result in increased cell resistance and, in some cases, electrical contact This can result in a loss of charge and removal of some of the active material from the ionic and electromigration cycle in the cell. Without wishing to be limited by theory, it is believed that the volume change of the active material For example, large volume changes during cell cycling may contribute to processes such as In electrodes incorporating certain active materials, such as silicon-based materials, which undergo oxidation, further decomposition Lithium intercalation and deintercalation processes may be observed. The process can accommodate such volume changes in some systems. These mechanical degradation processes can occur on any electrode, e.g., cathode, anode, positive electrode, negative electrode, Battery electrodes, capacitor electrodes, hybrid electrodes, or electrodes of other energy storage devices Increasing the uniformity of the electrode film material can alleviate these problems. It is expected to provide at least some relief.

[0021] More specifically, the uniform distribution of the binder in the electrode film leads to improved mechanical properties. Such an improvement can provide many practical advantages. For example, an electrode film with a uniformly distributed binder component can be made with less binder material. Reduced incidence and / or severity of defects compared to uniformly distributed electrode films For example, an electrode film in which the binder component is uniformly distributed can exhibit a decrease in the degree of adhesion. They may exhibit higher tensile strength and / or ductility, which may be beneficial for energy storage devices. Specifically, it is possible to manufacture electrodes having higher tensile strength and / or ductility. Polarized films are easier to apply to current collectors or other substrates. These factors are This may be particularly relevant when dry electrode processing techniques are used, and the electrode film may be The film is considered to be a free-standing film, which is further defined in the Specification as a "self-supporting film." may be treated.

[0022] Smaller particle sizes are, in principle, more efficient than conventional polymers containing active materials, binders, and other components. This may allow for a more uniform distribution of polar film material. Components can aggregate when reduced below a certain size threshold. The particle size of the various components may advantageously fall within a range. It was discovered that fibrillating binders can be incorporated into electrode films at specific particle sizes. Smaller particle size and more intimate contact of active materials, binders and additives The smaller particle size leads to better electrode filler. These electrode films can be manufactured using substantially the same process. Characteristics between electrode films produced using the same process and / or under substantially the same conditions The resulting product may be manufactured with reduced variation in properties.

[0023] If the electrode film is fabricated by a dry, solvent-free process, aqueous dispersions are not available. However, achieving a uniform dispersion of cellulose can be more difficult. C is generally about 40 to 70 μm D 50 The particle size is limited to the following: The size is limited to a certain degree of substitution. Larger particle size fragments are due to the uneven distribution of the CMC. uniformity, localized pressure during calendering, and adhesion of CMC particles to heated calender rollers This can cause various problems such as electrode film defects and other issues described herein. It is thought that the cellulose particle size can be reduced to match the active substance particle size. It is believed that the problems described in this specification can be improved by reducing the CMC. Since the particles are well dispersed and are on the order of the particle size of the active material particles, the calender pressure is It is believed that the density will be more evenly distributed throughout the room, which will result in more consistency and Damage to particles of active material such as graphite particles can be reduced. Improved consistency of formation may allow for the production of uniform continuous roll film.

[0024] Some embodiments provide an electrode film manufactured by a dry process for use in a battery. The electrode film comprises a particulate non-filamentous material having a particle size in the range of 0.5 to 40 μm. The composite material includes a fibrous binder and at least one fibrillating binder. particulate non-fibrillating binder particles having a size ranging from about 0.5 to about 40 μm; and an electrode film incorporating such particulate non-fibrillating binder particles. Dry electrodes and manufacturing processes are included. Such electrode films are made of active materials, binders, and Such particulate non-fibrillated fibers may have a more uniform distribution of the fibers, fibers, and other components. Electrode films incorporating indium particles exhibit improved tensile strength and / or processability. In certain embodiments, the particulate non-fibrillating binder may be, for example, The electrode film is made of cellulose, such as carboxymethyl cellulose (CMC). In certain embodiments, the electrode film is suitable for use as an anode in a nickel-ion battery. The formula contains graphite.

[0025] Dry or self-supporting electrodes incorporating such finely divided non-fibrillating binder particles are The electrode films can provide improved properties compared to typical electrode films For example, dry or self-supporting electrode films have the following advantages: improved film strength, improved cohesion, may provide one or more of improved adhesion, improved electrical performance, or reduced defect rates Defects can include holes, cracks, and surface pits in the electrode film. Adhesion is the adhesion between the electrode and the current collector. The electrical performance may be specific capacitance. The film strength may be tensile strength. may be.

[0026] An electrode film as described herein or an electrode incorporating an electrode film as described herein Energy storage devices have improved specific capacity (which can be measured in mAh / g) Further improvements that may be realized in various embodiments include: Includes reduced capacity fade over the life of the device.

[0027] Some embodiments relate to dry electrode process technology. The dry electrode manufacturing process is Patent Application Publication No. 2006 / 0114643, and U.S. Patent Application Publication No. 2006 / 0133 013, U.S. Patent No. 9,525,168, or U.S. Patent No. 7,935,155 and US Pat. No. 6,262,099, each of which is incorporated by reference. No. 6,299,499, filed on Dec. 1, 2003, which is hereby incorporated in its entirety.

[0028] Provided herein is a method for reducing the particle size of a particulate non-fibrillating binder. The pressurized jet milling process further provides a particle size distribution of the particulate non-fibrillating binder. For example, a non-fibrillating binder was placed in a jet mill. , "Jet Milling" to obtain the median (D 50 ) particle size In some embodiments, the active material can be further reduced in particle size by about 15 In a further embodiment, the graphite may have a median particle size of 100 μm. The particulate non-fibrillating binder may be, for example, a cellulose such as CMC. Suitable pressurized jet milling conditions include milling gas pressures of 100 to 500 psi. Milling can include separating the milled particles by particle size. For example, particles of a particulate non-fibrillating binder having a predetermined size can be separated by a classifier. It can be separated.

[0029] One embodiment is a method for manufacturing a free-standing electrode film. Referring to FIG. 6, Method 6 00 selects a non-fibrillating binder (605), Jet milling to form a particulate non-fibrillating binder having a median particle size. and (610). Step 610 includes grinding the non-fibrillating binder. to produce particles of the order of the particle size of the active material, for example, about 0.5 to about 40 μm. and mixing the particulate non-fibrillating binder particles with a fibrillating binder and one or more and combining the active material with the electrode film mixture (615). The rubber mixture is calendered to form a self-supporting and / or free-standing electrode film. (620). In some embodiments, each step is dry and solvent-free. In some embodiments, the particulate non-fibrillating binder is polyvinylidene fluoride (PVD In a further embodiment, the particulate non-fibrillating The binder is CMC. In yet another embodiment, the fibrillating binder is PTFE In yet another embodiment, the active material comprises graphite. The method may include one or more parallel processing steps such as those provided in FIG.

[0030] Referring to FIG. 7, the parallel processing method includes an upper (shown) parallel processing path 702 and a lower (shown) parallel processing path 703. The upper (shown) parallel processing path 702 starts with the bulk active The material 704 is non-destructively mixed with a non-fibrillating binder 706 to form a bulk An active material mixture 708 is formed. The non-fibrillating binder 706 is the same as previously described herein. It may also be a particulate non-fibrillating binder, as described in The polymeric binder 706 may be, for example, PVDF and / or CMC. The conductive material 704 may be graphite. In the lower (shown) parallel processing path 710: The second active material 712 and the structural binder 714 are combined under non-destructive mixing. The second active material 714 may be PTFE and the second active material 712 may be graphite. The mixed structural binder and second active material form a first binder mixture 716. and then jet milled in a high shear, high intensity process to form a structural binder mixture 718. The bulk active material mixture 708 is then mixed with the structural bulk active material mixture 708 in a non-destructive mixing process. and the binder mixture 718 to form a bulk active material and binder mixture 720. and then processed by low shear jet milling to form an electrode film mixture 722. Low shear jet milling is used, for example, to form the structural binder mixture 718. This may be performed at a higher feed rate compared to the initial jet milling used. The electrode film mixture 722 is pressed or bonded to a self-supporting and free-standing electrode film 724. The material may be calendered. Generally, no solvent is required at any stage of the process. It will not be done.

[0031] In various embodiments, a dry mixture, such as a mixture including binder particles and active material particles, is used. The dried powder can be mixed by gentle processes, for example, using convection, air pressure, or diffusion mixers. The mixture can be mixed as follows: in a tumbler (e.g., with or without a mixing medium) For example, glass beads, ceramic balls), paddle mixer, blade blender or The gentle mixing process is non-destructive with respect to any active ingredients in the mixture. Without limitation, after a gentle mixing process, the decomposition of the graphite particles may occur. In a further embodiment, the powder mixing sequence and conditions The conditions were modified to improve uniform distribution of the active material, binder, and any additives. obtain.

[0032] The materials and methods provided herein can be implemented in a variety of energy storage devices. As provided herein, the energy storage device may be a capacitor, a lithium-ion battery, or a combination thereof. On-capacitor (LIC), ultracapacitor, battery, lithium-ion battery, Or, it may be a hybrid energy storage device that combines two or more of the above aspects. In a preferred embodiment, the device is a lithium ion battery.

[0033] The energy storage device may be, for example, planar, spiral wound, button shaped, or powder coated. The energy storage device may be in any suitable form, such as a switch. , e.g., power generation systems, uninterruptible power supply systems, photovoltaic power generation systems, e.g., industrial machinery and / or energy recovery systems for use in transportation. -Storage devices are used in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PEVs), various electronic devices and / or may be used to power a vehicle.

[0034] FIG. 1 illustrates an electrode film comprising a particulate non-fibrillating binder as provided herein. 1 shows a schematic cross-sectional side view of an example of an energy storage device 100 having a foam. The device 100 may be, for example, a capacitor, a battery, a capacitor-battery hybrid, or In one embodiment, device 100 is a lithium ion battery. be.

[0035] The device includes a first electrode 102, a second electrode 104, and a first electrode 102 and a second electrode 105. The first electrode 102 and the second electrode 104 are connected to each other by a separator 106. 04 are adjacent to opposing surfaces of the separator 106. The device 100 facilitates ionic communication between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 118 may be a conductive material for the first electrode 102, the second electrode 103, and the like. 4, and may be in contact with the separator 106. The electrolyte 118, the first electrode 102, the second electrode 104, and the separator 106 may be in contact with the electrolyte 118, the first electrode 102, the second electrode 104, and the separator 106. The two electrodes 104 and separator 106 are contained within an energy storage device housing 120. One or both of the first electrode 102 and the second electrode 104 may be any of the electrodes described herein. The binder may include a particulate non-fibrillating binder so as to

[0036] one or more of the first electrode 102, the second electrode 104, and the separator 106; or These components may include a porous material. The pores within the porous material allow the housing 120 to providing containment and / or increased surface area for contact with the electrolyte 118 within the The energy storage device housing 120 can accommodate the first electrode 102, the second electrode 104, and and separator 106, and may be physically sealed from the surrounding environment. Good too.

[0037] In some embodiments, the first electrode 102 can be an anode (negative electrode), The second electrode 104 can be a cathode (positive electrode). Adjacent opposite sides of the separator 106, such as the electrode 102 and the second electrode 104 The two electrodes are electrically isolated while still allowing ionic communication between the two adjacent electrodes. The separator 106 may be made of a suitable porous, electrically insulating material. In some embodiments, the separator 106 can include a polymeric material. For example, the separator 106 can be made of a cellulose material (e.g., paper), polyethylene ( PE) material, polypropylene (PP) material, and / or polyethylene and polypropylene It may include a pyrene material.

[0038] Generally, the first electrode 102 and the second electrode 104 each include a current collector and an electrode film. The electrodes 102 and 104 include electrode films 112 and 114, respectively. The films 112 and 114 can have any suitable shape, size, and thickness. For example, the electrode film may be about 30 microns (μm) to about 250 microns, e.g., about 50 microns, approximately 100 microns, approximately 150 microns, approximately 200 microns, approximately 250 microns Ron, about 300 microns, about 400 microns, about 500 microns, about 750 microns, about It can have a thickness of 1000 microns, about 2000 microns, or any value therebetween. Electrode films generally contain one or more active materials, such as the active materials provided herein. The electrode films 112 and / or 11 4 is a dry and / or self-supporting electrode film as provided herein; and have advantageous properties such as tensile strength or capacity as provided herein. The first electrode film 112 and / or the second electrode film 114 may also be any of the films described herein. The binder may also contain one or more additional particulate non-fibrillating binders such as those described above. The electrode films 112 and / or 114 may include an insulator. The electrode films 112 and / or 11 may be prepared by a process such as that described above. 4 may be a wet or self-supporting dry electrode as described herein .

[0039] As shown in FIG. 1, the first electrode 102 and the second electrode 104 are each a first electrode filter. The first current collector 108 contacts the electrode film 112, and the second current collector 11 contacts the second electrode film 114. The first current collector 108 and the second current collector 110 have respective electrode fillers. The first current collector 108 and the second current collector 109 facilitate electrical connection between the system and an external electrical circuit (not shown). The second current collector 110 and / or the second current collector 110 may comprise one or more conductive materials and may be externally connected to the corresponding electrode. Any suitable shape and size selected to facilitate the transfer of charge to and from the internal circuitry. For example, the current collector may be made of aluminum, nickel, copper, rhenium, tantalum, and precious metals such as silver, gold, platinum, palladium, rhodium, osmium and materials containing aluminum, iridium, and alloys and combinations thereof. For example, the first current collector 108 and / or the second current collector 110 can be, for example, The first current collector 108 and / or the second current collector 109 may comprise aluminum foil or copper foil. The body 110 is sized to provide charge transfer between the corresponding electrode and an external circuit. It may have a rectangular or approximately rectangular shape.

[0040] In some embodiments, the at least one active material comprises a treated carbon material. The treated carbon material is described in U.S. Patent Application Publication No. 2014 / 0098464. As described above, the number of hydrogen-containing, nitrogen-containing, and / or oxygen-containing functional groups For example, the treated carbon particles may include a reduction in one or more of the surface areas of the treated carbon. The reduction of one or more functional groups, e.g., the reduction of one or more functional groups compared to an untreated carbon surface. The reduction can be from about 10% to about 60%, and can be from about 20% to about 50%. The carbon is bonded to a reduced number of hydrogen-containing, nitrogen-containing, and / or oxygen-containing functional groups. In some embodiments, the treated carbon material may comprise less than about 0.5% In some embodiments, the treated The carbon material contains less than about 0.5%, including less than about 0.1%, of nitrogen-containing functional groups. In some embodiments, the treated carbon material contains less than about 5% oxygen, including less than about 3%. In a further embodiment, the treated carbon material has a higher molecular weight than the untreated carbon material. Contains approximately 30% fewer hydrogen-containing functional groups.

[0041] In some embodiments, the energy storage device 100 may be a lithium ion battery. In some embodiments, the electrode film of the lithium ion battery electrode can be A particulate non-fibrillating binder as described herein, one or more active materials, and fibrils The binder matrix may include a binder.

[0042] In a further embodiment, the energy storage device 100 is charged with a suitable lithium-containing electrolyte. For example, the device 100 may be a liquid containing a lithium salt and a solvent, such as a non-aqueous or organic solvent. Generally, lithium salts contain redox-stable anions. In some embodiments, the anion may be monovalent. The salts are hexafluorophosphate (LiPF6), lithium tetrafluoroborate (L iBF4), lithium perchlorate (LiClO4), lithium bis(trifluoromethane sulfonylimide (LiN(SO2CF3)2), lithium trifluoromethanesulfonate LiSO3CF3, LiSO4CF3, LiSO5CF3, LiSO6CF3, LiSO7CF3, LiSO8CF3, LiSO9CF3, LiSO9CF3, LiSO10CF3, LiSO11CF3, LiSO12CF3, LiSO13CF3, LiSO14CF3, LiSO15CF3, LiSO16CF3, LiSO17CF3, LiSO18CF3, LiSO19CF3, LiSO19CF3, LiSO In this embodiment, the electrolyte comprises a quaternary ammonium cation and a hexafluorophosphate an anion selected from the group consisting of tetrafluoroborate, tetrafluoroborate, and iodide; In some embodiments, the salt concentration is from about 0.1 mol / L (M) to about 0.1 mol / L (M). It may be about 5M, about 0.2M to about 3M, or about 0.3M to about 2M. In some embodiments, the salt concentration of the electrolyte may be from about 0.7 M to about 1 M. In this case, the salt concentration of the electrolyte is about 0.2M, about 0.3M, about 0.4M, about 0.5M, and about 0.6M. M, approximately 0.7M, approximately 0.8M, approximately 0.9M, approximately 1M, approximately 1.1M, approximately 1.2M, or It may be any value between these.

[0043] In some embodiments, the electrolyte of the energy storage device can include a liquid solvent. The solvent does not need to dissolve all components, but rather must completely dissolve any component of the electrolyte. In a further embodiment, the solvent may be an organic solvent. In an embodiment, the solvent is selected from carbonates, ethers and / or esters. In some embodiments, the solvent may include a carbonate. In a further embodiment, the carbonate may be, for example, ethylene carbonate. Ethylene carbonate (EC), propylene carbonate (PC), vinyl ethylene carbonate (VEC) ), vinylene carbonate (VC), fluoroethylene carbonate (FEC), and Cyclic carbonates such as combinations thereof, or, for example, dimethyl carbonate ( DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and The carbonates may be selected from acyclic carbonates such as cyclic carbonates, ... In an embodiment, the electrolyte may include LiPF6 and one or more carbonates. .

[0044] In some embodiments, the lithium ion battery has a voltage of about 2.5 to 4.5 V, or 3. In a further embodiment, the device is configured to operate from 0 to 4.2V. The batteries are each configured to have a minimum operating voltage of about 2.5V to about 3V. In another embodiment, the lithium ion batteries have a maximum voltage of about 4.1 V to about 4.4 V, respectively. It is configured to have a large operating voltage.

[0045] The terms "battery" and "capacitor" as used herein are understood by those skilled in the art to mean "battery" and "capacitor" shall be given their ordinary and accustomed meanings. The terms "capacitor" and "battery" are not mutually exclusive. A capacitor or battery can operate independently. A single electric It can refer to a chemical cell.

[0046] As used herein, the voltage of an energy storage device is the voltage of a single battery or capacitor. The operating voltage for the capacitor cell. The voltage may exceed the rated voltage or may be voltage below the rated voltage or according to manufacturing tolerances.

[0047] As provided herein, a "self-supporting" electrode film is an electrode film or layer Support the film or layer so that it can stand on its own and maintain its shape This electrode film incorporates a binder matrix structure. When embedded in such a binder matrix, the self-supporting electrode film or active layer may be Generally, and depending on the method employed, such The electrode film acts as an energy storage device without external supporting elements such as current collectors or other films. It has sufficient strength to be used in the manufacturing process of the storage device. The electrode film is wound and removed without any other supporting elements during the electrode manufacturing process. The cathode electrode film has sufficient strength to be handled and unwound. The dry electrode films described herein, such as the anode or cathode electrode films, are self-supporting. may be.

[0048] As provided herein, a "solvent-free" electrode film is one that does not contain any detectable processing solvent. The electrode film is free of process solvent residues or process solvent impurities. The dry electrode films described herein, such as the polar or anode electrode films, , may be solvent-free.

[0049] The "wet" electrodes, "wet process" electrodes, or slurry electrodes provided herein are: At least one step comprising a slurry of active material, a binder, and optionally additives. Wet electrodes are generally electrodes that are prepared by the method described above. , due to the solvents used during processing, detectable amounts of processing solvent residues, and / or Contains solvent impurities.

[0050] As used herein, a "non-destructive" process refers to a process that removes the electrode active material, including the surface of the electrode active material. The active material is not substantially altered during the process. Analytical properties and / or performance in applications such as incorporation into energy storage devices may vary depending on the product. The coating on the active material is the same or nearly the same as that which has not been subjected to the process. The material may be undisturbed or substantially undisturbed during the process. Non-limiting examples of the process are "non-destructive mixing or blending" and include reducing pressure, increasing feed rate, Decrease in blending speed (e.g., blender speed) and / or changes in other process parameters The shear applied to the active material, such as by jet milling, is implemented in energy storage devices. remain below the threshold at which the analytical properties and / or performance of the active material are adversely affected when The "non-destructive" process involves mixing the electrode active material, such as the surface of the electrode active material. High shear may substantially modify the active material and substantially affect its analytical properties and / or performance. For example, high shear blending or jet milling can be distinguished from electrolytic processes. High shear processes can have a detrimental effect on the surface of the active material. without compromising the fibrillation of the binder material or the formation of a self-supporting electrode film. It is implemented to provide other benefits such as forming a binder / active material matrix to aid in Embodiments herein may be used to prevent harmful effects of excessive use of high shear processes. Generally, the non-destructive processes herein provide similar benefits while avoiding the impact of run at one or more of a higher feed rate, lower velocity, and / or lower pressure. This allows for a more efficient and cost-effective electrode, rather than a destructive process that substantially alters the electrode active material and impacts performance. This also results in a low shear process.

[0051] In some embodiments, the electrode films provided herein comprise at least one active The at least one active material comprises a binder. The active material can be any active material known in the art. At least one active material is The anode active material may be any material suitable for use in the node or cathode. For example, intercalation materials (such as carbon, graphite, and / or graphene), alloyed / unalloyed silicon, silicon oxide, tin, and / or tin oxide), metal alloys or are compounds (such as Si-Al and / or Si-Sn), and / or conversion materials (such as oxides manganese oxide, molybdenum oxide, nickel oxide, and / or copper oxide). The anode active material can be used alone or mixed to form a multiphase material (Si -C, Sn-C, SiOx-C, SnOx-C, Si-Sn, Si-SiOx, Sn-S nOx, Si-SiOx-C, Sn-SnOx-C, Si-Sn-C, SiOx-Sn, or Sn—SiOx—SnOx, etc.). For example, it may be a metal oxide, a metal sulfide, or a lithium metal oxide. Metal oxides include, for example, lithium nickel manganese cobalt oxide (NMC), lithium Manganese oxide (LMO), lithium iron phosphate (LFP), lithium cobalt oxide (L CO), lithium titanate (LTO), and / or lithium nickel cobalt aluminum In some embodiments, the cathode active material may be a niobium oxide (NCA). The material is, for example, a layered transition metal oxide (LiCoO2 (LCO), Li(NiMnCo)O 2(NMC) and / or LiNi 0.8 Co 0.15 Al 0.05 O2 (NCA) etc.), spinel manganese oxide (LiMn2O4 (LMO) and / or LiMn 1. 5Ni 0.5 O4 (LMNO) etc.) or olivine (LiFePO4 etc.) Good too.

[0052] The at least one active material may comprise one or more carbon materials. For example, graphite materials, graphite, graphite-containing materials, hard carbon, soft carbon, carbon nanotubes, porous The graphite may be selected from a porous carbon, a conductive carbon, or a combination thereof. Activated carbon can be synthetic or naturally derived. In some embodiments, the graphite material may be derived from a surface treated In some embodiments, the porous carbon may comprise activated carbon. In some embodiments, the porous carbon can include hierarchical carbon. In some embodiments, the porous carbon is a structured carbon nanotube, a structured carbon nanotube, a Some embodiments may include wires and / or structured carbon nanosheets. In some embodiments, the porous carbon can include graphene sheets. The porous carbon may be surface-treated carbon.

[0053] In some embodiments, a lithium ion battery or hybrid energy storage device The cathode electrode film of the present invention comprises at least one active material in an amount of from about 70% to about 92% by weight. or about 70% to about 96% by weight, or about 70% to about 98% by weight In some embodiments, the cathode electrode film comprises about 5 layers of porous carbon material. %, or from about 1% to about 5% by weight, including up to about 10% by weight In some embodiments, the cathode electrode film comprises about 1 wt % to about 1 wt % of the conductive additive. In some embodiments, the cathode may comprise up to about 5% by weight, including 3% by weight. The electrode film may contain up to about 20% by weight of binder, for example, about 1.5% to 10% by weight. , about 1.5% to 5% by weight, or about 1.5% to 3% by weight. In some embodiments, the cathode electrode film comprises about 1.5 wt % to about 3 wt % of the binder. It may contain % by weight.

[0054] In some embodiments, the anode electrode film comprises at least one active material, a bilayer, In some embodiments, the conductive layer may include a conductive material, and optionally a conductive additive. The conductive additive may include a conductive carbon additive such as carbon black. In this embodiment, at least one active material of the anode is selected from the group consisting of synthetic graphite, natural graphite, and the like. Carbon, hard carbon, soft carbon, graphene, mesoporous carbon, silicon, silicon oxide, silicon Zinc, tin oxide, germanium, lithium titanate, mixtures or composites of the foregoing materials In some embodiments, the anode electrode film may include at least one about 80% to about 98% by weight, or about 94% to about 97% by weight of one active ingredient In some embodiments, the composition may comprise from about 80% to about 98% by weight of The node electrode film contains up to about 5 wt %, including 1 wt % to about 3 wt %, of a conductive additive. In some embodiments, the anode electrode film may comprise a binder in an amount of about 1 0.5% to 10% by weight, about 1.5% to 5% by weight, or about 3% to 5% by weight In some embodiments, the anode electrode may comprise up to about 20% by weight, including up to about 20% by weight. The film comprises about 4% by weight of a binder. In some embodiments, the anode film may be free of conductive additives.

[0055] Some embodiments may include an anode and / or cathode having one or more binders. The one or more binders may be, as described herein, 0 a particulate non-fibrillating binder having a particle size in the range of 0.5 μm to 40 μm; In some embodiments, it is included in conjunction with a fibrillating binder. The indole may be cellulose or a derivative of cellulose. cellulose esters such as cellulose acetate, methyl cellulose, ethyl cellulose, Cellulose, hydroxypropyl cellulose (HPC), or hydroxyethyl cellulose cellulose ethers such as cellulose ether (HEC), cellulose nitrate, or e.g., carboxylates. Dimethylcellulose (CMC), carboxyethyl cellulose, carboxypropyl cellulose cellulose, or a carboxyalkyl cellulose such as carboxyisopropyl cellulose In a further embodiment, the cellulose or cellulose derivative may comprise In a further embodiment, the cellulose salt cation may be The cellulose may be selected from sodium, ammonium, or lithium. The cellulose derivatives include sodium cellulose ester, sodium cellulose ester, cellulose, sodium nitrate, or sodium carboxyalkylcellulose It can contain selected sodium cellulose or sodium cellulose derivatives. In a preferred embodiment, the particulate non-fibrillating binder is CMC. CMC is Sodium carboxymethylcellulose may also be included.

[0056] Cellulose derivatives can be characterized by their degree of substitution. For example, the degree of substitution is , about 0.7 to about 1.5, or about 1.2. In some cases, some substitution may be desirable to provide desired properties. However, commercially available CMC in powder form is found to be limited to a specific particle size and degree of substitution. For example, a commercially available CMC powder with a degree of substitution of 1.2 has a larger particle size. Smaller particle sizes, up to about 40 μm, were found to be only available in It was found that the degree of substitution was limited to 0.7, which is an undesirable degree of substitution. As mentioned above, smaller CMC powders are needed to meet the recognized need for such materials. It was not recognized and certainly not available at the desired degree of substitution.

[0057] In some embodiments, the cellulose or cellulose derivative may include cross-links Furthermore, cellulose or cellulose derivatives are generally characterized by their molecular weight, which is the number average molecular weight. In some embodiments, the cellulose or cell The sucrose derivatives may have an α-to-β ratio of about 10,000 to about 500,000, or about 50,000 to about 4 It has a number average molecular weight of 00,000.

[0058] The one or more binders may be polytetrafluoroethylene (PTFE), polyolefin, Polyalkylenes, polyethers, styrene-butadienes, polysiloxanes and polysiloxanes copolymers of oxanes, branched polyethers, polyvinyl ethers, their copolymers, and and / or mixtures thereof. The binder may include cellulose. Cellulose can be prepared from carboxymethylcellulose (CMC), for example. In some embodiments, the polyolefin may be a polyolefin. Ethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), The binder may include copolymers thereof, and / or mixtures thereof. Polyvinylene chloride, poly(phenylene oxide) (PPO), polyethylene-block copolymer -poly(ethylene glycol), poly(ethylene oxide) (PEO), poly(phenylene Polyethylene oxide (PPO), polyethylene-block-poly(ethylene glycol), Polydimethylsiloxane (PDMS), polydimethylsiloxane-coal alkylmethylsiloxane The polymers may include olefins, copolymers thereof, and / or mixtures thereof. In an embodiment, the fibrillating binder is PTFE. In some embodiments, the binder may include an interpenetrating network of the aforementioned binders. The one or more binders include CMC, PVDF, and PTFE.

[0059] The binder may include various suitable ratios of polymer components. The lysed binder can be up to 50% by weight of the binder. For example, particulate non-fibrillar binders. The polymerized binder is from about 0.1% to about 50% by weight, from about 0.5% to about 10% by weight, about 0.5% to about 5% by weight, about 0.5 to about 2% by weight, or about 0.5 to about 1% by weight %. The PTFE can be up to about 98% by weight of the binder, for example, from about 20% to about 95% by weight, about 20% to about 80% by weight, about 30% to about 70% by weight, about 30% to about 80% by weight about 20% to about 50% by weight, or about 50% to about 90% by weight In some embodiments, the one or more binders may be from about 0.1 to about 90% by weight. from about 0.1 to about 2 wt.% CMC, from about 0.1 to about 2 wt.% PVDF, and from about 1 to about 4 wt.% In certain embodiments, the one or more binders comprise about 1 wt. % CMC, It contains about 1% by weight of PVDF and about 2% by weight of PTFE.

[0060] In some embodiments, the particulate non-fibrillating binder particles are between about 0.5 μm and About 40 μm, for example, about 1 μm to about 25 μm, about 2 μm to about 20 μm, about 5 μm to The electrode filler may have a median particle size of about 15 μm, or about 10 μm to about 15 μm. The sphere mixture contains a mixture of particles other than fine, non-fibrillating binder particles having a selected size. It may further comprise binder particles, for example, PTFE binder particles. In some embodiments, the binder particles may be about 50 nm, about 100 nm, about 150 nm, about 200 nm, about 250nm, approx. 300nm, approx. 350nm, approx. 400nm, approx. 450nm, approx. 500nm , about 1μm, about 2μm, about 3μm, about 4μm, about 5μm, about 10μm, about 50μm, about 1 00 μm, or any value therebetween.

[0061] Dry manufacturing processes do not use or substantially use solvents to form the electrode film. For example, the process of forming an electrode film containing an active material and a binder The components of the film may include dry particles. In some embodiments, the dry particles may be combined to provide a dry particle electrode film mixture. , the electrode film is the weight percentage of the components of the electrode film and the dry particle electrode film The dry particle electrode filler is mixed so that the weight percentages of the components in the polymer mixture are substantially the same. In some embodiments, the polymer may be formed from a rubber mixture using a dry manufacturing process. The electrode film formed from the dry particle electrode film mixture is a solvent and the resulting It may be free or substantially free of any processing additives such as solvent residues. In some embodiments, the resulting electrode film is prepared using a dry process from a dry particle mixture. In some embodiments, the resulting electrode film is a self-supporting film. The film is a free-standing film formed using a dry process from a dry particle electrode film mixture. The process for forming the active layer or electrode film is fibrillating the fibrillating binder component to comprise a fibrillated binder matrix; In a further embodiment, the free-standing electrode film may include In yet a further embodiment, the electrode film may be formed in the absence of a film. The tissue may include a fibrillated polymer matrix so that the tissue is self-supporting. forming a matrix, lattice, or web of metals to provide mechanical structure to the electrode film. It is thought that this can be done.

[0062] In some embodiments, the electrode film comprises a particulate, non-fibrillated electrode film as described herein. Energy storage device electrodes that are dry and / or self-supporting films containing binders The film has a specific capacity of approximately 300mAh / g and approximately 325mAh / g during charging and discharging. , about 350mAh / g, about 375mAh / g, about 400mAh / g, about 425mAh / g , about 450 mAh / g, about 500 mAh / g, or a range of values ​​therebetween. In a further embodiment, the electrode film comprises a particulate non-fibrillar polymer film as described herein. The charge carrier of the energy storage device is a dry and / or self-supporting film containing a polymeric binder. Polarized films may have a porosity of about 90%, about 91%, about 92%, about 93%, or a range of values ​​therebetween. may provide a first cycle efficiency of

[0063] The electrode film can have a selected thickness suitable for a particular application. The thickness of the electrode film provided in is the thickness of the electrode film prepared by conventional processes. In some embodiments, the electrode film may be thicker than about 250 microns. , about 300 microns, about 350 microns, about 400 microns, about 450 microns, about 50 0 microns, about 750 microns, about 1 mm, or about 2 mm, or any value therebetween. It can have a range of thicknesses.

[0064] In some embodiments, a self-assembly composition comprising the particulate non-fibrillating binder described herein is provided. The upstanding and / or self-supporting electrode film may have a tensile strength of at least about 1 N. In further embodiments, the tensile strength is about 1 N, about 1.1 N, about 1.2 N, about 1.3 N, or about 1.4 N. N, approx. 1.4N, approx. 1.5N, approx. 1.6N, approx. 1.7N, approx. 1.8N, approx. 1.9N, approx. 2 N may be a value greater than about 2N, or a range of values ​​therebetween.

[0065] In some embodiments, the microparticles described herein, produced under substantially the same conditions, Setting of free-standing and / or self-supporting electrode films containing polymeric non-fibrillating binders The samples (e.g., a set of at least three electrode films) were measured with a standard deviation (s.d.) of less than approximately 3%. ), for example, about 2.5%sd, about 2%sd, about 1.5%sd, about 1%sd, about 0.5%sd d, or a range of values ​​therebetween.

[0066] In some embodiments, a composition comprising the particulate non-fibrillating binder described herein is Freestanding and / or self-supporting electrode films, including those made of equivalent active material, can be used, for example, in wet They may be characterized by a specific energy density 20-30% higher than battery electrodes.

[0067] In the specific examples below, electrode films were prepared containing particulate non-fibrillating binders. did.

[0068] Example 1 It contains 96% by weight of graphite and 4% by weight of binder, and the binder is 2% of PTFE, 1% A dry battery anode electrode film containing 1% CMC and 1% PVDF was fabricated. Polar film compositions can be envisioned and prepared, and the disclosure herein provides certain of the disclosed There is no limitation on the composition.

[0069] A Hosokawa 100AFG pressure jet mill with a classifier attachment was used. The received CMC powder was milled at a size output selection. Aldrich® sodium carboxymethylcellulose was used as the source material. It was used. 50 To select the size, the classifier rotation speed is 8000rpm. The grinding gas pressure was 120 psi and the initial chamber mass was 100 g. This resulted in a production rate of approximately 0.1 kg / hr. A photo of the 100AFG machine is shown in Figure 1. 2A and 2B. Received from SigmaAldrich® The CMC powder obtained has a D of approximately 70 μm. 50 particle size, while Hosokawa C after grinding The MC has a D of approximately 10 μm. 50 This difference can be seen in the SEM images of Figures 3A and 3B. Hosokawa crushed CMC can be used in the dry anode electrode parallel process. improved first cycle efficiency and cell-to-cell uniformity compared to as-received CMC. The electrochemical data for this comparison are shown in Figure 4. The charge-discharge specific capacities were 386 mAh / g and 348 mAh / g, respectively (efficiency 90 0.2%) were achieved with ground CMC. A charge-discharge specific capacity of 9 mAh / g (efficiency 90.9%) was achieved.

[0070] In addition to the improved electrochemical performance, the smaller D of CMC 50 The grain size is determined by the presence of holes, cracks or surfaces. Electrode defects such as surface pits have been improved. 50 Particle size 70 μm The dry powder formulation using CMC powder produced a free-standing electrode film with defects as shown in Figure 5. These defects were generated as shown in Figure 6. 50 The particle size was crushed to approximately 10 μm. This was avoided by using CMC. The basis for these experimental results is the smaller D 50 The larger surface area provided by the CMC particle size. At the weight ratio, a higher surface area results in a stronger bond strength to the active material powder matrix. , and used to produce films or to calender film thickness In contrast, a more viscous material may provide a weaker affinity to the heated rollers used to Bigger D 50 The CMC particle size results in weaker bond strength to the active material powder matrix, and and used to make films or to calender film thickness This may provide a stronger affinity to the heated rollers used for heating. This stronger affinity for the calender rollers allows the particles to be directly applied to the heated calender rollers during dry processing. The larger D of the CMC binder particles found in contact, unground powder 50 This can be attributed to the larger single spot size of the particle size. The particles are either accidentally removed from the electrode powder sample during powder-to-film formation or are present in the film. During the film-to-film thickness reduction process, defects are extracted from the film, creating defects in the electrode. The tensile strength of the free-standing electrode film was also measured using a finely ground CMC polymer binder. The results of tensile strength support the idea that there is strong bond cohesion strength in the smaller D5 Electrodes of similar thickness fabricated using CMC binder with zero particle size (10 μm vs. approximately 70 μm) The films are shown to be stronger than those made with larger particle sizes. The experimental results are shown in Table 1. Shown below.

[0071] [Table 1]

[0072] Although specific embodiments of the present invention have been described above, these embodiments are presented by way of example only. and are not intended to limit the scope of the present disclosure. Indeed, The novel methods and systems described herein may be embodied in a variety of other forms. Various omissions, substitutions, and modifications in the systems and methods described herein are intended to be illustrative and not restrictive of the present disclosure. The appended claims and their equivalents are intended to be illustrative and not restrictive. It is intended to cover such forms or modifications as would fall within the scope and spirit of the present disclosure. Accordingly, the scope of the present invention is defined solely by reference to the appended claims. can be.

[0073] Any features, materials, characteristics, or groups described with respect to a particular aspect, embodiment, or example may be used without notice. The group may be combined with any other aspect, embodiment, or method described in this section or elsewhere herein. Unless otherwise compatible with the examples, they should be understood to be applicable to them. All features disclosed in the accompanying claims, abstract and drawings, and / or or any step of any method or process so disclosed. Any feature and / or step is not mutually exclusive unless at least some of the features and / or steps are mutually exclusive. Protection is not limited to the details of the foregoing embodiments. Protection is granted to all inventions disclosed in this specification (including the accompanying claims, abstract and drawings). Any novel one or any novel combination of features or features so disclosed Any novel or novel combination of steps of any method or process It extends to the combination.

[0074] Furthermore, certain features that are described in this disclosure in the context of separate embodiments may also be used in a single embodiment. Conversely, the embodiments described in the context of a single embodiment may be implemented in combination. The various features may be implemented in multiple embodiments separately or in any suitable subcombination. Furthermore, features may be described above as acting in certain combinations. However, one or more features from a claimed combination may, in some cases, be deleted from the combination. The combination may be a subcombination or a variation of a subcombination. It may be claimed as a

[0075] Additionally, the operations may be shown in the figures or described herein in a particular order. However, such operations may not necessarily be performed in the particular order shown or in sequence to achieve a desired result. The operations do not have to be performed in the sequential order or all of the operations. Other operations may be incorporated into the exemplary methods and processes. For example, one or more may perform multiple additional operations before, after, simultaneously with, or between any of the operations described. Additionally, the operations may be rearranged or reordered in other embodiments. Those skilled in the art will appreciate that in some embodiments, the processes shown and / or disclosed It is understood that the actual steps taken in the process may differ from those shown in the drawings. Depending on the embodiment, some of the steps described above may be omitted. Further, certain embodiments disclosed above may be modified in various ways. The features and attributes may be combined in different ways to form additional embodiments. All of these are within the scope of the present disclosure. The separation of stem components is not intended to require such separation in all embodiments. The components and systems described should not be understood as a single product. It should be understood that the device may be integrated into a single product or packaged into multiple products. For example, any of the components for the energy storage systems described herein may be separately or may be integrated to form an energy storage system. (e.g., may be packaged together or attached together).

[0076] For purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not necessarily all such advantages may be achieved in accordance with any particular embodiment. Thus, for example, one skilled in the art would understand that the present disclosure does not It is understood that the present invention is not limited to the above and may be practiced in a variety of ways, including but not limited to, to achieve one benefit as taught herein without necessarily achieving other benefits as may be obtained. It will be recognized that the present invention may be implemented or performed in a manner that achieves a group of points or advantages. cormorant.

[0077] Conditional words such as "possible," "might," "could," and "may" are used unless otherwise specified. Unless otherwise understood, or in the context in which it is used, it generally refers to other implementations. While an embodiment may not include certain features, elements, and / or steps, it may be possible to implement a particular embodiment. Therefore, such conditional language is generally In some cases, features, elements, and / or steps may appear in one or more embodiments. What is required, or one or more embodiments may depend on the presence or absence of user input or prompting Regardless, these features, elements, and / or steps may be combined in any particular embodiment. To determine whether it should be included or implemented in any particular embodiment It is not intended to necessarily include the logic of

[0078] Unless otherwise specified, conjunctions such as the phrase "at least one of X, Y, and Z" Generally used to convey that an item, term, etc. can be either X, Y, or Z. Such conjunctions, understood apart from the context in which they are used, may be used to indicate that a particular embodiment is X, Require the presence of at least one of Y and at least one of Z. It is not generally intended.

[0079] As used herein, terms such as "approximately," "about," "generally," and "substantially" The degree of language used herein means that the device still performs the desired function or represents a value, amount, or characteristic that approximates a stated value, amount, or characteristic that achieves the result of

[0080] The scope of the present disclosure is limited to the preferred embodiments in this section or elsewhere herein. It is not intended to be limited by the specific disclosure of this section or this disclosure. As set forth elsewhere in this specification or as defined by the claims to be filed in the future. The claim language may be defined based on the language adopted in the claim. It should be broadly construed and not limited to the examples set forth herein, and the scope of the application The terms of the proceedings should be interpreted broadly and these examples should be construed as non-exclusive. should be.

Claims

1. A dry electrode film for an energy storage device, comprising: a dry active material; Fibrillating binder and D of about 0.5 to 40 μm ５０ Particulate non-filler with particle size a dry binder comprising a brilly binder; Freestanding dry electrode film.

2. The particulate non-fibrillating binder has a D of about 1 to 25 μm. ５０ having a particle size, Item 1. The dry electrode film according to item 1.

3. The dry binder comprises up to 50% by weight of the particulate non-fibrillating binder.

3. The dry electrode film according to claim 1 or 2.

4. The particulate non-fibrillating binder is at least one of cellulose and cellulose derivatives. The dry electrode film according to any one of claims 1 to 3, wherein the dry electrode film is selected from one of the following:

5. The particulate non-fibrillating binder is selected from the group consisting of cellulose, cellulose ester, cellulose ethers, cellulose nitrate, carboxyalkyl cellulose, cellulose salts and cellulose The dry electrode filter of claim 4, wherein the dry electrode filter is selected from at least one of the following: Room.

6. The particulate non-fibrillating binder is cellulose, cellulose acetate, methyl Cellulose, ethyl cellulose, hydroxypropyl cellulose (HPC), hydroxy Ethyl cellulose (HEC), cellulose nitrate, carboxymethyl cellulose (CMC) , carboxyethyl cellulose, carboxypropyl cellulose, carboxyisopropyl cellulose, sodium cellulose, sodium nitrate cellulose and carboxyalcohol 6. The composition according to claim 4 or 5, wherein the cellulose acetate compound is selected from at least one of sodium cellulose acetate. The dry electrode film described.

7. The particulate non-fibrillating binder is carboxymethyl cellulose (CMC) and and polyvinylidene fluoride (PVDF). The dry electrode film according to any one of claims 1 to 14.

8. The cellulose or the cellulose derivative has a molecular weight of about 10,000 to about 500,000. The dry electrode film according to any one of claims 4 to 7, having a number average molecular weight.

9. 9. The method according to claim 4, wherein the cellulose derivative has a degree of substitution of about 0.7 to about 1.

5.

10. The dry electrode film according to claim 1 .

10. 10. The method of claim 1, wherein the fibrillating binder comprises polytetrafluoroethylene (PTFE).

10. The dry electrode film according to any one of claims 4 to 9.

11. Claims 4 to 10, wherein the dry electrode film is substantially free of holes, cracks and surface pits. The dry electrode film according to any one of claims 1 to 10.

12. 12. Any one of claims 4 to 11, wherein the dry electrode film has a tensile strength of at least about 1 N. The dry electrode film according to any one of claims 1 to 14.

13. The dry active material according to any one of claims 4 to 12, wherein the dry active material comprises graphite. Electrode film.

14. The dry electrode film according to any one of claims 4 to 13, which is in contact with a current collector. an electrode.

15. A lithium ion battery comprising the electrode of claim 14.

16. A dry non-fibrillating binder is treated with high shear to produce a dry particulate non-fibrillating binder. forming a da; A dry fibrillating binder is combined with the dry particulate non-fibrillating binder. forming a dry electrode film composite; and calendering the dry electrode film mixture to form a free-standing dry electrode film. The degree, A method for manufacturing a dry electrode film for an energy storage device, comprising:

17. providing a dry particulate non-fibrillating binder; a first non-destructive mixing process for mixing the dry particulate non-fibrillating binder with a first with a dry active material to form a dry bulk active material mixture; The dry fibrillating binder is mixed with a second dry active material by a high shear mixing process. forming a dry structural binder mixture; The dry bulk active material mixture and the dry structural binder mixture are mixed in a second non-destructive mixing process. and mixing the mixture by a process to form a dry electrode film mixture. producing a free-standing dry electrode film from the dry electrode film mixture; A method for manufacturing a dry electrode film for an energy storage device, comprising:

18. The dry non-fibrillating binder is processed at high shear to form the dry particulate non-fibrillating binder. The method of claim 17 further comprising forming a runner.

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