Improved battery separator, electrode, cell, lithium battery, and related method

Abstract

To provide an improved battery separator and an energy cell including the improved battery separator.SOLUTION: An improved battery separator includes a porous membrane that, when wetted by electrolyte, has at least one of the following properties, no or low volume, no or low mass, soaks up as much liquid electrolyte as possible, blocks or removes any deleterious substances in the electrolyte, does not melt at any high temperature, does not react with the cathode or anode under any conditions, has mechanical strength equal to or greater than steel, is an electronic insulator under all conditions, and blocks metal dendrite growth.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Priority claim This application claims the benefit of and priority under 35 U.S.C. §119(e)(1) to U.S. Provisional Patent Application No. 62 / 473,596, filed March 20, 2017, which is incorporated herein by reference in its entirety.

[0002] According to at least selected embodiments, the present disclosure or invention is directed to new or improved separators, battery separators, electrodes, cathodes, anodes, batteries, cells, systems, and / or methods of designing, understanding, manufacturing, and / or using such separators, battery separators, electrodes, cathodes, anodes, cells, systems, etc. for lithium batteries, particularly secondary lithium batteries, e.g., secondary lithium-ion batteries, and / or CE, ESS, and / or EDV batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved methods for investigating or defining tortuosity, porosity, lithium deposition, and cell design using such new ideas, definitions, and / or data. Also disclosed herein are methods, systems, and battery components for improving battery life, reducing battery failure, reducing dendrites, reducing lithium deposition, maintaining charge and discharge rates, improved configuration, improved performance, and the like. [Background technology]

[0003] There is a need for improved battery separators, particularly lithium ion battery separators that, among other things, block dendrites and do not melt at high temperatures.

[0004] Carbonaceous materials have been commonly used as anode materials in lithium-ion batteries. Although the energy density of carbonaceous materials is very high, the charge and discharge voltages are very close to those of lithium deposition. Therefore, lithium deposition can occur due to excessive potential, especially under high charge rates, causing significant polarization. Lithium metal deposition in batteries poses serious safety concerns and can lead to thermal events, runaway, or explosion. Therefore, there is a need for lithium-ion batteries or cells that do not undergo lithium deposition even at high charge rates. Summary of the Invention [Problem to be solved by the invention]

[0005] According to at least selected embodiments, the present disclosure or invention may address the above-mentioned needs, challenges, or problems and / or is directed to new or improved separators, battery separators, electrodes, cathodes, anodes, batteries, cells, systems, and / or methods of designing, understanding, manufacturing, and / or using such separators, battery separators, electrodes, cathodes, anodes, cells, systems, etc. for lithium batteries, particularly secondary lithium batteries, e.g., secondary lithium-ion batteries, and / or CE, ESS, and / or EDV batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved methods for investigating or defining tortuosity, porosity, lithium deposition, and cell design using such new ideas, definitions, and / or data. Also disclosed herein are methods, systems, and battery components for improving battery life, reducing battery failure, reducing dendrites, reducing lithium deposition, maintaining charge and discharge rates, improved configuration, improved performance, and the like. [Means for solving the problem]

[0006] In one aspect, this application is directed to an improved battery separator. The improved separator, when wetted by an electrolyte, has at least one of the following properties: no or low volume; no or low mass; absorbs the liquid electrolyte as much as possible; blocks or removes any harmful substances in the electrolyte; does not melt at any high temperature; does not react with the cathode or anode under any conditions; has mechanical strength equal to or greater than that of steel; is an electronic insulator under any conditions; and blocks metal dendrite growth. In some embodiments, the separator has one or more of the above properties. In some embodiments, the separator has two or more of the above properties. In some embodiments, the separator has three or more of the above properties. In some embodiments, the separator has four or more of the above properties. In some embodiments, the separator has five or more of the above properties. In some embodiments, the separator has six or more of the above properties. In some embodiments, the separator has seven or more of the above characteristics, in some embodiments, the separator has eight or more of the above characteristics, in some embodiments, the separator has all nine or at least all nine of the above characteristics.

[0007] In some embodiments, the battery separator described herein above is a porous, microporous, or nanoporous battery separator, and the pores of the battery separator are filled with an ionically conductive medium. In some embodiments, a battery separator having pores filled with an ionically conductive medium conducts lithium ions when dry (no electrolyte added), when wetted with electrolyte, or both when dry (no electrolyte added) and when wetted with electrolyte.

[0008] In another embodiment, 3.0 C (1 C=2.3 mA / cm) without lithium deposition 2 ) or greater. In some embodiments, the cell may be capable of being charged at a charge rate that is 3.5C or greater, 4.0C or greater, 4.5C or greater, or 3.0C or greater and less than 5.0C.

[0009] The energy cell includes at least the following: an anode including lithium; and a cathode.

[0010] In some embodiments, the lithium-containing anode has a thickness of about 50 to about 200 microns. The thickness may be about 60 to about 200 microns, or about 60 to about 125 microns. The porosity of the anode may be 15% or more, 20% or more, 30% or more, or 40% or more in some embodiments. In some embodiments, the porosity of the anode may be 15% or more and 50% or less in some embodiments. The tortuosity of the anode may be 2.0 or less, 1.7 or less, 1.5 or less, 1.3 or less, or 1.2 or less in some embodiments. In some embodiments, the tortuosity is between 1.0 and 2.0, preferably between 1.2 and 2.0. Even more preferably, the tortuosity of the anode may be 1.2 or more and 1.3 or less.

[0011] In some embodiments, the lithium-containing anode is selected from the group consisting of lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni x Mn y Co z )O2), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni x CO y Al z )O2), where 0.8>x>0.9 and x+y+z=1; and combinations thereof.

[0012] In some embodiments, the cathode of an energy cell described herein has a thickness of about 50 to about 200 microns, about 75 to about 200 microns, or about 75 to about 150 microns. The porosity of the cathode, in some embodiments, may be 10% or more, 15% or more, 20% or more, 30% or more, or 10% or more but less than 40%. The tortuosity of the cathode, in some embodiments, may be 2.0 or less, 1.7 or less, 1.5 or less, 1.3 or less, or 1.2 or less. In some preferred embodiments, the tortuosity of the cathode may be 1.0 or more and 2.0 or less. Even more preferably, the tortuosity of the cathode may be 1.2 or more and 1.5 or less.

[0013] The cathode of the energy cell, in some embodiments, may be made of at least one material selected from the group consisting of natural graphite; artificial graphite; amorphous carbon; alloys containing tin and / or silicon; spinel lithium titanate; and combinations thereof.

[0014] Furthermore, in addition to the lithium-containing anode and cathode, the energy cells described herein may include an electrolyte. The electrolyte may be selected from the group consisting of ethylene carbonate (EC); ethyl methyl carbonate (EMC); diethyl carbonate (DEC); dimethyl carbonate (DMC); propylene carbonate (PC); and combinations thereof. In some embodiments, the electrolyte may include an electrolyte additive.

[0015] In some further embodiments, the energy cells described herein may include a separator, including the improved separators described herein. For example, the energy cells may include a lithium-containing anode, a cathode, and a separator. In some other embodiments, the energy cells may include a lithium-containing anode, a cathode, an electrolyte, and a separator.

[0016] In some embodiments, the energy cell may be a primary or secondary energy cell.

[0017] In another aspect, anodes comprising lithium are described herein. The lithium-containing anodes can be used in the energy cells described herein. In some embodiments, the lithium-containing anodes have a thickness of about 50 to about 200 microns. The thickness may be about 60 to about 200 microns, or about 60 to about 125 microns. The porosity of the anode may be 15% or more, 20% or more, 30% or more, or 40% or more in some embodiments. In some embodiments, the porosity of the anode may be 15% or more and 50% or less in some embodiments. The tortuosity of the anode may be 2.0 or less, 1.7 or less, 1.5 or less, 1.3 or less, or 1.2 or less in some embodiments. In some embodiments, the tortuosity is between 1.0 and 2.0, preferably between 1.2 and 2.0. Even more preferably, the tortuosity of the anode may be 1.2 or more and 1.3 or less.

[0018] In some embodiments, the lithium-containing anode is selected from the group consisting of lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni x Mn y Co z )O2), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni x CO y Al z )O2), where 0.8>x>0.9 and x+y+z=1; and combinations thereof.

[0019] In some embodiments, the void space in the cathode may include an ionically conductive medium.

[0020] In another aspect, a cathode that can be used in the energy cells described herein is disclosed. In some embodiments, the cathode has a thickness of about 50 to about 200 microns, about 75 to about 200 microns, or about 75 to about 150 microns. The porosity of the cathode, in some embodiments, may be 10% or more, 15% or more, 20% or more, 30% or more, or 10% or more but less than 40%. The tortuosity of the cathode, in some embodiments, may be 2.0 or less, 1.7 or less, 1.5 or less, 1.3 or less, or 1.2 or less. In some preferred embodiments, the tortuosity of the cathode may be 1.0 or more and 2.0 or less. Even more preferably, the tortuosity of the cathode may be 1.2 or more and 1.5 or less.

[0021] The cathode, in some embodiments, may be made of at least one material selected from the group consisting of natural graphite; artificial graphite; amorphous carbon; alloys containing tin and / or silicon; spinel lithium titanate; and combinations thereof.

[0022] In some embodiments, the cathode void may include an ionically conductive medium (ICM). [Brief explanation of the drawings]

[0023] [Figure 1] Figure 1 shows ion transport, tortuosity, and Gurley. [Figure 2] Figure 2 shows ion transport and tortuosity. [Figure 3] FIG. 3 illustrates the design principles of an exemplary Li-ion cell. [Figure 4] FIG. 4 shows the polarization of a Li-ion cell. [Figure 5] FIG. 5 is a graphical representation of the Li concentration in the electrode particles after high current discharge. [Figure 6] FIG. 6 shows the electrochemical, thermal, and chemical models. [Figure 7] Figure 7 shows the basic electrochemical equation. [Figure 8] FIG. 8 shows a review of the potential, charge, and discharge in Li-ion at equilibrium. [Figure 9] FIG. 9 is a graph of the lithium concentration distribution in a 100% porous li-ion cell according to Faraday's reaction law. [Figure 10] FIG. 10 includes a graph showing the lithium concentration in the electrolyte upon charging and discharging. [Figure 11] FIG. 11 includes a graph showing the cathode potential drop in a discharge and an enlargement of a portion of such graph. [Figure 12] FIG. 12 includes a graph showing the anode potential increase in a 4C discharge and an enlargement of a portion of such graph. [Figure 13] FIG. 13 includes two graphs showing the electrode potential drop at the anode during 4C charging. [Figure 14] FIG. 14 includes a graph showing anode potential drop upon 4C charging and an enlargement of a portion of such graph. [Figure 15] FIG. 15 includes a graph showing cathode potential increase upon 4C charging and an enlargement of a portion of such graph. [Figure 16] FIG. 16 contains graphs from DCIR measurements showing cell voltage over time. [Figure 17] FIG. 17 includes two graphs plotting potential (V) / SOC versus thickness x (m) for electrodes having two different thicknesses, 1X and 2X, at the starting state (t=0). [Figure 18] FIG. 18 includes two graphs plotting potential (V) / SOC versus thickness x (m) for electrodes with two different thicknesses in the dynamic state (t>0). [Figure 19] FIG. 19 is a chart showing when Li deposition begins when different charging rates are used on electrodes having different thicknesses. [Figure 20] FIG. 20 is a chart showing when Li deposition begins when different charging rates are used on electrodes with different porosity values. [Figure 21]FIG. 21 is a chart showing when Li deposition begins when different charging rates are used on electrodes with different tortuosity values. [Figure 22] FIG. 22 is a chart containing baseline cell parameters for a cell without Li deposition. DETAILED DESCRIPTION OF THE INVENTION

[0024] The embodiments described herein may be more readily understood by reference to the following detailed description, examples, and figures. However, the elements, devices, and methods described herein are not limited to the specific embodiments presented in the detailed description, examples, and figures. It should be recognized that these embodiments merely illustrate the principles of the invention. Numerous modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the invention.

[0025] It should also be understood that all ranges disclosed herein encompass any and all subranges incorporated therein. For example, a range stated as "1.0 to 10.0" should be taken to include any and all subranges beginning with a minimum value greater than or equal to 1.0 and ending with a maximum value less than or equal to 10.0, such as 1.0 to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.

[0026] All ranges disclosed herein are also to be construed as including the endpoints of the range, unless expressly stated otherwise. For example, the ranges "between 5 and 10," "from 5 to 10," or "5-10" are generally to be construed as including the endpoints 5 and 10.

[0027] Furthermore, when the phrase "up to" is used in conjunction with an amount or quantity, it should be understood that the amount is at least a detectable amount or quantity. For example, if a material is present "up to" a certain amount, the specified amount may be present from the detectable amount up to and including the specified amount.

[0028] Described herein, according to at least selected embodiments, are improved battery separators, improved energy cells that optionally include the improved battery separators, and / or improved anodes and cathodes that are optionally used with the improved battery separators or the improved energy cells described herein.

[0029] Battery separator Unless otherwise specified in a particular embodiment, the membrane or battery separator described herein is not particularly limited. In some embodiments, the battery separator may be an improved battery separator that includes a porous membrane that, when wetted by an electrolyte, has at least one of the following properties: no volume or low volume; no mass or low mass; absorbs the liquid electrolyte as much as possible; blocks or removes any harmful substances in the electrolyte; does not melt at any high temperature; does not react with the cathode or anode under any conditions; has mechanical strength equal to or greater than steel; is an electronic insulator (no electronic conduction) under any conditions; blocks metal dendrite growth.

[0030] One way to impart some of the above properties is by incorporating a ceramic into the battery separator. For example, in some embodiments, a ceramic coating may be applied to one or more surfaces of a porous membrane that is part of the battery separator. In some embodiments, a ceramic material may be incorporated into a microporous membrane. For example, when the membrane is formed by a dry process, such as the Celgard® dry-stretch process, the ceramic material may be co-extruded with the polymer used, such as a polyolefin polymer, to form the membrane. In some embodiments, when the membrane is a multilayer membrane formed by a dry process, such as the Celgard® dry-stretch process, the ceramic material may be present in only some of the layers and not in others. The ceramic material may be incorporated into some of the layers but not others by extruding the ceramic material with the polymer used to form some of the layers, rather than extruding the ceramic material with the polymer used to form the others of the layers.

[0031] Many ceramics can conduct ions even better than liquids. See, for example, the disclosure of U.S. Patent No. 6,432,586, which is incorporated herein by reference in its entirety. Ceramics can also block or remove harmful substances in the electrolyte. Ceramics do not melt even at very high temperatures and do not react with most anode or cathode materials under most conditions. Ceramics are mechanically strong. Therefore, ceramics are one preferred material for imparting some of the properties of the improved battery separator described herein.

[0032] porous membrane Unless otherwise stated in a particular embodiment, the porous membranes described herein are not limited. The porous membranes may be nanoporous, microporous, or macroporous. In some preferred embodiments, the porous membranes are microporous.

[0033] Microporous, as used herein, means that the membrane contains micropores or micrometer-sized pores. In some embodiments, the average pore size of the microporous membrane is less than 2 microns, and in preferred embodiments, the average pore size is less than 1 micron. In some embodiments, the average pore size is between 0.01 and 1 micron, preferably between 0.01 and 0.08 microns, more preferably between 0.01 and 0.06 microns, and in some embodiments, 0.01 to 0.04, 0.01 to 0.03, or 0.1 to 0.02 microns.

[0034] In some preferred embodiments, the microporous membrane itself has a thickness in the range of 2 to 50 microns, 4 to 40 microns, 4 to 30 microns, 4 to 20 microns, 4 to 10 microns, or less than 10 microns, without any coating thereon, such as a ceramic coating. The thickness can be measured in micrometers (μm) using a 210-A micrometer thickness tester and test procedure ASTM D374. Thin microporous membranes are preferred for some applications. For example, when used as battery separators, thinner separator membranes allow for the use of more anode and cathode material in the battery, resulting in higher energy and higher power density batteries.

[0035] In some preferred embodiments, the microporous membrane has a surface porosity, such as about 40 to about 70%, optionally about 40 to about 65%, optionally about 40 to about 60%, optionally about 40 to about 55%, optionally about 40 to about 50%, optionally about 40 to about 45%, etc. In some embodiments, the porosity can be as low as 70%, optionally about 40 to about 65%, optionally about 40 to about 60%, optionally about 40 to about 55%, optionally about 40 to about 50%, optionally about 40 to about 45%, etc., when desired for a particular application. It can be greater than 0% and less than 40%, although the range of 40-70% is an operating range for battery separators and is one way in which the disclosed microporous membranes can be used. Porosity is measured using ASTM D-2873 and is defined as the percentage of void space, e.g., pores, in the area of ​​the microporous membrane, measured in the machine direction (MD) and transverse direction (TD) of the substrate.

[0036] In some preferred embodiments, the microporous membrane may have a JIS Gurley in the range of 50 to 300, 75 to 300, and / or 100 to 300. However, unless otherwise stated in a particular embodiment, the JIS Gurley value is not so limited, and higher JIS Gurley values, e.g., greater than 300, or lower JIS Gurley values, e.g., less than 50, may be desirable for different purposes. Gurley is defined herein as in the Japanese Industrial Standards (JIS Gurley) and is measured using an OHKEN permeability tester. JIS Gurley is defined as the time (seconds) required for 100 cc of air to pass through a 1-inch square film at a constant pressure of 4.9 inches of water.

[0037] The microporous membrane may be produced by any method consistent with the goals described herein. For example, in some preferred embodiments, the microporous membrane is a dry-process microporous membrane, meaning that the film is formed without the use of a solvent. An exemplary dry process is a dry-stretch process comprising, consisting of, or consisting essentially of extruding a polymer to form a non-porous precursor and stretching the precursor to, among other things, form pores. An exemplary dry-stretch process is the Celgard® dry-stretch process. In some embodiments, the extrusion process may include coextrusion, in which two or more polymer mixtures, which may be the same or different, are coextruded. In other embodiments, the microporous membrane may be made by a particle stretch manufacturing process and a beta-nucleated biaxially stretched (BN-BOPP) manufacturing process. Alternatively, in other embodiments, the porous substrate may be produced by a wet process, including the use of solvents and / or oils, sometimes known as a phase separation or extraction process, from Celgard Korea, Limited, Korea, Asahi Kasei, Japan, and / or Tonen, Japan. Alternatively, in other embodiments, the microporous membrane may be a woven or nonwoven type membrane. For example, in some embodiments, the microporous membrane may be formed using an electrospinning coating process. The electrospinning process provides a method for applying a polymer composition in the form of nanoscale fibers without the nanoscale fibers themselves needing to be porous. The spaces between the fibers provide the necessary openings or porosity in the electrospun coating or layer.

[0038] In some embodiments, the microporous membrane may be a monolayer, bilayer, or multilayer membrane. The term "layer" as used herein (e.g., in the terms "monolayer," "bilayer," or "multilayer") includes a monoextruded or monocast layer having a thickness of 2 to 50 microns. A monolayer may be a monoextruded or monocast layer having a thickness of 2 to 50 microns. As will be understood by those skilled in the art, a monoextruded layer is a layer extruded by itself and is not coextruded with any other layer. Also, the layers of a coextruded bilayer or multilayer microporous membrane, respectively, are referred to as "layers" as used herein. The number of layers in a coextruded bilayer is two, and the number of layers in a coextruded multilayer film is three or more. The exact number of layers in a bilayer or multilayer coextruded film is determined by the die design and not necessarily the materials coextruded to form the coextruded film. For example, a coextruded bilayer or multilayer film may be formed by using the same material to form each of two or more layers, and these layers, although each made of the same material, are still referred to as separate layers. The exact number The thickness of each layer of the coextruded two or multilayer film may be 0.1 to 20 microns, preferably 0.1 to 5 microns, and most preferably 0.1 to 3 microns, 0.1 to 2 microns, 0.1 to 1 micron, 0.1 to 0.9 microns, 0.1 to 0.8 microns, 0.1 to 0.7 microns, 0.1 to 0.6 microns, 0.1 to 0.5 microns, 0.1 to 0.4 microns, 0.1 to 0.3 microns, or 0.1 to 0.2 microns, again determined by die design.

[0039] Similarly, a single-layer microporous membrane consists of a single extruded or cast layer that is not extruded or cast along with any other layer. The single layer can have a thickness of, for example, 2 to 50 microns.

[0040] In other embodiments, the microporous membrane may be a two-layer microporous membrane, which is composed of two single extruded (monoextrusion) or cast (monocast) films laminated together, or two coextruded layers produced by coextruding two different or the same polymer compositions to form a coextruded film. The total thickness of the two-layer microporous membrane (as opposed to the thickness of the individual layers making up the two-layer membrane) may be, for example, 0.2 to 50 microns. The thickness of the two films making up the two-layer microporous membrane may be 0.1 to 25 microns. The coextrusion method allows for the formation of thinner layers than the extrusion + lamination method.

[0041] In other embodiments, the microporous membrane may be a multilayer microporous membrane, e.g., a membrane comprising three or more layers. The multilayer microporous membrane may be a 3-layer, 4-layer, 5-layer, 6-layer, 7-layer, 8-layer, 9-layer, or 10-layer membrane. In other embodiments, the membrane may comprise 11 to 100 layers. The multilayer microporous membrane may be formed by individually forming three or more monolayers (e.g., by extrusion (e.g., monoextrusion) or casting (e.g., monocasting)) and then laminating them together. In these embodiments, the thickness of the multilayer microporous membrane may be 6 to 100 microns, with each layer of the multilayer microporous membrane having a thickness of 2 to 30 microns. In other embodiments, the multilayer microporous membrane may be formed by coextrusion of three or more polymer compositions, which may be the same or different. In this embodiment, the thickness of the multilayer microporous membrane may be as little as 1 micron or as much as 50 microns. The individual layers may have a thickness of 0.1 to 20 microns.

[0042] In other embodiments, multilayer microporous membranes may be formed by a combination of the following processes: forming a monoextruded or monocast layer; coextruding two or more layers; and laminating. For example, a monolayer can be extruded or cast, and then two polymer compositions can be extruded to form a coextruded bilayer, and then the monolayer and bilayer can be laminated together to form a multilayer microporous membrane. In some embodiments, two or more coextruded bilayers or multilayers are laminated together to form a multilayer microporous membrane. In some embodiments, multilayer microporous membranes can be formed using a blown film (or bubble) coextrusion method, in which the bubbles collapse on themselves. This method can form multilayer microporous membranes with 2 (bilayer), 4, 6, 8, 10, 12, or other even numbers of layers. This method does not form microporous membranes with 3, 5 (five layers), 7, 9, 11, or other odd numbers of layers.

[0043] For example, the microporous membrane may be a microporous membrane as described in PCT Publication No. WO / 2017 / 083633, which is incorporated herein by reference in its entirety.

[0044] In the embodiments described herein, lamination refers to the application of at least one of heat, pressure, or a combination thereof to attach separate films or layers. The films or layers that are laminated to form the bi-layer or multi-layer microporous membrane described herein may be subjected to at least one of annealing, MD stretching, TD stretching, calendering, heat setting, and combinations thereof before and / or after lamination. Alternatively, or additionally, the laminate formed by laminating these films or layers may be subjected to at least one of annealing, MD stretching, TD stretching, calendering, and combinations thereof. In this case, at least one of annealing, MD stretching, TD stretching, and calendering is performed after lamination.

[0045] Unless otherwise stated in a particular embodiment, the composition of the porous membranes described herein is not particularly limited. In some embodiments, the porous membranes may be composed of any extrudable polymer. In some preferred embodiments, the extrudable polymer is a polyolefin, including polyethylene, polypropylene, and mixtures thereof.

[0046] In some embodiments, the pores (e.g., nanopores, micropores, or macropores) of the porous membranes described herein can be filled with an ionically conductive medium (ICM). The ICM can include a polymer and a solvent electrolyte. For example, the ICM can include a polymer such as PVDF and an electrolyte. Lithium ions conduct in the ICM or liquid electrolyte in the pores. Microporous membranes conduct ions when the pores are filled with ICM, even when not wetted (dry) by the electrolyte. Microporous membranes with polymers in the pores (e.g., polymers from the ICM) have infinite Gurley (greater than 10,000). There are various electrolytes, including: pure liquid electrolytes—many can be immersed in a polymer film (Gurley = infinite) to form gel electrolytes, and many can be immersed within the pores of a porous film (Gurley with a certain value). Batteries work well with both types of polymer films. Currently, when a liquid electrolyte encounters a polymer, at least a portion of the liquid electrolyte will impregnate (wet, swell, or gel) the polymer to some extent. Depending on the amount of impregnated liquid electrolyte, we can refer to these as gel electrolytes or polymer electrolytes. 100% "pure liquid electrolyte" (often not present in cells due to the polymer wicking up of the liquid) is not possible. Our new mathematical definition of tortuosity for ICMs can describe the performance of the layer as a whole.

[0047] As illustrated in Figure 1, Li-ion transport in an ionically conductive medium is quite different from fluid flow, for example, the fluid flow of a liquid electrolyte through a porous material such as the porous membranes described herein. The ionically conductive medium does not flow. The tortuosity is determined by the MacMullin number (N) given by the following equation (1): where ε is the porosity; m ) and the resistance of the electrolyte (ρ e ) to the separator membrane resistance (ρ s ) is the ratio of (ρ s ) / (ρ e )=N m =τ 2 / ε (1)

[0048] The ionically conductive medium may be at least one of a solid electrolyte with infinite Gurley, a gel electrolyte, or a liquid electrolyte-entrapped polymer, but still be capable of transporting ions, and its τ or tortuosity is always equal to 1. The tortuosity (τ) is represented by the following equation (2): τ=L / x (2)

[0049] In equation (2), L is the actual length of the hole and x is the linear distance from one end of the hole to the other. Both L and x are shown in FIG. 1.

[0050] Energy Cell Unless otherwise stated in a particular embodiment, the energy cells described herein are not so limited and may be either primary or secondary energy cells. For example, in a preferred embodiment, the energy cells are electrochemical energy cells. The energy cells may also be primary or secondary cells. As will be understood by those skilled in the art, primary cells are batteries that are designed to be used only once and are not recharged by electricity and reused like secondary cells or rechargeable batteries. Generally, the electrochemical reactions in primary cells are not reversible, while the electrochemical reactions in secondary cells are reversible. In a preferred embodiment, the energy cells herein are secondary electrochemical energy cells.

[0051] The structure of the energy cell is also not particularly limited. It may include, consist of, or consist essentially of an anode, a cathode, an electrolyte, and a separator. In some embodiments, the energy cell may include, consist of, or consist essentially of an anode, a cathode, and a solid electrolyte. In some embodiments, the energy cell may include, consist of, or consist essentially of an anode, a cathode, a separator, and an electrolyte. The separator may be a separator described herein.

[0052] In at least one preferred embodiment, the energy cell herein comprises, consists of, or consists essentially of the following: a lithium-containing anode, a cathode, and at least one of an electrolyte and separator, a solid electrolyte and separator, or a solid electrolyte only.

[0053] Unless otherwise stated in a particular embodiment, the anode material is not so limited and may be any material known or found to be acceptable for use as an anode material. In some preferred embodiments, the anode material is a material known or found to be acceptable for use as an anode material that also contains lithium. For example, lithium-containing anode materials include: lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni x Mn y Co z )O2), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni x Co y Al z ) O2), where 0.8>x>0.9 and x+y+z=1; and at least one selected from the group consisting of combinations thereof.

[0054] The material of the cathode is also not particularly limited and can be any material known or found to be acceptable for use as a cathode material. In some preferred embodiments, the cathode comprises at least one material selected from the group consisting of natural graphite, artificial graphite, amorphous carbon, alloys containing tin and / or silicon, spinel lithium titanate, and combinations thereof.

[0055] Unless otherwise stated in a particular embodiment, the thickness of the anode is not significantly limited. In some preferred embodiments, the thickness of the anode is about 50 to about 200 microns, about 55 to 200 microns, about 60 to 200 microns, about 65 to 200 microns, about 70 to 200 microns, about 75 to 200 microns, about 80 to 200 microns, about 85 to 200 microns, about 90 to 200 microns, about 90 to 200 microns, about 100 to 200 microns, about 105 to 200 microns, about 110 to 200 microns, about 115 to 200 microns, about 120 to 200 microns, about 125 to 200 microns, about 130 to 200 microns, about 135 to 200 microns, about 140 to 200 microns, about 145 to 200 microns, about 150 to 200 microns, about 155 to 200 microns, or about 160 to 200 microns. , about 170-200 microns, about 180-200 microns, or about 200 microns. In some preferred embodiments, the anode thickness is about 61 microns or greater. In some preferred embodiments, the thickness is about 90 microns or greater. In other preferred embodiments, the thickness is about 122 microns or greater. When the electrode thickness is about 61 microns or greater, about 90 microns or greater, or about 122 microns or greater, lithium deposition occurs at a charge of 3.5 C (1 C=2.3 mA / cm). 2 ), Li deposition does not begin at charging rates above 5.0 C, 6.0 C, 7.0 C, 8.0 C, or 9.0 C. In some embodiments, Li deposition may also be avoided at charging rates above 5.0 C, 6.0 C, 7.0 C, 8.0 C, or 9.0 C. When referring to anode thickness, the term "about" means ±5 microns.

[0056] The thickness of the cathode is also not particularly limited. The thickness of the cathode is about 50 to about 200 microns, about 60 to 200 microns, about 70 to 200 microns, about 80 to 200 microns, about 90 to 200 microns, about 100 to 200 microns, about 110 to 200 microns, about 120 to 200 microns, about 130 to 200 microns, about 140 to 200 microns, about 150 to 200 microns, about 160 to 200 microns, about 170 to 200 microns, about 180 to 200 microns, or about 190 to 200 microns. In some preferred embodiments, the thickness of the cathode may be about 74 microns or more, about 111 microns or more, or about 148 microns or more. When the electrode thickness is about 74 microns or more, about 111 microns or more, or about 148 microns or more, lithium deposition occurs at a charge of 3.5 C (1 C=2.3 mA / cm). 2 ), Li deposition does not begin at charging rates above 5.0 C, 6.0 C, 7.0 C, 8.0 C, or 9.0 C. In some embodiments, Li deposition may also be avoided at charging rates above 5.0 C, 6.0 C, 7.0 C, 8.0 C, or 9.0 C. When referring to cathode thickness, the term "about" means ±5 microns.

[0057] Thickness and Li deposition during charging (safety). Thickness and cell rate performance, constant charge capacity. Discharge and charge kinetics are similar. We focus on charge kinetics. Note that for a given electrochemical system, immobilization chemistry, particle size of materials and other additives, we assume that the effective electrochemical reaction area is relatively fixed. Figure 17 shows the system at a 4C charge rate for electrode thicknesses 1X and 2X in the starting state (t=0). Figure 18 shows the system at a 4C charge rate for electrode thicknesses 1X and 2X in the dynamic state (t>0).

[0058] Unless otherwise specified in a particular embodiment, the porosity of the anode is not particularly limited. In some embodiments, the porosity is about 15% (0.15) or greater, in some embodiments, about 20% (0.2) or greater, in some preferred embodiments, about 30% (0.3) or greater, and in some even more preferred embodiments, about 40% (0.4) or greater. The term "about" when referring to the porosity of the anode means ±5%. As shown in FIG. 20, when the porosity of the anode is about 15% or greater, about 20% or greater, about 30% or greater, or about 40% or greater, lithium deposition does not initiate in the cell, even at charge rates of 3.0 C or greater. In some embodiments, Li deposition may not initiate at charge rates of 3.5 C, 4.0 C, 4.5 C, 5.0 C, 6.0 C, or 7.0 C or greater. In Figure 20, the electrode thickness is varied so that each example has the same amount of active material, and therefore the variable value does not affect the results.

[0059] The porosity of the cathode is also not limited. In some embodiments, the porosity is about 10% (0.1) or greater, or in preferred embodiments, about 15% (0.15) or greater, about 20% (0.20) or greater, or about 30% (0.3) or greater. The term "about" when referring to the porosity of the cathode means ±5%. As shown in Figure 20, cathode porosity of about 10% or greater, about 15% or greater, about 20% or greater, or about 30% or greater can be used. At times, lithium deposition does not initiate in the cells even when the charge rate is 3.5 C or higher. In some embodiments, Li deposition may not initiate at charge rates of 3.5 C, 4.0 C, 4.5 C, 5.0 C, 6.0 C, 7.0 C, or higher. In Figure 20, the electrode thicknesses are varied so that each example has the same amount of active material, and therefore the variables do not affect the results.

[0060] Unless otherwise specified in a particular embodiment, the degree of tortuosity of the anode is not particularly limited. In some preferred embodiments, the degree of tortuosity of the anode is about 1.2 or less, about 1.3 or less, about 1.5 or less, or about 1.7 or less. In some embodiments, the degree of tortuosity of the anode is 1.0 or more and 2.0 or less. In some preferred embodiments, the degree of tortuosity of the anode is about 1.0 to about 1.3 or 1.0 to 1.3. When referring to the degree of tortuosity of the anode, "about" means ±0.2. As shown in FIG. 21, when the degree of tortuosity of the anode is between 1.0 and 1.3, lithium deposition does not begin in the cell even at a charge rate of 3.5 C or more. When the degree of tortuosity is between 1.0 and 1.7, lithium deposition does not begin in the cell even at a charge rate of 3.0 C or more. In some embodiments, lithium deposition may not begin when the charge rate exceeds 4.0C, 4.5C, 5.0C, 6.0C, or 7.0C.

[0061] Similarly, unless otherwise specified in a particular embodiment, the cathode tortuosity is not particularly limited. In some preferred embodiments, the cathode tortuosity is about 1.7 or less, about 1.5 or less, about 1.3 or less, or about 1.2 or less. The cathode tortuosity can be as low as 1.0 or as high as about 2.0. In some preferred embodiments, the cathode tortuosity is between about 1.0 and about 1.5 or between about 1.2 and about 2.5. When referring to the cathode tortuosity, "about" means ±0.2. As shown in FIG. 21 , when the anode tortuosity is between 1.0 and 1.3, lithium deposition does not begin in the cell, even at charge rates of 3.5 C or higher. When the tortuosity is between 1.0 and 1.7, lithium deposition does not begin in the cell, even at charge rates of 3.0 C or higher. In some embodiments, lithium deposition may not begin when the charge rate exceeds 4.0C, 4.5C, 5.0C, 6.0C, or 7.0C.

[0062] The anode and cathode materials are as described above. In some preferred embodiments, the anode and cathode materials are combined with a binder to form the anode and cathode. Unless otherwise noted in a particular embodiment, the relative amounts of anode or cathode material and binder in this combination are not significantly limited. In some preferred embodiments, the amount of active material (i.e., cathode or anode material) is 80% to 99.9% by weight. In some preferred embodiments, the amount is 90 to 99.9% by weight, and in some other preferred embodiments, the amount is 95 to 99.9% by weight.

[0063] In FIG. 22, an exemplary cell according to the disclosure herein is provided.

[0064] In addition to the anode and cathode, the energy cells herein may include an electrolyte, or an electrolyte and a separator.

[0065] Unless otherwise stated in a particular embodiment, the separator is not so limited and may be any separator described herein. Unless otherwise stated in a particular embodiment, the electrolyte is not so limited and may be any electrolyte known or found to be useful in primary or secondary energy cells. In some preferred embodiments, the electrolyte is: ethylene carbonate (EC); ethyl methyl carbonate (EMC); diethyl carbonate (DEC); dimethyl propylene carbonate (PC); and combinations thereof.

[0066] In some embodiments, the electrolyte may have an electrolyte additive added thereto.

[0067] The electrolyte additives described herein are not particularly limited, so long as the electrolyte is consistent with the goals described herein. The electrolyte additive may be any additive typically added by battery manufacturers, particularly lithium battery manufacturers, to improve battery performance. For example, exemplary electrolyte additives are listed in A Review of Electrolyte Additives, incorporated herein by reference in its entirety. for Lithium-Ion Batteries, J. of Power Sources, vol. 162, issue 2, 2006, pp. 1379-1394. In some preferred embodiments, the electrolyte additive is at least one selected from the group consisting of an SEI improver, a cathode protectant, a flame retardant additive, a LiPF salt stabilizer, an overcharge protectant, an aluminum corrosion inhibitor, a lithium precipitation agent or improver, or a solvation promoter, an aluminum corrosion inhibitor, a wetting agent, and a thickener. In some embodiments, the additive may have more than one property, for example, it may be a wetting agent and a thickener.

[0068] Exemplary SEI improvers include VEC (vinyl ethylene carbonate), VC (vinylene carbonate), FEC (fluoroethylene carbonate), and LiBOB (lithium bis(oxalato)borate). Exemplary cathode protectants include N,N'-dicyclohexylcarbodiimide, N,N-diethylaminotrimethylsilane, and LiBOB. Exemplary flame retardant additives include TTFP (tris(2,2,2-trifluoroethyl)phosphate), fluorinated propylene carbonate, and MFE (methyl nonafluorobutyl ether). Exemplary LiPF6 salt stabilizers include LiF, TTFP (tris(2,2,2-trifluoroethyl)phosphite), 1-methyl-2-pyrrolidone, fluorinated carbamates, and hexamethylphosphoramide. Exemplary overcharge protectants include xylene, cyclohexylbenzene, biphenyl, 2,2-diphenylpropane, and phenyl-tert-butyl carbonate. Exemplary Li deposition improvers include AlI3, SnI2, cetyltrimethylammonium chloride, perfluoropolyethers, and tetraalkylammonium chlorides with long alkyl chains. Exemplary ionic solvation promoters include 12-crown-4 and TFPPB (tris(pentafluorophenyl)). Exemplary Al corrosion inhibitors include LiBOB, LiODFB, e.g., borate salts. Exemplary wetting agents and viscosity reducers include cyclohexane and P2O5.

[0069] Anode or Cathode Unless otherwise noted in a particular embodiment, the anodes or cathodes described herein are not so limited and may be similar to those incorporated into the energy cells described herein. However, the anodes and cathodes described under this heading have not been incorporated into energy cells, but may be in the future.

[0070] Complex, vehicle, or device A composite comprising a battery separator as described hereinabove and one or more electrodes, such as an anode, a cathode, or an anode and a cathode, disposed in direct contact therewith. The type of electrode is not particularly limited. For example, the electrode may be one suitable for use in a lithium-ion secondary battery.

[0071] Suitable anodes may have an energy capacity of 372 mAh / g or greater, preferably ≥ 700 mAh / g, and most preferably ≥ 1000 mAh / g. The anodes are composed of lithium metal foil or lithium alloy foil (e.g., lithium aluminum alloy), or mixtures of lithium metal and / or lithium alloy with materials such as carbon (e.g., coke, graphite), nickel, or copper. The anodes are not simply made of lithium-containing intercalation compounds or lithium-containing insertion compounds.

[0072] Suitable cathodes may be any cathode compatible with the anode and may include intercalation compounds, insertion compounds, or electrochemically active polymers. Suitable intercalation materials include, for example, MoS2, FeS2, MnO2, TiS2, NbSe3, LiCoO2, LiNiO2, LiMn2O4, VO 13 , V2O5, and CuCl2. Suitable polymers include, for example, polyacetylene, polypyrrole, polyaniline, and polythiophene.

[0073] Any separator, energy cell, or anode or cathode described herein above may be incorporated into any vehicle, e.g., an electric car, or device, e.g., a fully or partially battery-powered cell phone or laptop.

[0074] According to at least selected embodiments, aspects, or objectives, the present disclosure or invention may provide or be directed to new or improved separators, battery separators, electrodes, cathodes, anodes, batteries, cells, systems, and / or methods of designing, understanding, manufacturing, and / or using such separators, battery separators, electrodes, cathodes, anodes, cells, systems, and the like for lithium batteries, particularly secondary lithium batteries, e.g., secondary lithium-ion batteries, and / or CE, ESS, and / or EDV batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved methods for investigating or defining tortuosity, porosity, lithium deposition, and cell design using such new ideas, definitions, and / or data. Also disclosed herein are methods, systems, and battery components for improving battery life, reducing battery failure, reducing dendrites, reducing lithium deposition, maintaining charge and discharge rates, improved configuration, improved performance, and the like.

[0075] According to at least selected embodiments, aspects, or objectives, the present disclosure or invention may provide or be directed to new or improved separators, battery separators, electrodes, cathodes, anodes, batteries, cells, systems, and / or methods of designing, understanding, manufacturing, and / or using such separators, battery separators, electrodes, cathodes, anodes, cells, systems, etc. for lithium batteries, particularly secondary lithium batteries, e.g., secondary lithium-ion batteries, and / or CE, ESS, and / or EDV batteries, including, for example, the following:

[0076] When wetted by electrolyte, the following properties: No or low volume: Massless or low mass: Immerse as much liquid electrolyte as possible: Blocks or removes any harmful substances in the electrolyte: Does not melt at any high temperature: Does not react with cathode or anode under any conditions: Has mechanical strength greater than steel: It is an electronic insulator under both conditions: Blocking metal dendrite growth; Improved porous membrane or battery separator comprising a porous membrane having at least one of:

[0077] The battery separator above, which has no or low volume when wetted by electrolyte.

[0078] The battery separator above, which has no or low mass when wetted by electrolyte.

[0079] The battery separator as above, when wetted by the electrolyte, soaks as much of the liquid electrolyte as possible.

[0080] The battery separator as above, which blocks dendrites when wetted by electrolyte.

[0081] The battery separator above, which when wetted by the electrolyte does not melt at any elevated temperature.

[0082] The above battery separator, when wetted by the electrolyte, does not react with the cathode or anode under any conditions.

[0083] The battery separator above, which when wetted by electrolyte has a mechanical strength equal to or greater than that of steel.

[0084] The battery separator above, which is an electrical insulator under all conditions when wetted by electrolyte.

[0085] The battery separator above, which blocks metal dendrite growth when wetted by an electrolyte.

[0086] The battery separator as described above, having at least two of the above properties.

[0087] The battery separator as described above, having at least three of the above properties.

[0088] The battery separator as described above, having at least four of the above properties.

[0089] The battery separator, as described above, having at least five of the above properties.

[0090] The battery separator as above, having at least six of the above properties.

[0091] The battery separator, wherein the battery separator has at least seven of the above properties.

[0092] The battery separator, wherein the battery separator has at least eight of the above properties.

[0093] The battery separator, wherein the battery separator has at least nine of the above properties.

[0094] The battery separator above, wherein the battery separator is macroporous, microporous, or nanoporous, and the pores are filled with an ionically conductive medium.

[0095] When dry (without electrolyte) and / or wetted with electrolyte, the separator The battery separator as described above, wherein the separator conducts lithium ions.

[0096] The battery separator above, having an infinite Gurley value.

[0097] The battery separator above, having an infinite Gurley value.

[0098] 3.0C (1C = 2.3mA / cm) without lithium deposition 2 1. An energy cell that can be charged at a charge rate of at least: an anode comprising lithium; and cathode; The energy cell.

[0099] The above energy cell, wherein the charging rate is 3.5C or more.

[0100] The above energy cell, wherein the charging rate is 4.0C or more.

[0101] The above energy cell, wherein the charging rate is 4.5C or more.

[0102] The above energy cell, wherein the charging rate is 3.0C or more and less than 5.0C.

[0103] The above energy cell, wherein the thickness of the anode is about 50 to about 200 microns.

[0104] The above energy cell, wherein the thickness of the anode is about 60 to about 200 microns.

[0105] The above energy cell, wherein the anode has a thickness of about 60 to about 125 microns.

[0106] The above energy cell, wherein the cathode has a thickness of about 50 to about 200 microns.

[0107] The above energy cell, wherein the cathode has a thickness of about 75 to about 200 microns.

[0108] The above energy cell, wherein the cathode has a thickness of about 75 to about 150 microns.

[0109] The above energy cell, wherein the porosity of the anode is 15% or more.

[0110] The above energy cell, wherein the porosity of the anode is 20% or more.

[0111] The above energy cell, wherein the porosity of the anode is 30% or more.

[0112] The above energy cell, wherein the porosity of the anode is 40% or more.

[0113] The above energy cell, wherein the porosity of the anode is 15% or more and 50% or less.

[0114] The above energy cell, wherein the porosity of the cathode is 10% or more.

[0115] The above energy cell, wherein the porosity of the cathode is 15% or more.

[0116] The above energy cell, wherein the porosity of the cathode is 20% or more.

[0117] The above energy cell, wherein the porosity of the cathode is 30% or more.

[0118] The above energy cell, wherein the porosity of the cathode is 10% or more and less than 40%.

[0119] The above energy cell, wherein the bending degree of the anode is 2.0 or less.

[0120] The above energy cell, wherein the bending degree of the anode is 1.7 or less.

[0121] The above energy cell, wherein the bending degree of the anode is 1.5 or less.

[0122] The above energy cell, wherein the bending degree of the anode is 1.3 or less.

[0123] The above energy cell, wherein the bending degree of the anode is 1.2 or less.

[0124] The above energy cell, wherein the degree of bending of the anode is 1.2 or more and 1.3 or less.

[0125] The above energy cell, wherein the bending degree of the cathode is 2.0 or less.

[0126] The above energy cell, wherein the bending degree of the cathode is 1.7 or less.

[0127] The above energy cell, wherein the bending degree of the cathode is 1.5 or less.

[0128] The above energy cell, wherein the bending degree of the cathode is 1.3 or less.

[0129] The above energy cell, wherein the bending degree of the cathode is 1.2 or less.

[0130] The above energy cell, wherein the bending degree of the cathode is 1.2 or more and 1.5 or less.

[0131] The lithium-containing anode is selected from the group consisting of lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni x Mn y Co z )O2), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni x CO y Al z )O2), where 0.8>x>0.9 and x+y+z=1; and combinations thereof.

[0132] The above energy cell, wherein the cathode comprises at least one material selected from the group consisting of natural graphite; artificial graphite; amorphous carbon; alloys containing tin and / or silicon; spinel lithium titanate; and combinations thereof.

[0133] The above energy cell further comprising an electrolyte.

[0134] The above energy cell, wherein the electrolyte is selected from the group consisting of: ethylene carbonate (EC); ethyl methyl carbonate (EMC); diethyl carbonate (DEC); dimethyl carbonate (DMC); propylene carbonate (PC); and combinations thereof.

[0135] The above energy cell, wherein the electrolyte contains an electrolyte additive.

[0136] The energy cell, further comprising the membrane or battery separator.

[0137] an anode containing lithium;

[0138] The anode has a thickness of about 50 to about 200 microns.

[0139] The above anode has a thickness of about 60 to about 200 microns.

[0140] The above anode, wherein the thickness of the anode is about 60 to about 125 microns.

[0141] The anode, wherein the porosity of the anode is 15% or more.

[0142] The anode, wherein the porosity of the anode is 20% or more.

[0143] The anode, wherein the porosity of the anode is 30% or more.

[0144] The anode as described above, wherein the porosity of the anode is 40% or more.

[0145] The anode as described above, wherein the porosity of the anode is 15% or more and 50% or less.

[0146] The above anode, wherein the degree of bending of the anode is 2.0 or less.

[0147] The above anode, wherein the degree of bending of the anode is 1.7 or less.

[0148] The above anode, wherein the degree of bending of the anode is 1.5 or less.

[0149] The above anode, wherein the degree of bending of the anode is 1.3 or less.

[0150] The above anode, wherein the degree of bending of the anode is 1.2 or less.

[0151] The above anode, wherein the degree of bending of the anode is 1.0 or more and 2.0 or less.

[0152] The above anode, wherein the degree of bending of the anode is 1.2 or more and 1.3 or less.

[0153] Cathode.

[0154] The cathode has a thickness of about 50 to about 200 microns.

[0155] The cathode has a thickness of about 75 to about 200 microns.

[0156] The cathode has a thickness of about 75 to about 150 microns.

[0157] The cathode as described above, wherein the porosity of the cathode is 10% or more.

[0158] The cathode as described above, wherein the porosity of the cathode is 15% or more.

[0159] The cathode as described above, wherein the porosity of the cathode is 20% or more.

[0160] The cathode as described above, wherein the porosity of the cathode is 30% or more.

[0161] The cathode as described above, wherein the porosity of the cathode is 10% or more and less than 40%.

[0162] The cathode as described above, wherein the bending degree of the cathode is 2.0 or less.

[0163] The cathode as described above, wherein the bending degree of the cathode is 1.7 or less.

[0164] The cathode as described above, wherein the bending degree of the cathode is 1.5 or less.

[0165] The cathode as described above, wherein the bending degree of the cathode is 1.3 or less.

[0166] The cathode as described above, wherein the bending degree of the cathode is 1.2 or less.

[0167] The cathode as described above, wherein the bending degree of the cathode is 1.2 or more and 1.5 or less.

[0168] The lithium-containing anode may be selected from the group consisting of lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni x Mn y Co z )O2), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni x CO y Al z )O2), where 0.8>x>0.9 and x+y+z=1; and combinations thereof.

[0169] The cathode comprises at least one material selected from the group consisting of natural graphite; artificial graphite; amorphous carbon; alloys containing tin and / or silicon; spinel lithium titanate; and combinations thereof.

[0170] New or improved separators, battery separators, electrodes, cathodes, anodes, batteries, cells, systems, and / or methods of designing, understanding, making, and / or using such separators, battery separators, electrodes, cathodes, anodes, cells, systems, etc. for lithium batteries, particularly secondary lithium batteries, e.g., secondary lithium-ion batteries, and / or CE, ESS, and / or EDV batteries, as shown, described, or claimed herein; new or improved methods for investigating or defining tortuosity, porosity, lithium deposition, and cell design using such new ideas, definitions, and / or data; new or improved methods, systems, and battery components for improving battery life, reducing battery failure, reducing dendrites, reducing lithium deposition, maintaining charge and discharge rates, improved configuration, improved performance, and / or combinations thereof; and the like.

[0171] According to at least selected embodiments, the present disclosure or invention is directed to new or improved separators, battery separators, electrodes, cathodes, anodes, batteries, cells, systems, and / or methods of designing, understanding, manufacturing, and / or using such separators, battery separators, electrodes, cathodes, anodes, cells, systems, etc. for lithium batteries, particularly secondary lithium batteries, e.g., secondary lithium-ion batteries, and / or CE, ESS, and / or EDV batteries. According to at least certain embodiments, the present disclosure or invention is directed to new or improved methods for investigating or defining tortuosity, porosity, lithium deposition, and cell design using such new ideas, definitions, and / or data. Also disclosed herein are methods, systems, and battery components for improving battery life, reducing battery failure, reducing dendrites, reducing lithium deposition, maintaining charge and discharge rates, improved configuration, improved performance, and the like.

[0172] According to at least certain embodiments, an improved battery separator has the following properties when wetted by an electrolyte: no or low volume; no or low mass; absorbs as much liquid electrolyte as possible; blocks or removes any harmful substances in the electrolyte; does not melt at any high temperature; does not react with the cathode or anode under any conditions; and has mechanical strength equal to or greater than steel. The separator is disclosed herein, comprising a porous membrane having at least one of the following properties: a porous membrane that is electrically insulating under all conditions; an electronic insulator under all conditions; and a porous membrane that blocks metal dendrite growth. Also disclosed herein is an energy cell that does not undergo lithium deposition even at high charging rates. The energy cell may comprise the improved separator disclosed herein. The energy cell further comprises an anode comprising lithium, and in some embodiments, a cathode comprising a carbonaceous material. Also disclosed herein are anodes and cathodes that are separate from the energy cell but can be used in the energy cells disclosed herein.

[0173] The above detailed descriptions of structures and methods have been presented for illustrative purposes only. Examples are used to disclose exemplary embodiments, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any device or system, and practicing any incorporated methods. These examples are not intended to be exhaustive or to limit the invention to the precise steps and / or configurations disclosed; many modifications and variations are possible in light of the above teachings. Features described herein may be combined in any combination. Method steps described herein may be performed in any order that is physically possible. The patentable scope of the invention is defined by the appended claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims when they have structural elements that do not differ word for word from the claims, or when they include structural elements that are equivalent to the claims with only minor differences.

[0174] The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of certain aspects of the claims. Any compositions and methods that are functionally equivalent are intended to be within the scope of the claims. Various modifications of the compositions and methods, in addition to those shown and described herein, are intended to be within the scope of the appended claims. Furthermore, although only certain representative compositions and method steps disclosed herein have been specifically described, other combinations of compositions and method steps, even if not specifically recited, are also intended to be within the scope of the appended claims. Thus, although a step, element, component, or combination of components may be explicitly referred to herein or below, other combinations of steps, elements, components, and components are included, even if not explicitly described.

[0175] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from "about" one particular value and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of the antecedent "about," it is understood that the particular value forms another embodiment. It is further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. "Optionally" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that such description includes instances when the event or circumstance occurs and instances when it does not.

[0176] Throughout this specification and the claims, the word "comprise" and variations of that word, such as "comprising" and "comprises," mean "including but not limited to," e.g., For example, it is not intended to exclude other additives, components, integers, or steps. The terms "consisting essentially of" and "consisting of" may be used in place of "comprising" and "including" to provide more specific embodiments of the present invention, which are also disclosed. "Exemplary" means "an example of" and is not intended to convey an indication of a preferred or ideal embodiment. "For example" is used for descriptive or illustrative purposes, not in a limiting sense.

[0177] Except as stated, all numbers expressing geometric shapes, dimensions, and the like used in the specification and claims should at least be understood and not construed in light of the number of significant digits and ordinary rounding approaches, as an attempt to limit the application of the doctrine of equivalents to the claims.

[0178] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed invention belongs. The publications cited herein and the materials cited therein are specifically incorporated by reference.

[0179] Additionally, the invention illustratively disclosed herein may suitably be practiced in the absence of any element not specifically disclosed herein.

Claims

1. When wetted by electrolyte, the following properties: No or low volume: Having no mass or low mass: Immerse as much liquid electrolyte as possible: Block or remove any harmful substances in the electrolyte: Does not melt at any high temperature: Does not react with cathode or anode under any conditions: Has mechanical strength equal to or greater than that of steel: It is an electronic insulator under both conditions: Blocks metal dendrite growth; Improved battery separator comprising a porous membrane having at least one of:

2. the separator has no or low volume when wetted by electrolyte; the separator has no mass or a low mass when wetted by electrolyte; When wetted by the electrolyte, the separator soaks up as much liquid electrolyte as possible; the separator blocks dendrites when wetted by electrolyte; the separator does not melt at any elevated temperature when wetted by the electrolyte; the separator, when wetted by the electrolyte, does not react with the cathode or anode under any conditions; the separator has a mechanical strength equal to or greater than that of steel when wetted by an electrolyte; the separator is an electrical insulator under all conditions when wetted by the electrolyte; and The separator blocks metal dendrite growth when wetted by electrolyte.

10. The battery separator of claim 1, comprising at least one of:

3. The battery separator of claim 1 having at least two of said properties.

4. 10. The battery separator of claim 1 having at least three of said properties.

5. 10. The battery separator of claim 1 having at least four of said properties.

6. 10. The battery separator of claim 1 having at least five of said properties.

7. 10. The battery separator of claim 1 having at least six of said properties.

8. 10. The battery separator of claim 1 having at least seven of said properties.

9. 10. The battery separator of claim 1 having at least eight of said properties.

10. 10. The battery separator of claim 1 having at least nine of said properties.

11. the battery separator is macroporous, microporous, or nanoporous; The plurality of pores of the battery separator are filled with an ionically conductive medium; the separator conducts lithium ions when dry (without electrolyte) and / or when wetted with electrolyte; and the separator has an infinite Gurley value; The battery separator of any of claims 1 to 10, comprising at least one of:

12. 3.0 C (1 C = 2.3 mA / cm ) without lithium deposition ２ 1. An energy cell capable of being charged at a charge rate of at least: an anode comprising lithium; and cathode; The energy cell.

13. The charging rate is 3.5C or more; The charging rate is 4.0 C or more; The charging rate is 4.5C or more; the charging rate is equal to or greater than 3.0C and less than 5.0C; the thickness of the anode is from about 50 to about 200 microns; the thickness of the anode is from about 60 to about 200 microns; the thickness of the anode is from about 60 to about 125 microns; the cathode has a thickness of about 50 to about 200 microns; the cathode has a thickness of about 75 to about 200 microns; the cathode has a thickness of about 75 to about 150 microns; The porosity of the anode is 15% or more; The porosity of the anode is 20% or more; The porosity of the anode is 30% or more; The porosity of the anode is 40% or more; The porosity of the anode is 15% or more and 50% or less; The porosity of the cathode is 10% or more; The porosity of the cathode is 15% or more; The porosity of the cathode is 20% or more; The porosity of the cathode is 30% or more; The porosity of the cathode is 10% or more and less than 40%; The degree of tortuosity of the anode is 2.0 or less; The degree of curvature of the anode is 1.7 or less; The degree of curvature of the anode is 1.5 or less; The degree of curvature of the anode is 1.3 or less; The degree of curvature of the anode is 1.2 or less; The degree of curvature of the anode is 1.2 or more and 1.3 or less; The bending degree of the cathode is 2.0 or less; The tortuosity of the cathode is 1.7 or less; The bending degree of the cathode is 1.5 or less; The tortuosity of the cathode is 1.3 or less; The tortuosity of the cathode is 1.2 or less; The cathode has a tortuosity of 1.2 or more and 1.5 or less; The anode contains lithium and may be selected from the group consisting of lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni ｘ Mn ｙ Co ｚ ) O ２ ), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni ｘ CO ｙ Al ｚ ) O ２ ), wherein 0.8>x>0.9 and x+y+z=1; and combinations thereof; The cathode may be made of: natural graphite; artificial graphite; amorphous carbon; tin and / or silicon. Spinel lithium titanate; and combinations thereof; further comprising an electrolyte, said electrolyte being selected from the group consisting of: ethylene carbonate (EC); ethyl methyl carbonate (EMC); diethyl carbonate (DEC); dimethyl carbonate (DMC); propylene carbonate (PC); and combinations thereof; and the electrolyte comprises an electrolyte additive; 13. The energy cell of claim 12, having at least one of:

14. 14. The energy cell of claim 12 or 13, further comprising the separator of claim 1.

15. the anode having a thickness of about 50 to about 200 microns; the thickness of the anode is from about 60 to about 200 microns; the thickness of the anode is from about 60 to about 125 microns; The porosity of the anode is 15% or more; The porosity of the anode is 20% or more; The porosity of the anode is 30% or more; The porosity of the anode is 40% or more; The porosity of the anode is 15% or more and 50% or less; The degree of tortuosity of the anode is 2.0 or less; The degree of curvature of the anode is 1.7 or less; The degree of curvature of the anode is 1.5 or less; The degree of curvature of the anode is 1.3 or less; The degree of curvature of the anode is 1.2 or less; The degree of tortuosity of the anode is 1.0 or more and 2.0 or less; and The degree of curvature of the anode is 1.2 or more and 1.3 or less; 14. An energy cell according to claim 12 or 13, comprising at least one of:

16. the cathode has a thickness of about 50 to about 200 microns; the cathode has a thickness of about 75 to about 200 microns; the cathode has a thickness of about 75 to about 150 microns; The porosity of the cathode is 10% or more; The porosity of the cathode is 15% or more; The porosity of the cathode is 20% or more; The porosity of the cathode is 30% or more; The porosity of the cathode is 10% or more and less than 40%; The bending degree of the cathode is 2.0 or less; The tortuosity of the cathode is 1.7 or less; The bending degree of the cathode is 1.5 or less; The tortuosity of the cathode is 1.3 or less; The tortuosity of the cathode is 1.2 or less; and The cathode has a tortuosity of 1.2 or more and 1.5 or less; 14. An energy cell according to claim 12 or 13, comprising at least one of:

17. The anode may be made of lithium cobalt oxide (LCO); lithium manganese oxide (LMO); lithium iron phosphate (LFP); (Li(Ni ｘ Mn ｙ Co ｚ ) O ２ ), where 0.33>x>0.9 and x+y+z=1; NCA(Li(Ni ｘ CO ｙ Al ｚ ) O ２ 17. The energy cell of claim 16, comprising at least one material selected from the group consisting of: where 0.8>x>0.9 and x+y+z=1; and combinations thereof.

18. 14. The energy cell of claim 12 or 13, wherein the cathode comprises at least one material selected from the group consisting of: natural graphite; artificial graphite; amorphous carbon; alloys containing tin and / or silicon; spinel lithium titanate; and combinations thereof.

19. 14. An energy cell according to claim 12 or 13, comprising or included in a secondary lithium battery.

20. A lithium battery or cell, the improvement comprising a separator according to any one of claims 1 to 10.

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