Ultra-high molecular weight polyethylene (UHMWPE) particles and filled articles made therefrom

Abstract

Described herein are devices, systems, materials, and methods for preparing polyethylene electrodes for use in energy storage and transfer via dry electrode processing. Ultra-high molecular weight polyethylene (UHMWPE) particles and filler particles are used to form a blended composition. Shearing causes the UHMWPE to fibrillate, durably entangling the filler particles. The blended composition containing the fibrillated UHMWPE particles can then be used to form articles such as electrodes. The blended composition can contain less than 10% by weight of UHMWPE. The UHMWPE has a molecular weight of at least about 2,000,000 g / mol, a bulk density of about 0.04 g / mL to about 0.25 g / mL, and a melt enthalpy of at least 190 J / g. In some embodiments, the UHMWPE can be conditioned to modify particle size and / or shape. The conditioned UHMWPE particles have a median diameter of 5 microns to 300 microns.

Description

[Technical Field]

[0001] The present disclosure relates generally to solventless processing, and more specifically to devices, systems, materials, and methods for preparing polyethylene ("PE") electrodes for use in energy storage and transfer via dry electrode processing. [Background technology]

[0002] Electrical energy storage is important in many applications, including mobile electronic devices, electric vehicles, and solar energy capture. As new applications use electrical energy storage and technology transitions toward the use of electricity, various factors have driven the development of electrochemical energy storage devices. For example, some considerations include the cost and efficiency of manufacturing electrochemical energy storage devices, the size and weight of electrochemical energy storage devices, the environmental impact of manufacturing and disposing of electrochemical energy devices, and the efficiency and durability of electrochemical energy storage devices over time. The dominant electrochemical energy storage technology for many applications is the lithium-ion battery.

[0003] The current method, also known as the "wet process," used to manufacture many commercially available lithium-ion battery electrodes involves the use of large amounts of liquid processing aids (e.g., solvents such as N-methyl-2-pyrrolidone (NMP)) that are harmful to humans and / or the environment, as well as the use of large ovens to remove the liquid processing aids. Alternative methods for manufacturing lithium-ion battery electrodes have been developed, including the "dry electrode process," which does not require liquid processing aids or large ovens. Initial development of the dry electrode process focused on electrodes for supercapacitors. More recently, interest in applying the dry electrode process to other electrodes, such as lithium-ion batteries, has grown substantially. The primary motivation for switching from the wet process to the dry electrode process is to reduce the cost, physical footprint, and environmental impact of electrode manufacturing.

[0004] Thus, there is a need in the art for more efficient electrode manufacturing methods that reduce environmental impact and are scalable for mass production of articles that can be used in a variety of environments and industries. Summary of the Invention

[0005] According to one embodiment ("Embodiment 1"), a method of making an article includes shearing filler particles and UHMWPE particles having a molecular weight of at least 2,000,000 g / mol and a melt enthalpy of at least 190 J / g to form a mixed particle composition, and molding the mixed particle composition into an article, wherein the filler particles are durably entangled within fibrils formed by the UHMWPE particles, and at least 80% by weight of the article is filler particles.

[0006] In addition to embodiment 1, another embodiment ("embodiment 2") includes fibrillating the UHMWPE particles before shearing the filler particles and UHMWPE particles.

[0007] According to another embodiment ("embodiment 3"), in addition to embodiment 1 or embodiment 2, shaping the mixed particle composition into an article includes calendering the mixed particle composition.

[0008] According to another embodiment ("embodiment 4") in addition to any one of embodiments 1 to 3, the article has a DSC curve with a DSC peak at about 143°C to about 175°C, and the article has a fibrillation rate greater than 0%.

[0009] According to another embodiment ("Aspect 5") in addition to any one of Aspects 1 to 4, the particles include at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

[0010] In addition to any one of Aspects 1-5, another aspect ("Aspect 6") includes conditioning the UHMWPE particles before shearing the filler particles and UHMWPE particles, wherein the UHMWPE particles have a median Da of about 5 microns to about 300 microns.

[0011] According to another embodiment (“embodiment 7”) in addition to any one of embodiments 1-6, the mixed particle composition comprises less than 10% by weight of fibrillizable UHMWPE particles.

[0012] According to another embodiment ("Embodiment 8"), a composite material includes a filler material including filler particles and a binder system including ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least 2,000,000 g / mol and a melt enthalpy of at least 190 J / g, wherein the filler material and UHMWPE particles are sheared and formed into an article, and the composite material has a DSC peak between about 143°C and about 175°C.

[0013] In addition to Example 8, according to another example ("Example 9"), the composite material has a DSC curve with a DSC peak at about 143°C to about 175°C, and the fibrillation rate is determined by the integration of the DSC peak as a percentage of the integration of the DSC curve from about 100°C to about 175°C, and the article has a fibrillation rate greater than 0%.

[0014] According to another embodiment ("Aspect 10"), in addition to Aspect 8 or Aspect 9, the filler material is selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

[0015] According to another embodiment ("embodiment 11") in addition to any one of embodiments 7-10, the binder system includes less than 20% by weight of polytetrafluoroethylene.

[0016] According to another embodiment ("embodiment 12") in addition to any one of embodiments 7 to 11, the binder system does not include polytetrafluoroethylene.

[0017] According to another embodiment (“Embodiment 13”), a mixed particle composition includes filler particles and fibrillizable UHMWPE particles having a molecular weight of at least about 2,000,000 g / mol, a bulk density of about 0.04 g / mL to about 0.25 g / mL, and a melt enthalpy of at least 190 J / g, wherein the mixed particle composition includes less than about 10% by weight of fibrillizable binder particles therein.

[0018] In addition to Example 13, according to another example (“Example 14”), the mixed particle composition comprises less than about 5% by weight of fibrillizable binder particles.

[0019] According to another embodiment (“Aspect 15”), further to Aspect 13 or Aspect 14, the filler material includes at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

[0020] According to another embodiment ("embodiment 16") in addition to any one of embodiments 13 to 15, the UHMWPE particles are formed from agglomerates of fine particles, the fine particles having an average diameter of 10 nm or more and 2000 nm or less.

[0021] According to another embodiment ("Embodiment 17"), an article comprises filler particles and a binder system comprising fibrillated ultra-high molecular weight polyethylene (UHMWPE) particles, wherein the fibrillated UHMWPE particles have a molecular weight of at least about 2,000,000 g / mol, a median Da of about 5 microns to about 300 microns, and a melting enthalpy of at least 190 J / g, the article having a DSC peak at about 143°C to about 175°C, and the filler particles are durably entangled within the fibrils of the fibrillated UHMWPE particles.

[0022] In addition to Example 17, according to another example ("Example 18"), the UHMWPE particles have at least one of a median sphericity of about 0.820 to about 0.880, a median convexity of about 0.950 to about 0.990, and a median length-to-width ratio of about 1.50 to about 1.80.

[0023] According to another embodiment ("embodiment 19") in addition to embodiment 17 or embodiment 18, the article has an endotherm of about 145°C to about 155°C associated with the fibrillated UHMWPE particles.

[0024] According to another embodiment ("embodiment 20") in addition to any one of embodiments 17-19, the article has a DSC curve with a DSC peak at about 143°C to about 175°C, and the fibrillation rate is determined by the integration of the DSC peak as a percentage of the integration of the DSC curve from about 100°C to about 175°C, and the article has a fibrillation rate greater than 0%.

[0025] According to another embodiment ("Aspect 21") in addition to any one of Aspects 17 to 20, the filler particles are selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

[0026] According to another embodiment ("embodiment 22") in addition to any one of embodiments 17-21, the binder system includes less than 20% by weight of polytetrafluoroethylene.

[0027] According to another embodiment ("embodiment 23") in addition to any one of embodiments 17 to 22, the binder system does not include polytetrafluoroethylene.

[0028] In addition to any one of Aspects 17 to 23, according to another aspect ("Aspect 24"), the article is freestanding.

[0029] According to another embodiment ("embodiment 25") in addition to any one of embodiments 17 to 24, the fibrillated UHMWPE particles have a median Da of about 5 microns to about 300 microns.

[0030] According to another embodiment ("Embodiment 26"), a method of making an article includes shearing filler particles and UHMWPE particles having a molecular weight of at least about 2,000,000 g / mol, a melt enthalpy of at least 190 J / g, and a bulk density of about 0.04 m / mL to about 0.25 g / mL to form a mixed particle composition in which the filler particles are durably entangled within fibrils formed by the UHMWPE particles, and molding the mixed particle composition into an article, wherein the article comprises at least about 80% by weight of the filler particles.

[0031] In addition to Example 26, according to another example ("Example 27"), the article has a DSC curve with a DSC peak at about 143°C to about 175°C, and the article has a fibrillation rate greater than 0%.

[0032] In addition to embodiment 26 or embodiment 28, another embodiment ("embodiment 28") includes conditioning the UHMWPE particles before shearing the UHMWPE particles, such that the UHMWPE particles have a median Da of from about 5 microns to about 300 microns, or the UHMWPE particles have a median sphericity of from about 0.820 to about 0.880, or the UHMWPE particles have a median convexity of from about 0.950 to about 0.990, or the UHMWPE particles have a median length-to-width ratio of from about 1.50 to about 1.80.

[0033] According to another embodiment ("Embodiment 29"), an electrode includes a filler material and a binder system including fibrillated UHMWPE particles, the UHMWPE particles having a median Da of about 5 microns to about 300 microns, a median sphericity of about 0.820 to about 0.880, a median convexity of about 0.950 to about 0.990, and a median length-to-width ratio of about 1.50 to about 1.80, and the UHMWPE particles have a DSC peak between about 143°C and about 175°C.

[0034] In addition to Example 29, according to another example ("Example 30"), the filler material is at least 90% by weight of the electrode.

[0035] According to another embodiment ("embodiment 31"), in addition to embodiment 28 or embodiment 29, UHMWPE particles are 10% or less by weight of the electrode.

[0036] In addition to any one of Aspects 29 to 31, according to another aspect ("Aspect 32"), the electrode is free-standing.

[0037] According to another embodiment ("embodiment 33") in addition to any one of embodiments 29 to 32, the electrode has a DSC curve with a DSC peak at about 143°C to about 175°C, and the electrode has a fibrillation rate greater than 0%.

[0038] According to another embodiment ("Embodiment 34"), in addition to any one of Embodiments 29-33, the UHMWPE particles have a median Da value of about 5 microns to about 300 microns, or a median sphericity of about 0.820 to about 0.880, or a median convexity of about 0.950 to about 0.990, or a median length-to-width ratio of about 1.50 to about 1.80.

[0039] According to another embodiment ("embodiment 35") in addition to any one of embodiments 29-34, the binder system includes less than 20 wt. % polytetrafluoroethylene.

[0040] According to another embodiment ("embodiment 36") in addition to any one of embodiments 29 to 35, the binder system does not include polytetrafluoroethylene.

[0041] According to another embodiment (“Embodiment 37”), a method of making an electrode includes providing ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least about 2,000,000 g / mol, a fusion enthalpy of at least 190 J / g, and a bulk density in the range of about 0.04 g / mL to about 0.25 g / mL; providing filler particles selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles; dry-blending the UHMWPE particles with the filler particles to produce a dry mixture article having fibrillated UHMWPE particles therein; and forming the dry mixture article into a composite sheet, wherein the filler particles are durably entangled with the fibrillated UHMWPE particles.

[0042] In addition to Example 37, according to another example ("Example 38"), the composite sheet comprises at least 90% by weight dry filler particles.

[0043] According to another embodiment ("embodiment 39"), further to embodiment 37 or embodiment 38, the composite sheet comprises 10% by weight or less of fibrillated UHMWPE particles.

[0044] According to another embodiment ("embodiment 40") in addition to any one of embodiments 37 to 39, the composite sheet has a thickness of about 10 microns to about 500 microns.

[0045] According to another embodiment ("embodiment 41") in addition to any one of embodiments 37 to 40, the composite sheet has a tensile stress at maximum load of about 2,500 kPa to about 7,000 kPa.

[0046] In addition to any one of Aspects 37 to 41, according to another aspect ("Aspect 42"), the composite sheet has a DSC curve with a DSC peak at about 143°C to about 175°C, and the composite sheet has a fibrillation rate greater than 0%.

[0047] According to another embodiment ("embodiment 43") in addition to any one of embodiments 37 to 42, the composite sheet has a tensile strain at maximum load of about 3% to about 9%.

[0048] According to another embodiment ("embodiment 44") in addition to any one of embodiments 37 to 43, the composite sheet has a tensile strain at break of about 5% to about 50%.

[0049] In addition to any one of Aspects 37 to 44, another aspect ("Aspect 45") includes applying the composite sheet to a conductive substrate.

[0050] According to another embodiment ("embodiment 46") in addition to any one of embodiments 37-45, forming the dry mixture into the composite sheet includes one or more of applying pressure, calendaring, and heat.

[0051] According to another embodiment ("Aspect 47"), in addition to any one of Aspects 37 to 46, the filler particles are selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

[0052] According to another embodiment ("Embodiment 48"), a method for preparing conditioned fibrillizable ultra-high molecular weight polyethylene (UHMWPE) particles for use in a dry electrode process includes providing ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least about 2,000,000 g / mol, a melting enthalpy of at least 190 J / g, and a bulk density of about 0.04 g / mL to about 0.25 g / mL; and shear mixing the UHMWPE particles to modify the size and shape of the UHMWPE particles, conditioning the UHMWPE particles to have a median Da of about 5 to about 300 microns, a median length-to-width ratio of about 1.50 to about 1.80, or a median sphericity of about 0.820 to about 0.880, or a median convexity of about 0.950 to about 0.990.

[0053] According to another embodiment ("Embodiment 49"), an ultrahigh molecular weight polyethylene (UHMWPE) resin has a molecular weight of at least about 2,000,000 g / mole, a melt enthalpy of at least 190 J / g, a bulk density of about 0.04 g / mL to about 0.25 g / mL, a median Da of about 5 microns to about 300 microns, a median sphericity of about 0.820 to about 0.880 microns, a median convexity of about 0.950 to about 0.990, and a median length-to-width ratio of about 1.50 to about 1.80.

[0054] According to another embodiment ("Embodiment 50"), a binder system includes fibrillizable ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least about 2,000,000 g / mol, a melting enthalpy of at least 190 J / g, a median Da of from about 5 microns to about 300 microns, a median sphericity of from about 0.820 to about 0.880, a median convexity of from about 0.950 to about 0.990, and a median length-to-width of from about 1.50 to about 1.80.

[0055] In addition to Example 49, according to another example ("Example 51"), the fibrillizable UHMWPE particles can be manipulated for use in a dry electrode process.

[0056] According to another embodiment ("Aspect 52"), there is provided a method for producing an electrode using ultra-high molecular weight polyethylene (UHMWPE) resin particles as a binder, wherein each UHMWPE particle has a molecular weight of at least 2,000,000 g / mol, a melting enthalpy of at least 190 J / g, and a bulk density of 0.04 g / mL to 0.25 g / mL.

[0057] According to another embodiment (“Embodiment 53”), a composite binder system includes a plurality of filler particles characterized by a filler particle median value, Da, and UHMWPE resin particles having a resin particle median value, Da, a molecular weight of at least 2,000,000 g / mol, a melt enthalpy of at least 190 J / g, and a bulk density of 0.04 g / mL to 0.25 g / mL, wherein the ratio of the filler particle median value, Da, to the resin particle median value, Da, is 10:1 to 1:10.

[0058] According to another embodiment (“Aspect 54”), a composite binder system includes filler particles and ultra-high molecular weight polyethylene particles (UHMWPE), wherein the composite binder system has a force gradient of at least 200 N / mm as measured with a capillary rheometer on a test sample under the following conditions: 1. The test sample is a homogeneous mixture of 95 wt% filler particles and 5 wt% UHMWPE resin particles. 2. The barrel diameter is 12mm and the barrel length is 241.3mm. 3. The maximum test load is 20kN. 4. Temperature (barrel and die) is 130°C. 5. The reduction ratio of the tape die is 2.5. 6. The piston speed is 1 mm / sec. 7. Measure the normal force relative to the piston position and calculate the slope of the line of normal force versus piston position using the following formula: Formula for calculating slope: m = (y2 - y1) ÷ (x2 - x1) where m = slope, (x1, y1) = coordinates of a first point on the line of force (N) versus piston position (mm), and (x2, y2) = coordinates of a second point on the line of force (N) versus piston position (mm). The test sample is now capable of forming a solid extrudate.

[0059] According to another embodiment (“Embodiment 55”), the composition comprises ultra-high molecular weight polyethylene particles (UHMWPE) having a compressibility (%) of at least 20% at a normal stress of 15 kPa, as measured using a powder rheometer at 22° C.

[0060] According to another embodiment (“Embodiment 56”), the composition comprises ultra-high molecular weight polyethylene (UHMWPE) particles having a cohesive strength of at least 3 kPa as measured using a powder rheometer at 22° C.

[0061] According to another embodiment (“Embodiment 57”), the composition comprises ultra-high molecular weight polyethylene (UHMWPE) particles having an unconstrained yield stress (UYS) of at least 10 kPa, as measured using a powder rheometer at 22° C.

[0062] According to another embodiment (“Embodiment 58”), the composition comprises ultra-high molecular weight polyethylene (UHMWPE) particles having an angle of internal friction (AIF) of at least 25° as measured using a powder rheometer at 22°C.

[0063] According to another embodiment (“Embodiment 59”), a composition comprises conditioned ultra-high molecular weight polyethylene (UHMWPE) particles that exhibit a percent change in angle of internal friction (AIF) relative to the unconditioned ultra-high molecular weight polyethylene (UHMWPE) particles of at least 50%, as measured using powder rheometry at 22° C.

[0064] According to another embodiment (“Embodiment 60”), a composition comprises conditioned ultra-high molecular weight polyethylene (UHMWPE) particles, having a percent change in basic flowability energy (BFE) relative to the UHMWPE particles before conditioning of at least 10%.

[0065] According to another embodiment (“Embodiment 61”), a composition comprises conditioned ultra-high molecular weight polyethylene (UHMWPE) particles having a percent change in specific energy (SE) relative to the UHMWPE particles before conditioning of at least 20%.

[0066] According to another aspect ("Aspect 62"), the use of the composition of any one of claims 54 to 60 in a binder system.

[0067] According to another aspect ("Aspect 63"), the composition of any one of claims 54 to 60 is used as a binder in forming an anode, a cathode, or a combination thereof.

[0068] According to another aspect ("Aspect 64"), a composite binder system comprises the composition of any one of claims 54-60 and filler particles.

[0069] In addition to Example 64, according to another example ("Example 65"), the composite binder system has at least 95 wt% filler particles.

[0070] According to another embodiment ("embodiment 66"), an electrode comprises filler particles and the composition of any one of claims 54-60.

[0071] In addition to embodiment 66, according to another embodiment (“embodiment 67”), the composition comprises at least 95 wt% filler particles. [Brief explanation of the drawings]

[0072] BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings are included to provide a further understanding of the present disclosure, and are incorporated in and constitute a part of this specification, illustrate embodiments, and together with the description, serve to explain the principles of the present disclosure. The figures are not necessarily drawn to scale and may be exaggerated to show various aspects of the disclosure, and in that regard, the figures should not be construed as limiting.

[0073] [Figure 1] FIG. 1 is a half-cell of a power storage device implementing an electrode formed from mixed filler particles and binder particles according to embodiments disclosed herein.

[0074] [Figure 2] FIG. 2 is a differential scanning calorimetry (DSC) thermogram showing a single melting point for a UHMWPE resin polymerized according to embodiments disclosed herein.

[0075] [Figure 3] FIG. 3 is a differential scanning calorimetry (DSC) thermogram showing a typical single melting point for an article made using conventional ultra-high molecular weight polyethylene (UHMWPE) particles according to embodiments disclosed herein.

[0076] [Figure 4]FIG. 4 is a differential scanning calorimetry (DSC) thermogram of an article made from UHMWPE particles conditioned according to embodiments disclosed herein, the thermogram showing the melting point associated with extended chain crystalline (ECC) fibrillation.

[0077] [Figure 5] FIG. 5 is a differential scanning calorimetry (DSC) thermogram of UHMWPE particles conditioned according to embodiments described herein.

[0078] [Figure 6] FIG. 6 is a graph of Freeman FT4 powder rheometer dynamic testing data for Resin A and Resin A conditioned according to embodiments described herein.

[0079] [Figure 7] FIG. 7 is a graph of Freeman FT4 powder rheometer dynamic testing data for Resin B and Resin B conditioned according to embodiments described herein.

[0080] [Figure 8] FIG. 8 is a graph of Freeman FT4 powder rheometer shear test data for Resin A and Resin A conditioned according to embodiments described herein.

[0081] [Figure 9] FIG. 9 is a graph of Freeman FT4 powder rheometer shear test data for Resin B and Resin B conditioned according to embodiments described herein.

[0082] [Figure 10] FIG. 10 is a graph of capillary rheometer data of slope (N / mm) values for mixtures of Resin A and filler and mixtures of conditioned Resin A and filler. DETAILED DESCRIPTION OF THE INVENTION

[0083] Detailed Description Definitions and Terminology The present disclosure is not to be construed in a limiting sense. For example, the terms used in this application should be interpreted broadly in the context of the meaning that one of ordinary skill in the art would give such terms.

[0084] With respect to the term imprecision, the terms "about" and "approximately" can be used interchangeably to refer to measurements that include the stated measurement and also measurements that are reasonably close to the stated measurement. A measurement that is reasonably close to the stated measurement deviates from the stated measurement by a reasonably small amount that is understood and readily ascertained by one of ordinary skill in the relevant art. If it is determined that such a reasonably small difference would not be readily ascertainable by one of ordinary skill in the relevant art, then the terms "about" and "approximately" can be understood to mean plus or minus 10% of the stated value.

[0085] As used herein, the term "fibril" refers to the characteristic shape of an element within the structure of a material. The structural characteristic of fibrils can be described as small fibers, generally 10 nm to 900 nm in width.

[0086] As used herein, the term "fibrillizable" refers to the ability to form fibrils in a polymer.

[0087] As used herein, the term "fibrillated" refers to the presence of fibrils in a polymer.

[0088] As used herein, the term "fibrillate" refers to the process of forming fibrils in a polymer.

[0089] As used herein, the terms "fibrillatable," "fibrillate," and "fibrillation" refer to the ability of a polymer to form a fibril microstructure upon solid-state deformation. The fibril microstructure can durably entangle other particles within the fibrils. The ability of a polymer to form a fibril microstructure under solid-state deformation, and the ability of the fibril microstructure to durably entangle other particles within the fibrils, can be characterized, for example, by the presence of an extended chain crystallization (ECC) fibrillation peak. In at least some embodiments, this is understood to be related to the formation of extended chain crystals. Because fibrillating polymers can have other particles durably entangled within the fibril microstructure of the fibrillated polymer, the fibrillating polymer can be used to bind other particles.

[0090] As used herein, the term "fibrillated" is intended to refer to a polymer that includes a fibril microstructure formed by solid-state deformation.

[0091] As used herein, the term "fibrillating" refers to the process of forming a fibrillated polymer by solid-state deformation.

[0092] As used herein, the term "DSC peak" refers to an endothermic peak identified in differential scanning calorimetry data, which endothermic peak is typically associated with a phase transition of a material.

[0093] As used herein, the term "initial peak" refers to the DSC peak characteristic of a melt of a polymerized resin.

[0094] As used herein, the term "reversible melting peak" refers to the DSC peak characteristic of a melt of a material that has been melted at least once. The reversible melting peak is typically observed at a temperature lower than that associated with the initial peak. The temperature at which the "reversible melting peak" is observed typically does not change significantly with repeated measurements.

[0095] As used herein, the term "extended chain crystalline fibrillation peak" or "ECC fibrillation peak" refers to the DSC peak characteristic of a phase transition of a material that has been processed by solid-state deformation and exhibits fibrillation. The ECC fibrillation peak is higher than the initial peak. It should be understood that the ECC fibrillation peak of a fibrillated polymer is distinct from the initial peak and the reversible melting peak.

[0096] The current method used to manufacture most commercially available lithium-ion batteries is called the "wet process." As used herein, the term "wet process" refers to a process in which the materials to be coated (e.g., electrode components such as active material, conductive carbon, and binder) are suspended or homogenized in a liquid processing aid (e.g., a solvent such as N-methylpyrrolidone (NMP) or water), and the resulting mixture (sometimes called a slurry or paste) is coated onto a substrate (e.g., a metal foil) by a thin-film liquid coating technique (e.g., slot-die coating), dried to substantially remove the liquid processing aid, and optionally calendered to a desired thickness. The materials to be coated, liquid processing aids, substrates, and thin-film liquid coating techniques described in this paragraph are for illustrative purposes only and are not intended to limit the definition of "wet process."

[0097] As used herein, the terms "solventless process" and "solventless processing" refer to a process in which a material is shaped into an article using a method that is substantially free of liquid processing aids, thus substantially avoiding the need for a drying step to remove the liquid processing aids. "Solventless" processes include several processes, including, but not limited to, dry powder spraying, dry hot pressing, dry 3D printing, melt extrusion, and dry electrode processing (DE processing).

[0098] As used herein, the term "dry electrode process" (DE process) is intended to refer to a process in which the formation of an electrode involves applying shear forces to a mixture of binder and filler particles to cause the fibrillizable particles to fibrillate and bind the filler particles together. The resulting electrode may or may not be freestanding, and may optionally be calendered to a desired thickness and / or attached to a substrate such as a metal foil, all of which are considered within the scope of this disclosure.

[0099] As used herein, the term "solvent" is used broadly and inclusively to refer to liquids such as water, common organic solvents such as N-methylpyrrolidone (NMP), alcohols, ketones, mixtures of alkanes, and other liquid processing aids, and is not intended to limit the definition of "solventless process" to only those in which a dissolved solute is present.

[0100] As used herein, "UHMWPE" includes ultra-high molecular weight homopolymer polyethylene and modified UHMWPE resins having a molecular weight of 2,000,000 g / mol or greater, a melt enthalpy of about 190 J / g, and a bulk density of about 0.04 g / mL to about 0.25 g / mL.

[0101] As used herein, the terms "filler" and "filler particles" refer to functional particles other than binders. For example, filler particles can include materials that have properties that promote a particular function of an article when the filler particles are processed as part of the article. In a more specific example, filler particles that are processed to form an electrode can include an electrically conductive material and an electrochemically active material (e.g., a lithium intercalation compound).

[0102] As used herein, the terms "binder" and "binder particles" refer to particles and materials whose primary purpose is to bind other materials and particles into a cohesive structure.

[0103] As used herein, the term "loading" refers to the percentage of filler by weight in a filler and binder mixture.

[0104] As used herein, the terms "condition" and "conditioned" are intended to refer to a process in which the size and / or shape of UHMWPE particles are altered.

[0105] As used herein, the term "area equivalent diameter" (Da) corresponds to the diameter of a circle equal to the area of a particle image. In some embodiments, Da can be measured via a Microtrac Sync Particle Analyzer (combining laser diffraction analysis (ISO 13320:2020) and dynamic image analysis (ISO:13322-2)) (Microtrac MRB, Pennsylvania, USA). Furthermore, Da can be used to quantify particle shape.

[0106] As used herein, the term "sphericity" is a measure of the shape of a two-dimensional image of an object and refers to its proximity to a perfect circle. Sphericity values range from 0 to 1, with 1 being a perfect circle. Sphericity can be used to quantify the shape of a particle.

[0107] As used herein, the term "convexity" refers to a measure of surface roughness. Convexity values range from 0 to 1, with 1 being smooth. As the value approaches 1, the measure of circularity increases.

[0108] As used herein, the term "L / W ratio" refers to the ratio of the major and minor axes of the best-fit Legendre ellipse. The L / W ratio can be measured from particle images taken with a Microtrac Sync Particle Analyzer, available from Microtrac MRB, Pennsylvania, USA. Additionally, the L / W ratio can be used to quantify particle shape.

[0109] As used herein, the terms "composition" and "mixture" may be used interchangeably.

[0110] In this specification, the terms "resin particles" and "resin powder" can be used interchangeably.

[0111] Description of Various Embodiments Those skilled in the art will readily appreciate that various aspects of the disclosure may be implemented by any number of methods and apparatuses configured to perform their intended functions.

[0112] Historically, a major obstacle to the adoption of dry electrode processes has been the limited selection of viable binders. The binder requirements for dry electrode processes differ significantly from those for wet processes. In wet processes, binders form adhesive bonds between electrode components, "gluing" them together. Typical binders include polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), and styrene butadiene rubber (SBR). This type of binder is sometimes referred to as an adhesive binder. However, dry electrode processes use binders that form fibrils under the application of shear forces. Despite discussion and speculation that other polymers have been used as fibril-forming binders, in practice, dry electrode processes have relied on the use of polytetrafluoroethylene (PTFE). This discrepancy is due to the fact that having a polymer capable of producing fibrils is not a sufficient criterion for enabling dry electrode processes (e.g., incorporating fillers into the product). Based on the preceding discussion, a distinction is made between "fibrillizable" and "fibrillatable" binders, the latter formed by solid-state deformation. Durable entanglement of filler particles within the binder's fibril microstructure formed during solid-state deformation is important to enable dry electrode processing. This is because while other polymers may fibrillate under certain conditions, they do not fibrillate sufficiently to durably entangle filler materials when subjected to currently used dry electrode processes.

[0113] PTFE is well known to fibrillate simply by handling the PTFE resin at room temperature. Furthermore, PTFE can be substantially deformed in the solid state. One factor that allows PTFE resin to fibrillate directly is that it is polymerized with a very high degree of crystallinity. This high degree of crystallinity indicates a low level of entanglement. Another factor that allows PTFE resin to fibrillate directly is its very high molecular weight. This combination allows PTFE to achieve high expansion ratios in the solid state. PTFE's solid-state deformation properties are relied upon in many PTFE processes, including currently used dry electrode processes. This high solid-state deformation capability is made possible, at least in part, by the low level of entanglement in polymerized PTFE resin. In dry electrode processes, PTFE resin can be added to the process and directly fibrillated in the solid state, durably entangling filler particles. These properties of PTFE allow for high filler loadings when used in dry electrode processes.

[0114] While PTFE is a versatile polymer suitable for many applications, it does have some limitations that make it less than optimal in all cases. For example, PTFE is not completely stable in contact with lithium metal or under the strongly reducing conditions of a typical (i.e., graphite-based) lithium-ion anode. Also, PTFE's density is approximately twice that of hydrocarbon-based binders, which can result in reduced gravimetric energy density. Also, PTFE's very low surface energy can cause electrolyte wetting issues.

[0115] Because of these properties and characteristics of PTFE, there is interest in identifying additional or alternative materials (e.g., non-lithium reactive materials, lighter weight materials, etc.) that can be fibrillated to durably entangle filler particles in dry electrode processes.

[0116] While it is known in the art that some polymers are fibrillable, fibril formation alone is inherently insufficient to provide high-strength, durable entanglement of filler particles at high loadings. Some have speculated about potential fibrillable binders other than PTFE that could be used in dry electrode processes (e.g., as described in U.S. Patent Publication No. 2005 / 0057888, published March 17, 2005, by Mitchell et al., which states, "Other potential fibrillable binders include ultra-high molecular weight polypropylene, polyethylene, copolymers, polymer blends, and the like."), but have not understood how PTFE differs from other fibrillable polymers. PTFE is a fibrillizable polymer, meaning it can undergo solid-state deformation to form fibrils. A fibrillizable binder is necessary to provide high-strength, durable entanglement of filler particles at high loadings. Many other fibrillogenic polymers are not fibrillizable, for example, capable of forming fibrils primarily through thermoplastic extrusion rather than solid state deformation.

[0117] Within the field of polyolefins (e.g., polypropylene, polyethylene, etc.), polyethylene encompasses many categories into which polyethylene can be classified. These categories include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), high-molecular-weight polyethylene (HMWPE), and ultra-high-molecular-weight polyethylene (UHMWPE). Based on the findings reported herein, LDPE, LLDPE, MDPE, and HDPE may be suitable for fibril formation in thermoplastic processes. UHMWPE is not suitable for thermoplastic processes due to its high viscosity. Within the UHMWPE category, there are a few low-entanglement resins (sometimes referred to as "dUHMWPE"). To maintain the low entanglement state of dUHMWPE resins, UHMWPE resins should be processed below their melting point. Furthermore, UHMWPE resins have a low elongation rate. This low elongation rate is incompatible with the high shear rates typically used in dry electrode processes. In other words, high speed blending or milling is not compatible with the deformation capabilities of less entangled UHMWPE resins.

[0118] PTFE resins can vary greatly in particle size and / or shape, with granular PTFE being more common. While practitioners of dry electrode processes discuss the use of PTFE as a binder, the morphology of the PTFE resin is not identified as a critical factor. This disclosure confirms, first, that high molecular weight, low-entanglement polyethylene resins are necessary for high solid-state deformation, and second, that the particle morphology of low-entanglement, high-molecular weight polyethylene resins is a critical factor in the production of highly loaded articles. High-loading articles can be produced by dry electrode processes due to the ability of low-entanglement, high-molecular weight resins with the particle morphology described herein to fibrillate to durably entangle filler particles.

[0119] The present disclosure relates to a method for forming a UHMWPE article by a dry electrode process. The present disclosure further relates to a dry electrode process in which UHMWPE is implemented as a viable binder. Specific properties of UHMWPE that facilitate its use in dry electrode processes are discussed. The UHMWPE particles as described herein have specific properties that enable the formation of fibrillated articles. The fibrillizable UHMWPE particles and / or fibrillated UHMWPE particles described herein are compatible with solid-state transformation processes, including those associated with dry electrode processes (including, but not limited to, high-speed blending, milling, and calendering). More specifically, the UHMWPE particles and processes described herein fibrillate in a dry electrode process, and the fibrillation is evidenced by an ECC fibrillation peak in the DSC graph of the produced article.

[0120] Solvent-free processing of materials, particularly dry electrode processing, reduces material consumption, energy consumption, and environmental impact. The disclosed processes and materials increase the strength of the manufactured articles, thus facilitating increased article loading. In one example, the disclosed processes and materials facilitate the use of minimal UHMWPE required to bond the materials via dry electrode processing. While specific examples of articles are provided herein, it is understood that any number of articles can be manufactured via the disclosed methods and compositions, which can be implemented in a variety of settings and industries. It is understood that the solvent-free processes described herein are intended to include embodiments that are substantially solvent-free but may contain nominal amounts of water or other liquids.

[0121] The UHMWPE particles as described herein can be implemented in a variety of processes, including dry electrode processes, for example, as a binder (e.g., as part of a binder system). The use of UHMWPE particles as described herein as a binder facilitates the production of highly loaded articles.

[0122] In some examples, the fibrillating and / or fibrillizable binder particles can include ultra-high molecular weight polyethylene (UHMWPE). The UHMWPE particles can have an average molecular weight (Mv) (i.e., viscosity average molecular weight) of at least 2,000,000 g / mol, or at least 3,000,000 g / mol, or at least 4,000,000 g / mol, or at least 5,000,000 g / mol, or at least 6,000,000 g / mol, or at least 7,000,000 g / mol. In some embodiments, the UHMWPE particles can have an average molecular weight in the range of 2,000,000 g / mol to 20,000,000 g / mol, or 2,000,000 g / mol to 15,000,000 g / mol, or 4,000,000 g / mol to 10,000,000 g / mol, or 5,000,000 g / mol to 8,000,000 g / mol, or any other range encompassed by these endpoints.

[0123] In some embodiments, the fibrillating binder particles and / or fibrillizable binder particles can have a high degree of crystallinity. The crystallinity of the UHMWPE particles can be measured by differential scanning calorimetry (DSC). The crystallinity of the UHMWPE particles is maintained or substantially maintained before or after conditioning, as described herein. The UHMWPE particles have a first melting enthalpy of at least about 190 J / g (i.e., dUHMWPE). In some embodiments, the first melting corresponds to an initial peak. As used herein, the phrases "high crystallinity" or "highly crystalline" are intended to refer to UHMWPE particles having a first melting enthalpy of greater than about 190 J / g, as measured by DSC (i.e., integration of the DSC curve from 100°C to 175°C). In another embodiment, the UHMWPE particles have a first enthalpy of melting of greater than about 195 J / g, about 200 J / g, about 205 J / g, about 210 J / g, about 215 J / g, about 220 J / g, about 225 J / g, about 230 J / g, about 235 J / g, about 245 J / g, about 250 J / g, about 255 J / g, about 260 J / g, about 265 J / g, about 270 J / g, or about 275 J / g. The UHMWPE particles have a melting point (e.g., first melt) of about 139°C to about 143°C (e.g., initial peak). Note that the terms "melting temperature," "melting temperature," and "melting point" may be used interchangeably herein. In at least one embodiment, the UHMWPE particles have a melting point of approximately 140°C. Subsequent remelting of the UHMWPE particles occurs at a temperature of about 127°C to about 137°C (e.g., a reversible melting peak). Furthermore, the crystallinity of the UHMWPE particles can be described as at least 70%. In some embodiments, the lower limit of the crystallinity of the UHMWPE particles is about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%.

[0124] In some embodiments, the UHMWPE particles have an intrinsic viscosity ranging from about 5 dL / g to about 60 dL / g. The approximate range of intrinsic viscosity from about 5 dL / g to about 60 dL / g is measured in decalin at 135° C. In some embodiments, the intrinsic viscosity ranges from about 10 dL / g to about 45 dL / g, and in still other embodiments, from about 15 dL / g to about 40 dL / g.

[0125] The UHMWPE particles may be provided as an agglomerate of fine particles. The average diameter of the fine particles is determined by observation using a scanning electron microscope (SEM). In some embodiments, the average diameter of the fine particles of the UHMWPE particles is about 10 nm or more and less than about 3,000 nm. In some embodiments, the average diameter of the fine particles of the UHMWPE particles is about 10 nm or more and less than about 2,000 nm, and in other embodiments, about 10 nm or more and less than about 1,000 nm. In some embodiments, the average diameter of the fine particles of the UHMWPE particles is 1 nm or more and 300 nm or less, 1 nm or more and 250 nm or less, 1 nm or more and 200 nm or less, 1 nm or more and 150 nm or less, 1 nm or more and 100 nm or less, or 1 nm or more and 50 nm or less. As discussed herein, UHMWPE particles refer to agglomerates of the described fine particles.

[0126] As described in Mitsui Chemicals Patent Publication WO2012 / 053261, published April 26, 2012, UHMWPE resins can be manufactured such that the UHMWPE particles are formed from agglomerates of fine particles, the agglomerates containing spaces or interstices within and between the agglomerates that are approximately equal in size to the fine particles.

[0127] Furthermore, the UHMWPE particles (i.e., aggregates of fine particles) can be a homopolymer of ethylene or a copolymer of ethylene and at least one comonomer. Suitable comonomers that can be used to form the UHMWPE copolymer include, but are not limited to, alpha-olefins or cyclic olefins having 3 to 20 carbon atoms. Non-limiting examples of suitable comonomers include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, cyclohexene, and dienes containing up to 20 carbon atoms (e.g., butadiene or 1,4-hexadiene). The comonomer can be present in the UHMWPE copolymer in an amount ranging from about 0.001 mol % to about 10 mol %, from about 0.01 mol % to about 5 mol %, from about 0.1 mol % to about 1 mol %, or any other amount included within these endpoints.

[0128] In some embodiments, UHMWPE particles (i.e., aggregates of fine particles) can be provided in a UHMWPE resin. The UHMWPE resin can include fibrillizable UHMWPE particles as described herein (e.g., having a molecular weight of at least 2,000,000 g / mol, a melting enthalpy of at least 190 J / g, and a bulk density of about 0.04 g / mL to about 0.25 g / mL). The bulk density of the UHMWPE resin can range from about 0.04 g / mL to about 0.25 g / mL, from about 0.04 g / mL to about 0.15 g / mL, from about 0.04 g / mL to about 0.12 g / mL, from about 0.04 g / mL to about 0.10 g / mL, from about 0.05 g / mL to about 0.15 g / mL, or from about 0.06 g / mL to about 0.08 g / mL. Once conditioned, the UHMWPE particles of the UHMWPE resin may have, on average, a median sphericity of about 0.820 to about 0.880, a median convexity of about 0.950 to about 0.990, and a median L / W ratio of about 1.5 to about 1.80.

[0129] In some embodiments, the UHMWPE particles (i.e., agglomerates of fine particles) may be conditioned before mixing with the filler particles. In some embodiments, the UHMWPE particles may be conditioned, by way of non-limiting example, shear mixing, to alter the size and shape of the UHMWPE particles. Some examples of particle size and shape of conditioned UHMWPE particles for several samples are shown in Table 1 (included in Example 1). Sample 1 shows the particle size and length / width ratio of UHMWPE particles for unconditioned UHMWPE resin, while Samples 2-7 show the UHMWPE particle size and length / width ratio for conditioned UHMWPE.

[0130] Once the UHMWPE particles (i.e., agglomerates of particulates) are conditioned, the UHMWPE particles (i.e., agglomerates of particulates) can have a median Da of less than about 300 microns. In some embodiments, the conditioned UHMWPE particles can have a median Da of about 5 microns to about 300 microns. In some embodiments, the UHMWPE particles can have a median Da of about 5 microns to about 275 microns, about 5 microns to about 250 microns, about 5 microns to about 225 microns, about 5 microns to about 200 microns, about 5 microns to about 175 microns, about 5 microns to about 150 microns, about 5 microns to about 125 microns, about 5 microns to about 100 microns, about 5 microns to about 75 microns, about 5 microns to about 50 microns, about 5 microns to about 15 microns, about 5 microns to about 10 microns, or about 5 microns to about 8 microns. In some embodiments, the conditioned UHMWPE particles have a median Da of about 10 microns to about 300 microns, about 10 microns to about 200 microns, about 10 microns to about 100 microns, about 10 microns to about 50 microns, about 10 microns to about 40 microns, about 10 microns to about 30 microns, or about 10 microns to about 20 microns. In some embodiments, the conditioned UHMWPE particles have a median Da of about 20 microns to about 25 microns, about 25 microns to about 30 microns, about 30 microns to about 35 microns, about 35 microns to about 40 microns, about 40 microns to about 45 microns, about 45 microns to about 50 microns, about 50 microns to about 55 microns, about 55 microns to about 60 microns, about 60 microns to about 65 microns, about 65 microns to about 70 microns, about 70 microns to about 75 microns, about 75 microns to about 80 microns, about 80 microns to about 90 microns, about 90 microns to about 100 microns, about 100 microns to about 120 microns, about 100 microns to about 140 microns, about 100 microns to about 160 microns, about 100 microns to about 220 microns, about 100 microns to about 260 microns, about 100 microns to about 280 microns, about 100 microns to about 290 microns, about 200 microns to about 300 microns, about 25 microns to about 30 microns, about 30 microns to about 35 microns, about 35 microns to about 40 microns, about 40 microns The median Da may be from 0 microns to about 85 microns, from about 85 microns to about 90 microns, from about 90 microns to about 95 microns, from about 95 microns to about 100 microns, from about 100 microns to about 125 microns, from about 125 microns to about 150 microns, from about 150 microns to about 175 microns, from about 175 microns to about 200 microns, from about 200 microns to about 225 microns, from about 225 microns to about 250 microns, from about 250 microns to about 275 microns, or from about 275 microns to about 300 microns.

[0131] Once the UHMWPE particles (i.e., agglomerates of particulates) are conditioned, the UHMWPE particles (i.e., agglomerates of particulates) can have a median sphericity of about 0.820 to about 0.880. In some embodiments, the UHMWPE particles can have a median sphericity of about 0.820 to about 0.825, about 0.825 to about 0.830, about 0.830 to about 0.835, about 0.835 to about 0.840, about 0.840 to about 0.845, about 0.845 to about 0.850, about 0.850 to about 0.855, or about 0.855 to about 0.860.

[0132] Once the UHMWPE particles (i.e., agglomerates of particulates) are conditioned, the UHMWPE particles (i.e., agglomerates of particulates) can have a median convexity of about 0.950 to about 0.990. In some embodiments, the UHMWPE particles can have a median convexity of about 0.950 to about 0.955, about 0.955 to about 0.960, about 0.960 to about 0.965, about 0.965 to about 0.970, about 0.970 to about 0.975, or about 0.975 to about 0.980.

[0133] Once the UHMWPE particles (i.e., agglomerates of particulates) are conditioned, the UHMWPE particles (i.e., agglomerates of particulates) can have a median L / W ratio of about 1.50 to about 1.80. In some embodiments, the UHMWPE particles can have a median L / W ratio of about 1.60 to about 1.62, about 1.62 to about 1.64, about 1.64 to about 1.66, about 1.66 to about 1.68, or about 1.68 to about 1.70.

[0134] As previously mentioned, when the UHMWPE particles are conditioned, the crystallinity of the UHMWPE particles is preserved or substantially preserved, such that both the conditioned and unconditioned particles have approximately the same crystallinity.

[0135] Fibrillating and / or fibrillizable binder particles, including UHMWPE particles (conditioned or unconditioned), can be mixed with filler particles. The filler particles are selected to perform a specific function in the final product, including, but not limited to, electronic conduction, ionic conduction, electrochemical reaction, etc. In some embodiments, the filler particles can be selected to conduct electricity and / or function as reagents in an energy storage device (e.g., for use in an electrode). The fibrillating and / or fibrillizable binder particles are selected to bind the filler particles. The fibrillating and / or fibrillizable binder particles have sufficient strength and stability to provide the structural qualities desired to maximize the ratio of filler particles to fibrillating and / or fibrillizable binder particles for a particular purpose (e.g., maximizing filler loading or maximizing article strength). Multiple binders may be included in the blend (i.e., "binder system"), and the binders may be of multiple types (e.g., a combination of a fibrillizable binder and an adhesive binder). In some embodiments, the filler particles may include organic particles, inorganic particles, and combinations thereof, added to facilitate a specific function within the composite article (comprising the filler particles durably entangled with the polymer binder of the present invention). In other embodiments, the filler particles may include, but are not limited to, electrically conductive materials, electrochemically active materials, thermally conductive materials, catalytically active materials (e.g., inorganic catalysts, enzymes, etc.), thermal insulating materials, electronic insulating materials, coloring materials, opacifiers, reinforcing fibers, and the like.

[0136] In some embodiments, filler particles can be selected based on their various properties and characteristics. In some embodiments, filler particles can be selected based on their electrical conductivity or corrosion resistance. Some examples of filler particles that can be selected, alone or in combination, include, but are not limited to, lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide (e.g., NMC-111, NMC-532, NMC-622, NMC-811), lithium nickel cobalt aluminum oxide, lithium iron phosphate, lithium manganese iron phosphate, and other lithium ion battery cathode materials (collectively referred to as "lithium compound particles"), graphite, silicon, lithium titanate, and others. lithium-ion battery anode materials, carbon black, solid electrolytes (e.g., garnet-type, perovskite-type, sulfide-type, LiPON-type, LiN-type, polymer-type, LISICON, NASICON), activated carbon, hard carbon, carbon nanotubes, graphene, fullerenes and other carbon allotropes, sulfur, sodium transition metal oxides, nickel, iron, cobalt, alloys thereof, oxides and mixed oxides thereof, other transition metal compounds (including both supported (e.g., on carbon or ceria) and unsupported), etc. In some embodiments, other materials that can be implemented as filler particles include any other material that can be implemented in lithium-ion battery cathodes, lithium-ion battery anodes, solid-state batteries, alternative battery chemistries, supercapacitors, electrodes, etc.

[0137] Considering the mixed particle composition, in some embodiments, the mixed particle composition comprises less than 10% by weight of fibrillating and / or fibrillizable binder particles. In some embodiments, the mixed particle composition can comprise at least 90% by weight of filler particles and 10% by weight or less of fibrillating and / or fibrillizable binder particles. In some embodiments, the ratio of filler particles to fibrillating and / or fibrillizable binder particles in the mixed particle composition allows an article formed from the mixed particle composition to be self-supporting. In some embodiments, the mixed particle composition can comprise at least about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, or about 99% (or more) of filler particles by weight. In some embodiments, the mixed particle composition can include about 10%, about 9%, about 8%, about 7%, about 6%, about 5%, about 4%, about 3%, about 2%, or about 1% or less of fibrillating and / or fibrillizable binder particles by weight. Other filled articles formed from the mixed particle composition include about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or about 85% filler particles by weight, with at least a portion of the remainder of the mixed particle composition comprising fibrillating and / or fibrillizable binder particles (e.g., about 95%, about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%, about 55%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, or about 15% by weight). The article can be a sheet, fiber, tube, or three-dimensional structure, and the article can be attached to a substrate (e.g., a sheet-like article can be adhered to a metal foil). Additionally, articles include articles formed by powder application processes, where a blended mix of filler and binder particles is formed or adhered directly onto a substrate. The substrate can be, for example, a metal foil.

[0138] With reference to some specific embodiments, the filler particles can comprise at least about 90% by weight of the mixed particle composition. In some embodiments, the high ratio of filler particles to binder particles facilitates substantially maintaining the properties and characteristics of the filler particles throughout the mixed particle composition (e.g., the properties and characteristics for which the filler particles are selected are not substantially diminished or diluted). It is understood that different ratios of filler particles to binder particles may be desirable for different applications. The UHMWPE particles described herein can be mixed and calendered with filler particles in a manner generally described in U.S. Patent Publication No. 2005 / 0057888 to Mitchell et al., published March 17, 2005, to produce composite materials having at least the properties (e.g., tensile stress and strain load) shown in Table 1. By using the specific UHMWPE particles described herein, the resulting composite materials have sufficient filler particle content (e.g., high loading) and sufficient strength imparted by the fibrillated UHMWPE particles to perform the intended function of the article produced from the mixed particle composition.

[0139] When UHMWPE particles as described herein (e.g., particle morphology and other properties and characteristics described herein) are fabricated into an article by dry electrode processing, the UHMWPE particles comprise a fibril structure (e.g., a substantially fibril structure) that imparts certain properties to the article, such as tensile strength (i.e., as indicated by tensile stress at maximum load). The UHMWPE can have an endotherm at about 145°C to about 155°C, about 150°C, or about 152°C (i.e., the ECC fibrillation peak) associated with fibrillation (i.e., durably entangled or capable of durably entanglement) of the UHMWPE (i.e., DSC peak determination can be performed relative to the ECC fibrillation peak by integrating data from a DSC thermograph between 143°C and 175°C). As explained, DSC can be used to identify the phase transition temperatures of UHMWPE particles within an article. FIG. 4 shows a DSC thermogram of an example UHMWPE article having a reduced phase transition temperature (e.g., a reversible melting peak) of approximately 132°C and an endotherm (e.g., an ECC fibrillation peak) of approximately 152°C. This peak (or endotherm) at approximately 152°C indicates fibrils formed during fibrillation, e.g., solid-state transformation, of the UHMWPE article. It should be understood that the endothermic peak at approximately 152°C is absent in conventionally processed UHMWPE articles but is present in filled UHMWPE articles produced by the dry electrode process according to the present disclosure and illustrated in the examples contained herein. The endothermic peak at approximately 152°C is also described, for example, in U.S. Patent No. 9,926,416 issued March 27, 2018 to W.L. Gore & Associates, Inc. For reference, a DSC thermogram of a UHMWPE resin is shown in FIG. 2. This DSC thermogram shows an initial peak of a polymerized resin at approximately 140°C. For further reference, a DSC thermograph of a conventional UHMWPE article is shown in Figure 2, showing a single melting peak at approximately 134°C (DSC peak determination can be performed for the reversible melting peak by integrating the DSC thermograph data from 100°C to 143°C).

[0140] If fibrillation of UHMWPE (according to the present disclosure) occurs during the dry electrode process, the manufactured article will have a DSC peak at about 152°C. The degree of fibrillation of UHMWPE can be characterized by the integral of the ECC fibrillation peak relative to the portion of the DSC curve that includes both the ECC fibrillation peak and the reverse melting peak, and any residual initial peak (e.g., the integral of the DSC curve of the peak from 143°C to 175°C compared to the integral of the DSC curve from 100°C to 175°C, hereafter "fibrillation rate"). Conversely, the degree to which UHMWPE does not fibrillate can be characterized by the integral of the DSC curve of the peak from 100°C to 143°C compared to the integral of the DSC curve from 100°C to 175°C, and any residual initial peak (e.g., the integral of the DSC curve of the peak from 100°C to 143°C compared to the integral of the DSC curve from 100°C to 175°C, hereafter "non-fibrillation rate"). UHMWPE particles that do not have the properties and characteristics described herein exhibit low fibrillation (e.g., low fibrillation rate). Low fibrillation is manifested by a low ratio of the ECC fibrillation peak compared to the sum of the ECC fibrillation peak and the reverse melting peak and the residual initial peak (e.g., low fibrillation rate), and also by a high ratio of the reverse melting peak compared to the sum of the ECC fibrillation peak and the reverse melting peak (e.g., high non-fibrillation rate). The integration method for these peaks as described in this paragraph assumes that the DSC peaks are due to the UHMWPE resin as described herein, and not, for example, to a filler. If artifacts, for example, due to a filler, are present in the DSC data, the DSC data must be corrected, for example, by subtracting an appropriate background to substantially isolate the peaks due to the UHMWPE particles.

[0141] As described herein, articles made using UHMWPE having the properties described herein and subjected to the processes described herein exhibit fibrillation, as indicated by the article having a fibrillation rate of greater than 0%. In some embodiments, articles made in accordance with the discussion herein have a fibrillation rate of about 1% or more, about 2% or more, about 3% or more, about 4% or more, about 5% or more, about 6% or more, about 7% or more, about 8% or more, about 9% or more, about 10% or more, about 15% or more, about 20% or more, about 25% or more, about 30% or more, about 35% or more, about 40% or more, about 45% or more, about 50% or more, about 55% or more, about 60% or more, about 65% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, or about 100%. In some embodiments, an article produced in accordance with the discussion herein can have a fibrillation rate of about 20% to about 25%, about 25% to about 30%, about 30% to about 35%, about 35% to about 40%, about 40% to about 45%, about 45% to about 50%, about 50% to about 55%, about 55% to about 60%, about 60% to about 65%, about 65% to about 70%, about 70% to about 75%, about 75% to about 80%, about 80% to about 85%, about 85% to about 90%, about 90% to about 95%, or about 95% to about 100%. The produced article can be fibrillated and have a fibrillation rate indicative of fibrillation as described herein, and can then be post-treated above the melt temperature (e.g., above 152°C). It is understood that post-processing above the melting temperature after fibrillation may reduce or even eliminate the ECC fibrillation peak in the DSC data. The present disclosure is not intended to be limited to final products having the fibrillation percentages described above, but rather to include articles at any point in their manufacture that have been processed according to the present disclosure and thus contain the properties and characteristics as described herein.

[0142] In one embodiment, the mixed particle composition (e.g., filler particles and fibrillating and / or fibrillizable binder particles) can be implemented to form an article such as a three-dimensional structure or sheet (e.g., a free-standing or non-free-standing sheet). In some embodiments, the mixed particle composition can be applied (e.g., deposited, adhered, bonded, etc.) directly to a secondary substrate. Some articles can be formed from the mixed particle composition by calendering. Some embodiments include articles formed from a mixed particle composition comprising at least 90% by weight filler particles and 10% by weight or less binder particles.

[0143] The mixed particle composition can be prepared by treating filler particles and UHMWPE particles (conditioned or unconditioned, having the properties discussed herein) under sufficient shear to promote fibrillation of the UHMWPE particles (e.g., as generally discussed in U.S. Patent Publication No. 2005 / 0057888 to Mitchell et al., published March 17, 2005). The mixed particle composition can then be used to form various articles. For example, the mixed particle composition can be fabricated into a composite sheet (e.g., freestanding) of filler particles durably entangled in a binder (e.g., fibrillated UHMWPE particles). The composite sheet has a thickness of about 10 microns or more (for example, about 10 microns to about 500 microns, about 10 microns to about 20 microns, about 20 microns to about 30 microns, about 30 microns to about 40 microns, about 40 microns to about 50 microns, about 50 microns to about 60 microns, about 60 microns to about 70 microns, about 70 microns to about 80 microns, about 80 microns to about 90 microns, about 90 microns to about 100 microns, about 100 microns to about 12 0 microns, about 120 microns to about 140 microns, about 140 microns to about 160 microns, about 160 microns to about 180 microns, about 180 microns to about 200 microns, about 200 microns to about 250 microns, about 250 microns to about 300 microns, about 300 microns to about 350 microns, about 350 microns to about 400 microns, about 400 microns to about 450 microns, or about 450 microns to about 500 microns).

[0144] The composite sheet can have a tensile stress at maximum load of about 2,500 kPa to about 7,000 kPa (e.g., about 2,500 kPa to about 3,000 kPa), about 3,000 kPa to about 3,500 kPa, about 3,500 kPa to about 4,000 kPa, about 4,000 kPa to about 5,500 kPa, about 4,500 kPa to about 5,000 kPa, about 5,000 kPa to about 5,500 kPa, about 5,500 kPa to about 6,000 kPa, about 6,000 kPa to about 6,500 kPa, or about 6,500 kPa to about 7,000 kPa). The composite sheet may have a tensile strain at maximum load of about 3.0% to about 10.0% (e.g., about 3.0% to about 3.5%, about 3.5% to about 4.0%, about 4.0% to about 4.5%, about 4.5% to about 5.0%, about 5.0% to about 5.5%, about 5.5% to about 6.0%, about 6.0% to about 6.5%, about 6.5% to about 7.0%, about 7.0% to about 7.5%, about 7.5% to about 8.0%, about 8.0% to about 8.5%, about 8.5% to about 9.0%, about 9.0% to about 9.5%, or about 9.5% to about 10.0%). The composite sheet can have a tensile strain at break of about 5.0% to about 50.0% (e.g., about 5.0%, about 6.0%, about 7.0%, about 8.0%, about 9.0%, about 10.0%, about 15%, about 20%, about 25%, about 30%, about 40%, or about 50%). Formation of the article (e.g., sheet) can be accomplished by calendering.

[0145] The mixed particle composition can be formed into a variety of other articles (e.g., films, sheets, tapes, etc.), which can be implemented in a variety of settings. In some embodiments, an article made from the mixed particle composition can be applied to another substrate. In one embodiment, an article made from the mixed particle composition can be applied to a substrate (e.g., a conductive substrate). An article formed from the mixed particle composition, alone or in combination with other components (e.g., a conductive substrate, a battery separator or spacer, etc.), can then be used as an electrode article in a variety of settings. An article formed from the mixed particle composition, and optionally a substrate to which the article is applied, can be used to form an anode and / or a cathode. When the article is applied to a substrate, the article and the substrate can include an adhesive.

[0146] In some embodiments, the electrode can include a composite sheet (or film) formed from filler particles (e.g., filler particles described herein) and fibrillated and / or fibrillizable UHMWPE particles (e.g., UHMWPE particles described herein). The composite sheet (in some embodiments, a free-standing sheet, or alternatively, a composite sheet formed on a supporting substrate, e.g., via direct deposition) can have a thickness of from about 10 microns to about 500 microns or more. A method for manufacturing an electrode can include fibrillating UHMWPE particles having a molecular weight of at least 2,000,000 g / mol and a fusion enthalpy of at least 190 J / g, e.g., dry-mixing (e.g., shearing) the UHMWPE particles with dry filler particles (including substantially dry filler particles) selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite, carbon black, and lithium compound particles (or any other additional filler particles, including those enumerated herein) to form a dry mixture, and forming the dry mixture into a composite sheet (e.g., a free-standing or non-free-standing composite sheet) of dry filler particles durably entangled with fibrillated UHMWPE, wherein the composite sheet is at least 90% by weight dry filler particles and has a thickness of about 10 microns to about 500 microns.

[0147] The electrodes described herein can be implemented in an electrochemical energy storage device, which includes at least a housing, an anode, a cathode, and an electrolyte (e.g., a non-aqueous electrolyte), and in some embodiments, a separator. The anode can be disposed within the housing and include a composite sheet formed from at least 90% by weight of filler particles and no more than 10% by weight of binder particles. The filler particles and binder particles can be as described herein. In some embodiments, the anode binder particles can be fibrillated UHMWPE particles having a molecular weight of at least 2,000,000 g / mol and a melt enthalpy of at least 190 J / g, as described herein, prior to being subjected to a dry electrode process. The cathode can also be disposed within the housing and include a composite sheet formed from at least 90% by weight of filler particles and no more than 10% by weight of binder particles. The cathode can be formed from filler and binder particles as described herein. In some embodiments, the cathode binder particles can be fibrillated UHMWPE particles having a molecular weight of at least 2,000,000 g / mol, a melting enthalpy of at least 190 J / g, and a bulk density of about 0.04 g / mL to 0.25 g / mL. Specific examples of electrodes are provided in the Examples section herein. The anode and / or cathode can be bonded (e.g., adhered, deposited, or otherwise applied) to a secondary substrate (e.g., a conductive element). The electrodes described herein can be implemented in various types of batteries, including, but not limited to, lithium-ion batteries, lithium-sulfur batteries, sodium-ion batteries, etc. While the examples provided below refer to half cells (i.e., cells using a lithium metal electrode in combination with one of the lithium-ion anodes or lithium-ion cathodes disclosed herein), it is understood that full cells can be formed using the electrodes disclosed herein as the anode, cathode, or both.

[0148] Freeman Identification of Suitable UHMWPE Resin Particles Using Powder Rheology Testing In one embodiment, powder rheology testing (see Methods section below) can be used to identify UHMWPE particles with suitable properties based on measurements of compressibility, cohesive strength, unrestrained yield stress (UYS) and / or angle of internal friction (AIF).

[0149] In one embodiment, a composition is provided that includes UHMWPE particles having a percent (%) compressibility of at least 20%, 30%, 40%, or 50% at a normal stress of 15 kPa as measured using a powder rheometer at 22°C.

[0150] In another embodiment, there is provided a composition comprising UHMWPE particles having a cohesive strength of at least 3 kPa, 4 kPa, or 5 kPa as measured using a powder rheometer at 22°C.

[0151] In another embodiment, there is provided a composition comprising UHMWPE particles having an unrestrained yield stress (UYS) of at least 10 kPa, 15 kPa, or 20 kPa as measured using a powder rheometer at 22°C.

[0152] In another embodiment, there is provided a composition comprising UHMWPE particles having an angle of internal friction (AIF) of at least 25°, 30°, or 35° as measured using a powder rheometer at 22°C.

[0153] Powder rheology is also used to identify suitable conditioned UHMWPE particles based on the percent change in angle of internal friction (AIF) (compared to nearby particles before conditioning), the percent change in basic flowability energy (BFE), and / or the percent change in specific energy (SE).

[0154] In one embodiment, a composition is provided comprising conditioned UHMWPE particles, which have a percent change in the angle of internal friction (AIF) relative to the UHMWPE particles before conditioning of at least 50%, 75%, 100%, 125%, 150%, 175%, or 200%, as measured using powder rheometry at 22°C.

[0155] In another embodiment, a composition is provided comprising conditioned UHMWPE particles having a percent change in basic flowability energy (BFE) of at least 10%, 20%, 30%, 40%, or 50% relative to the UHMWPE particles before conditioning.

[0156] In another embodiment, a composition is provided comprising conditioned UHMWPE particles having a percent change in specific energy (SE) of at least 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140% or 150% relative to the UHMWPE particles before conditioning.

[0157] In one embodiment, a composition comprising one or more of the above properties as determined by powder rheology is suitable for use in a binder system, hi another embodiment, a composition comprising one or more of the above properties as determined by powder rheology is suitable for use as a binder in forming an electrode, anode, or cathode.

[0158] In another embodiment, there is provided a composite binder system comprising a composition having one or more of the properties identified herein by powder rheology and a plurality of filler particles. In another embodiment, there is provided an electrode comprising a composition having one or more of the properties identified herein by powder rheology and comprising a plurality of filler particles. In a further embodiment, the composite binder system and / or electrode comprises a composite binder system wherein the composite binder comprises at least 95% by weight of the filler particles.

[0159] Identifying Suitable Binder Systems Using Capillary Rheology In one embodiment, a capillary rheology assay (see below) can be used to identify a suitable composite binder system comprising filler particles and UHMWPE particles.

[0160] In one embodiment, a composite binder system is provided that includes filler particles and UHMWPE resin particles, wherein the composite binder system has a force gradient of at least 200 N / mm, 300 N / mm, 400 N / mm, 500 N / mm, 600 N / mm, 700 N / mm, 800 N / mm, 900 N / mm, or 1000 N / mm as measured with a capillary rheometer on a test sample under the following conditions: 1. The test sample is a homogeneous mixture of 95 wt% filler particles and 5 wt% UHMWPE resin particles. 2. The barrel diameter is 12mm and the barrel length is 241.3mm. 3. The maximum test load is 20kN. 4. Temperature (barrel and die) is 130°C. 5. The reduction ratio of the tape die is 2.5. 6. The piston speed is 1 mm / sec. 7. Measure the normal force versus piston position and calculate the slope of the line of normal force versus piston position using the following equation: m=(y2-y1)÷(x2-x1) (where m = slope, (x1, y1) = coordinates of a first point on the line of force (N) versus piston position (mm), and (x2, y2) = coordinates of a second point on the line of force (N) versus piston position (mm).) The test sample is then capable of forming a solid extrudate.

[0161] Ratio of UHMWPE particle size to filler particle size to prepare suitable composite binder systems In another embodiment, a suitable composite binder system is prepared from UHMWPE resin particles and filler particles having similar particle sizes (median Da) with a relative size ratio not exceeding 10:1. In one embodiment, the composite binder system comprises: a plurality of filler particles characterized by a filler particle median value Da; The resin particles include UHMWPE resin particles, Resin particle median Da, a molecular weight of at least 2,000,000 g / mol; a fusion enthalpy of at least 190 J / g, and Bulk density of 0.04g / mL to 0.25g / mL, and The ratio of filler particle median Da to resin particle median Da is 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8, 7:1 to 1:7, 6:1 to 1:6, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2, and about 1:1.

[0162] Synthesis of ultra-high molecular weight polyethylene resin particles with less chain entanglement and low bulk density Polyolefin catalyst systems used to produce highly disentangled (also called "weakly entangled") UHMWPE reactor fines are typically based on separating and / or reducing the density of active sites, using lower monomer concentrations, adjusting the reaction medium, and / or reducing the reaction temperature.

[0163] These "single-site" catalyst systems are designed to control the density and spacing of active sites, as well as low temperatures, which increases the likelihood that growing polymer chains will form aligned crystalline lamellae rather than chain entanglements. Typical examples of such catalyst systems include, but are not limited to, metallocene, post-metallocene, and Fujita catalysts (FI catalysts). Polyolefin catalyst systems often incorporate aluminoalkyl and / or aluminoalkoxy cocatalysts. Examples of such catalytic systems include MgCl2-based heterogeneous Ziegler-Natta catalysts modified with polyhedral oligomeric silsesquioxane (4-OH POSS) (Guo et al., Ind. Eng. Chem. Res., 2022, 61, 16711-16720), MgCl2-based Ziegler-Natta catalysts modified with polyhedral oligomeric silsesquioxane (POSS) (Chen et al., Ind. Eng. Chem. Res. 2021, 60, 3354-3362), and FI catalysts such as bis(phenoxyimine) and bis(phenoxyketimine) group 4 transition metal complexes, which are heteroatom-coordinated early transition metal complexes combining a pair of asymmetric phenoxyimine [O-,N] chelating ligands with a group 4 transition metal (Makio and Fujita, Accounts of Chem. Res. (2009) 42(10), 1532-1544).

[0164] The polyolefin catalyst system used to produce the UHMWPE binder system of the present invention should be designed to produce a fine UHMWPE reactor powder with minimal crystalline lamella thickness, low bulk density, and very little entanglement. In one embodiment, the UHMWPE binder system comprises UHMWPE particles having a bulk density of about 0.04 g / mL to about 0.25 g / mL, about 0.04 g / mL to about 0.15 g / mL, about 0.05 g / mL to about 0.12 g / mL, or about 0.06 g / mL to about 0.08 g / mL. In a further embodiment, the binder system comprises UHMWPE particles having a bulk density of about 0.04 g / mL to about 0.25 g / mL, about 0.04 g / mL to about 0.15 g / mL, about 0.05 g / mL to about 0.12 g / mL, or about 0.06 g / mL to about 0.08 g / mL. a molecular weight of at least 2,000,000 g / mol, or at least 3,000,000 g / mol, or at least 4,000,000 g / mol, or at least 5,000,000 g / mol, or at least 6,000,000 g / mol, or at least 7,000,000 g / mol; a first fusion enthalpy greater than about 190 J / g, about 195 J / g, about 200 J / g, about 205 J / g, about 210 J / g, about 215 J / g, about 220 J / g, about 225 J / g, about 230 J / g, about 235 J / g, about 245 J / g, about 250 J / g, about 255 J / g, about 260 J / g, about 265 J / g, about 270 J / g, or about 275 J / g; and The bulk density is about 0.04 g / mL to about 0.25 g / mL, about 0.04 g / mL to about 0.15 g / mL, about 0.05 g / mL to about 0.12 g / mL, or about 0.06 g / mL to about 0.08 g / mL.

[0165] In one embodiment, the polyolefin catalyst system includes a solid catalyst support. In one embodiment, the polyolefin catalyst system includes a polyolefin catalyst support in the form of fine particles (see U.S. Pat. No. 9,181,359 B2 to Nishio et al.). In some embodiments, the catalyst support includes fine catalyst support particles having an average particle size of about 1 nm to 300 nm. In another embodiment, the use of fine particles as a polyolefin catalyst support can be used with various single-site catalysts capable of producing weakly entangled UHMWPE resin particles (e.g., metallocene, post-metallocene, FI catalysts, and modified Ziegler-Natta catalyst systems, including, but not limited to, MgCl-based Ziegler-Natta catalysts modified with polyhedral oligomeric silsesquioxanes (POSS)). In some embodiments, the present method for producing UHMWPE resin powder (neat) is prepared using a catalyst support in the form of fine particles according to U.S. Pat. No. 9,181,359 B2 to Nishio et al.

[0166] In the present invention, it is also desirable that the particle morphology be such as to reduce the level of connections created during the production of the polymer. These connections can be either entanglements or crystalline connections between separately grown crystals that are in contact with each other. A low bulk density of the polymer is an indication of the desired interstices between individual polymer crystals.

[0167] The choice of catalyst system is not limited as long as the polymer particles have the required properties described herein.

[0168] It should be understood that the composite materials and articles formed therefrom can also be implemented in a variety of other systems, such as supercapacitors, and are not intended to be limited to any of the specific examples provided herein.

[0169] Test Method Contact Thickness Measurement The thickness was measured using a manual Mitutoyo thickness gauge (Mitutoyo Corporation, Kawasaki, Japan) with a 6.3 mm metal plate.

[0170] Tensile strength Tensile strength was measured using the process described in ASTM D638-5. Unless otherwise specified, tensile strengths described here are reported as engineering stress (i.e., force normalized to the initial cross-sectional area of the sample).

[0171] Particle size and shape Particle size distribution measurements were performed on a Microtrac Series 5000-3L Sync particle size and shape analysis system (Microtrac MRB, York, PA, USA), which combines laser diffraction and dynamic image analysis. The instrument is controlled using Microtrac FLEX 12 software (Microtrac) with default parameters unless otherwise specified. This instrument combines two techniques into one instrument. Laser diffraction analysis is performed using scattered light from multiple lasers through a stream of suspended particles. Dynamic image analysis of the particle stream is also performed using a high-speed, high-resolution camera.

[0172] Samples are prepared as follows: Approximately 0.5 grams of sample powder is placed in a vial and dispersed in several milliliters of reagent-grade isopropyl alcohol (IPA) (Sigma Aldrich, St. Louis, MO, USA). An ultrasonic horn is used to aid in breaking down particle agglomerates within the sample (Qsonica, Newtown, CT, USA). If the suspension is stable to settling, it can be used directly for analysis. If not, the addition of a small amount of a suitable surfactant may be necessary.

[0173] The test procedure is generalized as follows: (1) After filling the Sync instrument with fresh IPA, the Sync transducer was zeroed using the SetZero procedure. (2) After zeroing, the "sample loading" procedure was initiated, and the sample suspension was added dropwise to the instrument reservoir until the light transmittance measured by the Sync was within the acceptable range, typically 88%-90%T. (3) The optical parameters (e.g., refractive index) of the particles and solvent were entered for subsequent calculations. (4) Data collection was then initiated using the FLEX software.

[0174] Particle size analysis is performed by the software once the scattered light is collected and averaged. Particle size distributions are calculated using Mie scattering theory and expressed on a volumetric basis. Various data analysis methods are provided, including normal particle size distribution plots, cumulative distribution plots, percentiles, and other moments of the distribution.

[0175] Particle shape analysis is performed on a large number of images (typically around 100,000). In addition to the raw image, there are approximately 20 descriptors used to quantify the shape distribution. These include parameters describing circularity, shape, roughness, and geometric class, and are expressed on a numerical basis.

[0176] Da (area equivalent diameter) corresponds to the diameter of a circle equal to the area of a particle image. The median Da of a particular particle distribution (i.e., D50Da) corresponds to the Da value at which 50% of the particles in the population have a smaller Da and 50% have a larger Da.

[0177] DSC measurement Differential scanning calorimetry (DSC) data were collected using a TA Instruments Discovery DSC (TA Instruments, Newcastle, DE) at either -50 °C or 35 °C to 200 °C at a heating rate of 10 °C / min. For resin samples, approximately 5 mg of powder was placed into a standard pan and lid combination available from TA Instruments. Samples were prepared by punching out 4 mm disks. The 4 mm disks were placed flat in the pan, and the lid was crimped to sandwich the composite sheet disk between the pan and lid. Melting enthalpy data were integrated using a linear integration scheme from 100 °C to 175 °C. Subsequent deconvolution of the melting region was performed using SeaSolve Software's PeakFit software (PeakFit v4.12 for Windows, Copyright 2003, SeaSolve Software Inc.). Standard conditions were used to fit the baseline (after inverting the data to generate a "positive" peak), and the observed data were then decomposed into individual melting components.

[0178] Freeman FT4 Powder Rheology Test Powder properties are important material characteristics that affect powder processing and therefore the quality of the final product. For the evaluation of PE resin and filler powders, a Freeman FT4 powder rheometer (Freeman Technology, UK) was used to perform (1) compressibility tests, (2) dynamic tests, and (2) shear tests at room temperature (approximately 22°C). Prior to the actual tests, a powder conditioning process was performed, which involved traversing the blade downwards and then upwards. This process removes any packing history, such as pre-solidification or excess air. All tests on the FT4 powder rheometer were performed at room temperature. The results of the powder rheology tests are shown in Example 14.

[0179] Definitions of terms used to describe powder rheology results Bulk Density: Measured in grams per cubic centimeter (g / mL), it is the mass per unit volume of the sample tested.

[0180] Compressibility: The percentage change in volume after compression is measured in %.

[0181] Basic Flow Energy (BFE): This is the amount of energy (work) required to move the rotating blade from the top to the bottom of the sample container, i.e., during a downward traverse, through a bed of sample powder. BFE is measured in millijoules (mJ).

[0182] Specific Energy (SE): This is the amount of energy (work) required to move the rotating blade from the bottom to the top of the sample container, i.e., during an upward traverse, through the bed of sample powder. It is then normalized to the mass of the sample. SE is measured in millijoules per gram (mJ / g).

[0183] Cohesive Strength: The shear stress required to break (yield) a sample at a normal stress of 0 as measured in a shear test. Cohesive strength is specified in kilopascals (kPa).

[0184] Unconfined Yield Stress (UYS): The normal stress required to break an unconfined powder sample at zero shear stress as measured in a shear test. UYS is specified in kilopascals (kPa).

[0185] Angle of Internal Friction (AIF): In a shear test, the shear stress value is measured at various normal stress levels. Typically, the shear stress value continues to increase as the normal stress to the sample increases. The AIF is the angle made by the shear stress value on the Y-axis and the line of normal stress on the X-axis in a shear test. The AIF is specified in degrees (°).

[0186] Compressibility Test The compressibility of polyethylene resin powder was measured using the Freeman FT4 standard method for compressibility measurement. This test method also produced bulk density values. Compressibility and density data are reported in Example 14. In this test, a vented piston was used to compress the sample under increasing normal stress. The powder sample was first preconditioned to remove any compaction within the powder. The vented piston used in this test consists of a woven stainless steel mesh compression surface, designed to allow entrapped air within the powder to escape uniformly across the surface of the powder bed. Each normal stress was applied for a specified time to allow the powder to reach equilibrium. The piston travel distance was measured for each applied normal stress, and compressibility was calculated as the percentage change in volume. The compressibility test was performed using a 50 mm inner diameter sample container with a capacity of 85 ml.

[0187] Dynamic Tests for Measuring Basic Flowing Energy (BFE) and Specific Energy (SE) Dynamic testing was performed using a 48 mm diameter blade, a 50 mm inner diameter, and a 160 mL powder sample container. Prior to the actual test, a powder conditioning process was performed in which the blade traversed downward and then upward. This process removed any packing history, such as prior solidification or excess air. The result of the test was a single flow energy value representing the resistance to flow in this downward flow mode, called the basic flow energy (BFE). BFE is measured in mJ. During this test, the flow pattern was a downward counterclockwise movement of the blade, creating a compressible, relatively high-stress flow mode in the powder. BFE was calculated from the work done when moving the blade through the powder from the top of the container to the bottom. Another material property obtained from the dynamic test was the specific energy (SE), calculated by dividing the work done when moving the rotating blade through the layer of sample powder from the bottom of the container to the top by the mass of the sample. SE is measured in mJ / g. The tip speed of the moving blade was 100 mm / s. The helix angle of the rotating blade was 5°. The same test was repeated eight times at a tip speed of 100 mm / s to examine the effect of test repetition on the resin samples. After the eighth test, the final three tests were performed at speeds of 70, 40, and 10 mm / s, respectively, to understand the material's response at lower blade tip speeds. Figure 6 shows the total energy in mJ measured during dynamic testing of Resin A and Conditioned Resin A. Figure 7 shows the dynamic test results for Resin B and Conditioned Resin B. Table 17 in Example 14 shows the BFE and SE values for UHMWPE resin powder samples.

[0188] Shear Test Shear tests were conducted using a 48 mm blade, 50 mm diameter, and an 85 mL sample container. The FT4 rheometer consists of a container for the powder sample and a shear head, which induces both normal and rotational stresses. During the test, the shear head moves downward, inserting the blade into the powder and inducing normal stress when the shear head face contacts the top of the powder. The shear head continues to move downward until the required normal stress s is established. A slow rotation of the shear head then begins, inducing shear t. The shear plane is established directly beneath the edge of the blade. As the powder bed resists the shear head rotation, the shear stress increases until the bed breaks or shears, at which point the maximum shear stress is observed. The normal stress is maintained constant throughout the shearing process. A shear rate of 18° / min was used for all shear tests. This maximum shear is recorded as the yield point. For the shear tests, the powders were preconditioned to remove any pre-consolidation of the powder. Shear stress values for the powder samples were measured at normal stress values of 5, 6, 7, 8, 9, and 15 kPa. Figure 8 shows the yield points of Resin A and conditioned Resin A powder samples. Figure 9 shows the yield points of Resin B and conditioned Resin B powder samples. The results of the shear tests are described in Example 14.

[0189] Capillary Rheology Test Rheological tests of the dry mixture (filler particles + UHMWPE resin powder) and UHMWPE resin powder were performed using a GOTTFERT capillary rheometer (GOTTFERT Werkstoff-Prufmaschinen, GmbH, SiemensstraBe 2, 74722 Buchen, Germany) with a test load of 20 kN. A barrel size of 12 mm diameter and 241.3 mm length was used. A flat tape die with a reduction ratio (the minimum cross-sectional area of the die divided by the cross-sectional area of the barrel) of 2.5 was used for the experiments. Normal force data were collected at a piston speed of 1 mm / s. A piston speed of 1 mm / s was used for all experiments. Experiments were performed at two die and barrel temperature settings: 125 °C and 130 °C. During testing, the dry powder sample was loaded into the barrel of the capillary rheometer, and the absence of bubbles or voids in the material was confirmed. Before the actual run, the open end of the barrel was locked and a force of 500 N was applied to compress the powder sample inside the barrel.

[0190] After the powder was compressed, the compression force was removed and the powder sample was allowed to sit in the barrel for 5 minutes to reach a uniform temperature. The lock bolt was replaced with the die, and the actual test began. During the test, normal force and piston position data were collected using the rheometer software. Piston force and position data were recorded, and visual observations were performed to assess the quality of the extrudate. Typically, as the piston begins to move within the barrel and compress the powder sample within it, the force required to push the material out of the die continues to increase, and as soon as the material exits the die, the normal force decreases with the advancement of the piston position. Force and piston position data were collected for all samples tested. The slope of the force versus piston position data was calculated for all samples using a linear trendline (y = mx + b) in Microsoft Excel (Microsoft Corp., Redmond, WA), where m = slope, x = piston position, b = intercept, and y = normal force. m=(y2-y1)÷(x2-x1) (x1,y1) = coordinates of the first point on the line of force (N) versus piston position (mm) (x2,y2) = coordinates of the second point on the line of force (N) versus piston position (mm).

[0191] Example 15 shows the capillary rheology data for the samples tested. Figure 10 shows the slope (N / mm) data for the Resin A + filler mixture and the conditioned Resin A + filler mixture. [Example]

[0192] In the examples, the following nomenclature is used:

[0193] Resin A is an ultra-high molecular weight polyethylene (UHMWPE) resin having a molecular weight of at least 2,000,000 g / mol, a melt enthalpy of at least 190 J / g, and a bulk density of about 0.04 g / mL to about 0.25 g / mL.

[0194] The conditioned resin A is a resin A in which the size and shape of the polyethylene resin A particles have been changed to a median value Da of about 5 microns to 300 microns.

[0195] Resin B is an ultra-high molecular weight polyethylene (UHMWPE) resin with a molecular weight of at least 1,800,000 g / mol, a melting enthalpy of 200 J / g, and a bulk density of about 0.43 g / mL, commercially available as PM-200 from Mitsui Chemicals, Inc. (Tokyo, JP).

[0196] Conditioned Resin B is Resin B in which the size and shape of UHMWPE Resin B particles have been modified to have a median Da of about 5 microns to about 20 microns.

[0197] Example 1 Lithium-ion battery anode fabricated using unconditioned Resin A A composite blend of 95.15 wt. % graphite (commercially available from Superior Graphite, Chicago, IL, USA), 1.5 wt. % carbon black (commercially available from Imerys SA, Bironica, Switzerland), and 3.35 wt. % Resin A was blended with shear mixing in the manner generally taught in U.S. Patent Publication No. 2005 / 0057888 to Mitchell et al., published March 17, 2005. The resulting free-standing porous fibrillated UHMWPE composite sheet contained the filler described above durably entangled within the UHMWPE fibrillated microstructure. The composite sheet had a thickness of 140 microns and an areal weight of 216 g / m. 2 , envelope density is 1.54 g / cm 3 The tensile stress at maximum load was approximately 380 kPa (ASTM D638-5 Rev 8). This composite sheet was designated Sample 1. Table 1 shows the properties of Resin A used to prepare Sample 1 and the properties of composite sheet Sample 1. Table 2 shows the DSC peak integration data for Sample 1. [Table 1] [Table 2]

[0198] Example 2 Lithium-ion battery anodes fabricated using conditioned resin A Prior to mixing with graphite, Resin A was conditioned by applying shear to alter the size and shape of the resin. A composite blend of 95.15 wt. % graphite (Superior Graphite, supra), 1.5 wt. % carbon black (Imerys SA, supra), and 3.35 wt. % conditioned Resin A was then blended with shear mixing in a manner generally taught in U.S. Patent Publication No. 2005 / 0057888 to Mitchell et al., published March 17, 2005. The resulting free-standing porous fibrillated UHMWPE composite sheet contained the filler described above durably entangled within the fibrillated UHMWPE microstructure. A total of six composite sheet samples were produced using this process (conditioning Resin A, fabricating composite sheets from conditioned Resin A). These samples were designated Samples 2–7. Table 1 lists the properties of Resin A and the conditioned Resin A used to fabricate Samples 2–7, as well as the properties of the composite sheets of Samples 2–7. Table 2 contains the DSC peak integration data for Samples 2-7.

[0199] For the assembly of half-cells, five 15.6 mm diameter disks were punched out from each of Samples 2, 3, and 4 (15 disks in total). These disks were designated Samples 2A-2E, 3A-3E, and 4A-4E, respectively. The average mass per area of Samples 2A-2E was 214 g / m. 2 , the average thickness is 135 microns and the envelope density is 1.59 g / cm 3 The average mass per area of Samples 3A to 3E was 216 g / m 2 , the average thickness is 131 microns and the envelope density is 1.65 g / cm 3 The average mass per area of Samples 4A to 4E was 226 g / m 2 , average thickness is 142 microns, envelope density is 1.59 g / cm 3 It was.

[0200] Example 3 Lithium-ion battery cathodes fabricated using conditioned resin A Before mixing with graphite, Resin A was conditioned by applying shear to change the size and shape of the resin. The size and shape data are shown in Table 1. Next, 94.3 wt% Lithium Nickel Manganese Cobalt Oxide NMC-111 (Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 A composite blend of 02 (available from MSE Supplies LLC, Tucson, Arizona), 1.5 wt. % carbon black (Imerys SA, supra, C65), 2.5 wt. % graphite (Imerys SA, supra, SFG6-L), and 1.6 wt. % conditioned Resin A was sheared and blended in a manner generally taught in U.S. Patent Publication No. 2005 / 0057888 to Mitchell et al. to produce a free-standing cathode having a thickness of 145 microns to 160 microns. The resulting free-standing porous fibrillated UHMWPE composite sheet contained the filler described above durably entangled within the fibrillated matrix. The porous fibrillated UHMWPE composite sheet had a thickness of 151 microns and an areal mass of 501 g / m. 2 , bulk density is 3.30 g / cm 3 This composite sheet was named Sample 8.

[0201] For the assembly of half-cells, five disks with a diameter of 15.6 mm were punched out from Sample 8. These disks were named Samples 8A to 8E. The average mass per area of Samples 8A to 8E was 501 g / m 2 , the average thickness is 151 microns and the average envelope density is 3.31 g / cm 3 It was.

[0202] Comparative Example 1 Control lithium-ion battery anode preparation The control lithium-ion battery anode composition was as follows (dry mass fraction): 94% Superior Graphite SLC1520T graphite, commercially available from Superior Graphite, USA; 1.5% C65 carbon black, commercially available from Imerys SA, Belgium; 1.5% BH1000 NaCMC (NaCMC = sodium carboxymethylcellulose), commercially available from Wealthy Chemical Industry (Suzhou) CO, Ltd., Jiangsu Province, China; 3% styrene butadiene rubber (SBR), available from MTI Corp., Richmond, Calif.

[0203] The nominal intrinsic densities (or skeletal densities) of these materials are listed in Table 3. Using these values, mass fractions can be easily converted to volume fractions, allowing one skilled in the art to easily calculate electrode porosity without undue burden. The properties of the fabricated lithium-ion battery anodes are listed in Table 4. [Table 3] [Table 4]

[0204] A control lithium-ion battery anode was prepared by the following steps. a) Dissolve NaCMC in deionized water and allow to equilibrate overnight (approximately 14-18 hours). b) Disperse the C65 using a 1.5 inch diameter Cowles blade at 2000 revolutions per minute (RPM). c) Disperse SLC1520T graphite using a 1.5 inch diameter Cowles blade at 2000 RPM. d) Dilute with DI water as needed to adjust viscosity to maintain a vortex for efficient mixing. e) Blend into SBR at 1000 RPM using a 1.5 inch diameter Cowles blade. f) Cast onto 10 μm copper foil using a doctor blade. g) Dry on a large hot plate in air at 35°C. h) To remove residual solvent, the air-dried electrodes are transferred to a vacuum oven and dried under vacuum at 110°C overnight. i) Punch out 1 inch diameter electrode pieces and weigh them to determine the mass per area of the active layer (the mass of the foil substrate must be subtracted). j) Use a drop micrometer to measure the thickness of a 1-inch diameter electrode to determine the thickness of the active layer (the thickness of the foil substrate must be subtracted), and calender it so that the density of the active layer is approximately 1.6 g / cc.

[0205] The coated and dried control lithium-ion battery anode sheet (corresponding to the material at the end of step (h) above) is designated Sample 9. The cut and calendered samples (corresponding to the material at the end of step (j) above) are designated Samples 9A-9E. The average mass per area (not including the foil) of the control lithium-ion battery anode was 19.2 mg / cm. 2 The nominal foil thickness was 10 microns. The average initial electrode thickness (with foil, before calendering) was 191 microns. The average final electrode thickness (with foil, after calendering) was 128 microns, corresponding to an average density of 1.63 g / cc and an average porosity of 24%. Note that the electrode density is the so-called "envelope" density, calculated by dividing the mass per area of the active layer by the thickness of the active layer.

[0206] Comparative Example 2 Preparation of control lithium-ion battery cathode The control lithium-ion battery cathode composition was (dry mass fraction) as follows: 93% of NCM-111 (NCM-111 is Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 O2), MSE Supplies LLC, Tucson, Arizona, USA; 3% Kynar® HSV-900 PVDF (Polyvinylidene Fluoride) Arkema Inc., King of Prussia, PA, USA 1.5% C65 carbon black, Imerys SA, Belgium; 2.5% SFG6-L conductive graphite, Imerys SA, Belgium.

[0207] The nominal intrinsic densities (or skeletal densities) of these materials are listed in Table 5. Using these values, one skilled in the art can easily convert the mass fraction to volume fraction and calculate the porosity of the electrode. The properties of the fabricated lithium-ion battery cathodes are listed in Table 6. [Table 5] [Table 6]

[0208] A control cathode was prepared according to the following steps. a) All mixing steps were carried out under an argon atmosphere. b) PVDF was dissolved in dry NMP (NMP is N-methylpyrrolidone). c) A 1.5 inch diameter Cowles blade was used to disperse the C65 at 2000 RPM. d) SFG6-L conductive graphite was dispersed using a 1.5 inch diameter Cowles blade at 2000 RPM. e) NCM-111 was dispersed using a 1.5 inch diameter Cowles blade at 2000 RPM. f) Diluted with dry NMP if necessary. g) Cast onto 15 μm aluminum foil using a doctor blade. h) Dried on a large hot plate in air at 80°C. i) To remove residual solvent, the air-dried electrodes were transferred to a vacuum oven and dried under vacuum at 110°C overnight. j) One inch diameter electrode pieces were cut and weighed to determine the mass per area of the active layer (the mass of the foil substrate must be subtracted). k) The thickness of a 1 inch diameter electrode was measured using a drop micrometer to determine the thickness of the active layer (the thickness of the foil substrate must be subtracted) and calendered to give an active layer density of approximately 3.0 g / cc.

[0209] The coated and dried control lithium-ion battery cathode sheet (corresponding to the material at the end of step (i) above) is designated Sample 10. The cut and calendered samples (corresponding to the material at the end of step (k) above) are designated Samples 10A-10D. The average mass per area (not including the foil) of the control lithium-ion battery cathode was 43.6 mg / cm. 2 The nominal foil thickness was 15 microns. The average initial electrode thickness (with foil, before calendering) was 210 microns. The average final electrode thickness (with foil, after calendering) was 162 microns, corresponding to an average envelope density of 2.97 g / cc and an average porosity of 31%. Note that the electrode density is the so-called "envelope" density, calculated by dividing the mass per area of the active layer by the thickness of the active layer.

[0210] Example 6 Assembly of half-cells Lithium-ion battery anode and lithium-ion battery cathode samples were tested as half-cells 10 in standard 2032 cell hardware. Each half-cell, shown in Figure 1, 1) included a housing 12 containing a positive can 14 and a negative can 16. The half-cell 10 included a conical spring 18, a spacer 20, a separator 22, and an electrolyte 24, as well as a lithium disk 26. Each half-cell 10 contained either a lithium-ion battery anode or a lithium-ion battery cathode as the positive electrode 100. For all half-cells 10, a lithium disk 26 (16 mm diameter, 500 microns thick) was used as the negative electrode, and the electrolyte 24 was 1 M LiPF6 in EC:EMC (Soulbrain MI, Northville Township, MI, USA), in a 3:7 weight ratio (EC is ethylene carbonate, EMC is ethyl methyl carbonate). The "anode" half-cell was constructed with a lithium-ion battery anode (e.g., a graphite-based material) as the positive electrode 100. The cathode half-cell was constructed with a lithium-ion battery cathode (e.g., an NMC-based material) as the positive electrode. The lithium-ion battery cathode had a diameter of 15.6 mm. The separator 22 in the anode half-cell was glass fiber filter paper (WHATMAN®, grade GF / F, available from MilliporeSigma, Burlington, Massachusetts, USA). The separator 22 in the cathode half-cell was a polypropylene / polyethylene / polypropylene trilayer membrane (CELGARD® 2320, Cellgard LLC, Charlotte, North Carolina, USA). The diameter of the separator 22 was 19 mm.

[0211] The 2032 hardware was obtained from Shenzhen TICO Technology Co., Ltd., Shenzhen, China. (Note that a grommet was incorporated into the negative can 16 to seal the cell and electrically isolate the two terminals when the cell was crimped.) The cathode half-cell hardware was made from 316 stainless steel, and the anode half-cell hardware was made from 304 stainless steel. An exploded view of the half-cell components is shown in Figure 1. The spacer 20 for the anode half-cell was 304 stainless steel, 1 mm thick and 16 mm in diameter. The spacer 20 for the cathode half-cell was 316 stainless steel, 1 mm thick and 16 mm in diameter. The conical spring 18 for the anode half-cell was 304 stainless steel, described by the manufacturer as "15.4 x 1.1 for 20-series batteries." The conical spring 18 for the cathode half-cell was 316 stainless steel, described by the manufacturer as "15.4 x 1.1 for 20-series batteries."

[0212] All cells (i.e., the half-cells described above) were assembled in an argon-filled glove box. The lithium disks 26, electrolyte 24, and CELGARD® 2320 were stored in the argon glove box to minimize moisture content. Prior to cell assembly, the cell hardware (positive electrode can 14, negative electrode can 16, spacer 20, conical spring 18), lithium-ion electrodes 100, 200, and glass fiber filter paper were dried overnight under vacuum at 80°C. The following steps were followed when assembling the cell: a) A 16 mm lithium disk 26 was brushed on both sides with a stainless steel brush. b) A lithium disk 26 was placed in the anode can 16. c) 150 μL of electrolyte 24 was added to negative electrode can 16 . d) A 19 mm separator 22 was aligned over the anode can 16 (note that the separator diameter is larger than the anode can diameter). e) The positive electrode 100 was aligned on top of the separator 22 (active material side down, if there was a metal foil) and placed in the center of the negative can 16. f) A 1.0 mm spacer 20 was aligned on top of the positive electrode 100. g) The separator 22, positive electrode 100, and spacer 20 were pressed into the negative electrode can 16 (the edges of the separator encase the electrodes 100, 200, and spacer 20 to prevent shorting at the edges of the separator). h) The conical spring 18 was placed on top of the spacer 20 and was open wide towards the spacer 20. i) The positive electrode can 14 was placed on top and compressed to 7,500 to 9,000 kPa to clean the residual electrolyte 24 from the cell surface. j) The half-cell 10 was placed in an oven (ambient pressure in an air environment) at 45° C. for 16 hours to promote wetting of the electrolyte.

[0213] Full cells can be assembled similarly to cathode half cells (i.e., cell hardware is 316 stainless steel, separator is Celgard tri-ply, and lithium-ion anode is used instead of lithium disc). In some cases, the diameter of the negative electrode can be slightly larger than the cathode to prevent edge artifacts. Like cathode half cells, full cells are discharged when assembled.

[0214] Example 7 Anode half-cell test All half-cells were charged and discharged using a Neware battery cycler (CT-4008T-5V50mA-164-U Three Range Battery Testing Equipment, Neware Battery Testers Int., Belleville, IL, USA). Note that the anode half-cell was in a charged state when assembled, so one cycle counts as a discharge followed by a charge. The voltage range of the anode half-cell was 0.01 V to 1.5 V. The anode half-cell was discharged in CCCV (constant current-constant voltage) mode (i.e., discharging the cell at a constant current until a lower voltage limit was reached, then discharging at a constant voltage until the current decreased to a C / 20 rate) (corresponding to the lithiation of the positive electrode) and charged in CC (constant current) mode (i.e., charging the cell at a constant current until an upper voltage limit was reached). Charge and discharge capacities are reported in mAh / g, and mass indicates the amount of active material (e.g., SLC1520T graphite for the anode half-cell). In the first cycle, the constant-current discharge and charge were performed at a nominal rate of C / 20. The current required for a nominal rate of 1C was determined assuming 355 mA / g, where mass refers to the mass of the active material (e.g., SLC1520T graphite). To calculate the initial capacity loss, the first discharge capacity was subtracted from the first charge capacity, and the difference was divided by the first discharge capacity. The discharge / charge C rates for the initial formation and power testing of the half-cells are shown in Table 7. After cycle 25, 49 additional cycles were performed in the same manner with a 0.2C discharge (lithiation) and a 0.5C charge (delithiation) to evaluate capacity fade. The discharge / charge capacity and energy for each cycle were determined, along with the areal series resistance. Additionally, ex-situ measurements of the through-plane electrical resistance of the positive electrode were performed for comparison with the half-cell data. Table 8 shows the first discharge capacity, first charge capacity, and initial capacity loss of a "control" lithium-ion anode sample (i.e., an anode prepared according to Example 4). Table 9 shows the first discharge capacity, first charge capacity, and initial capacity loss of the inventive lithium-ion anode samples of the present disclosure (i.e., anodes prepared according to Example 2). [Table 7] [Table 8] [Table 9]

[0215] Example 8 Cathode half-cell test All half-cells were charged and discharged using a Neware battery cycler (CT-4008T-5V50mA-164-U 3-range battery tester). Because the cathode half-cell was in a discharged state when assembled, one cycle was counted as a charge followed by a discharge. The voltage range of the cathode half-cell was 3.0 V to 4.3 V. The cathode half-cell was charged in CCCV (constant current-constant voltage) mode (i.e., charging the cell at a constant current until the upper voltage limit was reached, then charging at a constant voltage until the current decreased to a C / 20 rate) (corresponding to delithiation of the positive electrode) and discharged in CC (constant current) mode (i.e., discharging the cell at a constant current until the lower voltage limit was reached). Charge and discharge capacities are reported in mAh / g, where mass refers to the amount of active material (e.g., NMC-111 from MSE Supplies, LLC for the cathode half-cell). The charge and discharge of the first constant current portion was performed at a nominal rate of C / 20. The current required for a nominal rate of 1C was determined assuming 155 mA / g, where mass refers to the mass of the active material (e.g., NMC-111). To calculate the initial capacity loss, the first charge capacity was subtracted from the first discharge capacity and the difference was divided by the first charge capacity. The charge / discharge C-rates for the initial formation and power testing of the half cells are shown in Table 10. The first charge capacity, first discharge capacity, and initial capacity loss of the "control" lithium-ion cathode sample (i.e., the cathode prepared according to Example 5) are shown in Table 11. Table 12 shows the first charge capacity, first discharge capacity, and initial capacity loss of the inventive lithium-ion cathode sample of the present disclosure (i.e., the cathode prepared according to Example 3). After cycle 25, an additional 49 cycles were performed in the same manner at 0.2C charge (delithiation) and 0.5C discharge (lithiation) to evaluate capacity fade. The discharge / charge capacity and energy were measured at each cycle, along with the areal series resistance. Additionally, ex-situ measurements of the through-plane electrical resistance of the positive electrode were performed for comparison with the half-cell data. Full lithium-ion cells (or "full cells") can be tested using the same protocol as the cathode half-cells. The current density corresponding to a 1C rate is determined based on the cathode electrode, just as for the cathode half-cells. [Table 10] [Table 11] [Table 12]

[0216] Example 9 DSC scan of the UHMWPE resin used in Examples 1 and 2 The DSC thermograms of Resin A used to prepare Sample 1 in Example 1 and the DSC thermograms of the conditioned Resin A used to prepare Samples 2-7 in Example 2 are shown in FIG. 5.

[0217] Example 10 High mass fraction of filler (low binder content) Three composite blends of varying compositions were prepared as described in Example 2. The compositions included: 1) A composite blend of 95.99 wt% graphite (Superior Graphite, supra), 1.51 wt% carbon black (Imerys SA, supra) and 2.5 wt% conditioned resin A; 2) A composite blend of 96.48 wt% graphite (Superior Graphite, supra), 1.52 wt% carbon black (Imerys SA, supra) and 2.0 wt% conditioned resin A; 3) A composite blend of 96.97 wt% graphite (Superior Graphite, supra), 1.53 wt% carbon black (Imerys SA, supra) and 1.50 wt% conditioned resin A. The results for the three composite blends are shown in Table 13. [Table 13]

[0218] Example 11 Direct electrode formation on metal foil Anodes for lithium-ion batteries were fabricated using conditioned Resin A and copper foil (thickness: 10 microns). The foil was rolled between rolls and dropped along one side of the roll. A composite blend of 95.15 wt% graphite (Superior Graphite, as above), 1.5 wt% carbon black (Imerys SA, as above), and 3.35 wt% conditioned polyethylene Resin A was co-fed onto the roll and foil, and the laminated electrode was directly processed. An electrode with the anode composite integrated onto the copper foil was obtained. The thickness was 220 microns and the mass per area was 528 g / m. 2 It was.

[0219] The conditioned resin A and aluminum foil (thickness: 15 microns) were used to fabricate cathodes for lithium-ion batteries. The foil was dropped between rolls along one side of the roll. 94.3 wt% lithium nickel manganese cobalt oxide NMC-111 (Li 1.05 Ni 0.33 Mn 0.33 Co 0.33 A composite blend of 02 (available from MSE Supplies LLC, Tucson, Arizona), 1.5 wt.% carbon black (Imerys SA, supra, C65), 2.5 wt.% graphite (Imerys SA, supra, SFG6-L), and 1.6 wt.% conditioned polyethylene resin A was fed together into a roll and foil for direct processing. A cathode composite integrated onto aluminum foil was obtained. The film had a thickness of 200 microns and a mass per area of 704 g / m. 2 The compressive electrical resistance of these samples was measured. For comparison, the compressive electrical resistance of anode and cathode electrode samples adhered to foil with an adhesive was also measured. Table 14 shows the compressive electrical resistivity. The compressive resistance measurement was performed at a pressure of 2 cm. 2 The electrical resistance in the thickness direction was measured when a pressure of 30 kg was applied from the circular terminal. In order to stabilize the measured value, a second measurement was carried out and the value was used. [Table 14]

[0220] Comparative Example 3 Comparative Example for Resin Conditioning Additional composite electrodes were fabricated using different UHMWPE binders than those described in Example 2. For the comparative polyethylene composite, a composite blend of 95.15 wt. % graphite (Superior Graphite, as above), 1.5 wt. % carbon black (Imerys SA, as above), and 3.35 wt. % Resin B was used. For the PTFE composite, a composite blend of 91.27 wt. % graphite (Superior Graphite, as above), 1.44 wt. % carbon black (Imerys SA, as above), and 7.30 wt. % PTFE was used. Composite electrode samples were fabricated using Resin A, Resin B, and PTFE in the compositions listed. Additionally, composite samples were fabricated using conditioned Resin A, conditioned Resin B, and conditioned PTFE. A total of six composite sheets were produced. The data are shown in Table 15. [Table 15]

[0221] Example 12 Anodes fabricated with alternative active materials Anode samples were prepared according to the procedure described above in Example 2. After conditioning the UHMWPE resin, a composite blend consisting of 95.15 wt% graphite (Nippon Graphite, CGB-6R), 1.5 wt% carbon black (Imerys SA, as above), and 3.35 wt% conditioned Resin A was used to prepare anode samples with a thickness of 175 microns and a mass per area of 322.5 g / m. 2 This composite material functioned as an electrode.

[0222] Example 13 Cathodes fabricated with alternative active materials Additional cathode samples were prepared according to the procedure described in Example 3 above. After conditioning Resin A, a composite blend of 94.3 wt% lithium cobalt oxide LiCoO2 (Cellseed C-5H, Nippon Chemical), 1.5 wt% carbon black (Imerys SA, supra; C65), 2.5 wt% graphite (Imerys SA, supra; SFG6-L), and 1.6 wt% conditioned Resin A was used to prepare a cathode with a thickness of 170 microns and a mass per area of 567.6 g / m. 2 This composite material functioned as an electrode.

[0223] Example 14 Powder rheology testing of UHMWPE resins Powder rheology testing was performed on several UHMWPE resins, including Resin A, Conditioned Resin A, Resin B, and Conditioned Resin B. Data Tables 16-18 show the change in resin properties using the FT4 Powder Rheometer compressibility test, dynamic test, and shear test, respectively. Table 16 shows the bulk density and compressibility values measured in the powder rheometer compressibility test. The data also shows the percentage change in bulk density and compressibility after conditioning for Resin A and Resin B. Table 17 shows the dynamic test results and the percentage change in basic flow energy (BFE) and specific energy (SE) after conditioning for Resin A and Resin B. Table 18 shows the shear test results, including the percentage change in cohesion, unconfined yield stress (UYS), and angle of internal friction (AIF), for polyethylene resins. The data in the table also shows the percentage change in properties such as cohesion, unconfined yield stress, and angle of internal friction after conditioning for Resin A and Resin B.

[0224] A significant change in bulk density was observed when Resin A was conditioned to Resin A Conditioning 1 and Resin A Conditioning 2. As shown in Table 16, bulk densities increased by 43.88% and 52.24%, respectively, when Resin A was conditioned to Resin A Conditioning 1 and Resin A Conditioning 2. However, only a 1.38% increase in bulk density (g / cc) was observed when Resin B was conditioned. A 48.43% increase in resin compressibility (%) was observed when Resin A was conditioned to Resin A Conditioning 1. A 47.29% increase in resin compressibility (%) was observed when Resin A was conditioned to Resin A Conditioning 2. A 21.25% increase in compressibility (%) was observed when Resin B was conditioned. [Table 16]

[0225] Table 17 shows the powder rheology dynamic testing results for Resin A and Resin B, as well as Conditioned Resin A and Conditioned Resin B. As shown in the data in Table 17, the BFE value of Resin A increased by 56.06% and 34.18%, respectively, after conditioning to Resin A Conditioning 1 and Resin A Conditioning 2. However, conditioning Resin B decreased the BFE value by 6.67%. Resin A also showed a significant increase in SE value after conditioning, increasing by 158.85% after conditioning to Resin A Conditioning 1 and 154.71% after conditioning to Resin A Conditioning 2. Resin B showed a very small increase of 1.94% after conditioning to Resin B Conditioning.

[0226] Table 18 shows the powder rheology shear test data for Resin A and Resin B, as well as conditioned Resin A and conditioned Resin B. The percent increase in cohesion value when Resin A was conditioned to Resin A Conditioning 1 was 3.68. The percent increase in cohesion value when Resin A was conditioned to Resin A Conditioning 2 was 2.02. However, when Resin B was conditioned to Resin B Conditioning, the cohesion value decreased by 19.84%. The UYS value of Resin A increased by 66.62% and 59.63% when conditioned to Resin A Conditioning 1 and Resin A Conditioning 2, respectively. The UYS value increased by 22.30% when Resin B was conditioned to Resin B Conditioning. The AIF value of conditioned Resin A increased by 202.23% and 192.06% when conditioned to Resin A Conditioning 1 and Resin A Conditioning 2, respectively. However, when Resin B was conditioned with Resin B Conditioning, the AIF value of Resin B decreased by 5.12%. [Table 17] [Table 18]

[0227] Example 15 Capillary Rheology Data UHMWPE resins and blends of UHMWPE with fillers shown in Table 19 were tested in a capillary rheometer as described in the test methods above. Table 19 shows the results of the capillary rheometer testing. All experiments were performed at a die and barrel temperature of 130°C. [Table 19]

[0228] Example 16 Filler binder mixing It was determined that better mixing and satisfactory (stronger, more uniform) tape formation was achieved when powders with similar or more similar particle sizes were used compared to powders with less similar particle sizes. When Resin A particles with a median particle size of 314 microns were mixed with filler particles with a median particle size of 14 microns, tape formation was unsatisfactory. When Resin A conditioned to 36 or 28 microns was used, tape formation with 14 micron filler particles was satisfactory. The closer the particle sizes of the UHMWPE resin and filler particles, the stronger the tape formation. Table 20 shows the various particle sizes of the binder UHMWPE and filler particles in each composition. For optimal mixing, a ratio of UHMWPE particle size to filler particle size close to 1 is preferred. Table 20 also shows the shape parameters of the resin particles and filler particles, the ratio of length to width (L / W). [Table 20]

[0229] Example 16 Foil adhesives and electrode adhesion to foil A conductive adhesive material was prepared to bond the freestanding electrode to the metal foil. The conductive materials used were high-purity artificial graphite (SP-270, manufactured by Nippon Graphite Industries Co., Ltd.) with an average particle size of 8 microns and acetylene black (Denka Black, manufactured by Denki Kagaku Kogyo Kabushiki Kaisha). Poly-N-vinylacetamide (PNVA GE191-104, manufactured by Showa Denko K.K.) was used as the binder. These materials were mixed to a material content of graphite, acetylene black, PNVA, and water = 3.5:3.5:54:39 wt%. Copper foil (10 microns thick) was prepared as the anode current collector, and aluminum foil (15 microns thick) was prepared as the cathode current collector.

[0230] The conductive adhesive was coated onto one side of the current collector foil using a brush. After coating, an electrode was laminated onto the conductive adhesive-coated side of the foil (i.e., one side) and passed through a compression roll to produce a laminated sheet. The laminated electrode was heated in a continuous hot air dryer set at 100°C for 10 minutes to remove the dispersant from the conductive adhesive. A laminated electrode was obtained.

[0231] Example 17 Conditioning of Resin A Composite blends of 95.15 wt% graphite (commercially available from Superior Graphite, Chicago, IL, USA), 1.5 wt% carbon black (commercially available from Imerys SA, Bironica, Switzerland), and 3.35 wt% Resin A were blended according to the method described in Example 1. Sample 1 used Resin A, while Samples 2, 3, and 4 used three different conditioned forms of Resin A. Table 21 lists the properties of Resin A used in the preparation of Samples 1-4 and the properties of composite sheet Samples 1-4. Table 22 provides the DSC peak integration data for Samples 1-4. [Table 21] [Table 22]

[0232] The invention of this application has been described above generally and with reference to specific embodiments. It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments without departing from the scope of the present disclosure. Therefore, it is intended that the embodiments cover the modifications and variations of the present invention provided they come within the scope of the appended claims and their equivalents.

Claims

1. shearing filler particles with ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least 2,000,000 g / mol and a melt enthalpy of at least 190 J / g to form a mixed particle composition, wherein the filler particles are durably entangled within fibrils formed by the UHMWPE particles; and forming the mixed particle composition into an article; wherein the article contains at least 80% by weight of filler particles.

2. The method of claim 1 , further comprising fibrillating the UHMWPE particles prior to shearing the filler particles and the UHMWPE particles.

3. The method of claim 1 or 2, wherein shaping the mixed particle composition into an article comprises calendering the mixed particle composition.

4. The method of any one of claims 1 to 3, wherein the article has a DSC curve with a DSC peak between about 143°C and about 175°C, and the article has a fibrillation rate greater than 0%.

5. The method of any one of claims 1 to 4, wherein the particles comprise at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

6. 6. The method of any one of claims 1 to 5, comprising conditioning the UHMWPE particles prior to shearing the filler particles and the UHMWPE particles, wherein the conditioned UHMWPE particles have a median Da of from about 10 microns to about 300 microns.

7. The method of any one of claims 1 to 6, wherein the mixed particle composition comprises less than 10% by weight of the fibrillizable UHMWPE particles.

8. a filler material comprising filler particles; and a binder system comprising ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least 2,000,000 g / mol and a melt enthalpy of at least 190 J / g; A composite material comprising: The filler material and the UHMWPE particles are sheared and molded into an article, the composite exhibiting a DSC peak between about 143°C and about 175°C.

9. 9. The composite material of claim 8, wherein the composite material has a DSC curve with a DSC peak at about 143°C to about 175°C, and the article has a fibrillation rate greater than 0% when the fibrillation rate is determined by the integration of the DSC peak as a percentage of the integral of the DSC curve from about 100°C to about 175°C.

10. 10. The composite material of claim 8 or 9, wherein the filler material is selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

11. The composite material of any one of claims 8 to 10, wherein the binder system comprises less than 20% by weight of polytetrafluoroethylene.

12. The composite material of any one of claims 8 to 11, wherein the binder system does not include polytetrafluoroethylene.

13. Filler particles; Fibrillizable ultra-high molecular weight polyethylene (UHMWPE) particles A mixed particle composition comprising: The UHMWPE particles have a molecular weight of at least about 2,000,000 g / mol, a bulk density of about 0.04 g / mL to about 0.25 g / mL, and a melt enthalpy of at least 190 J / g; A mixed particle composition comprising less than about 10% by weight of fibrillizable binder particles in said mixed particle composition.

14. 14. The mixed particle composition of claim 13, wherein the mixed particle composition comprises less than about 5% by weight of fibrillizable binder particles.

15. 14. The mixed particle composition of claim 12 or 13, wherein the filler material comprises at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

16. The mixed particle composition according to any one of claims 12 to 15, wherein the UHMWPE particles are formed from aggregates of fine particles, and the fine particles have an average diameter of 10 nm or more and 2000 nm or less.

17. Filler particles; a binder system including fibrillated ultra-high molecular weight polyethylene (UHMWPE) particles; An article comprising: the fibrillated UHMWPE particles have a molecular weight of at least about 2,000,000 g / mol, a median Da of about 5 microns to about 300 microns, and a melting enthalpy of at least 190 J / g; The article is characterized in that it has a DSC peak between about 143°C and about 175°C, and the filler particles are durably entangled within the fibrils of the fibrillated UHMWPE particles.

18. 18. The article of claim 17, wherein the UHMWPE particles exhibit at least one of a median sphericity of about 0.820 to about 0.880, a median convexity of about 0.950 to about 0.990, and a median length-to-width ratio of about 1.50 to about 1.

80.

19. 19. The article of claim 17 or 18, wherein the article has an endotherm of about 145°C to about 155°C associated with the fibrillated UHMWPE particles.

20. The article of any one of claims 17 to 19, wherein the article has a DSC curve with a DSC peak at about 143°C to about 175°C, and when the fibrillation rate is determined by integration of the DSC peak as a percentage of the integral of the DSC curve from about 100°C to about 175°C, the article has a fibrillation rate of greater than 0%.

21. The article of any one of claims 17 to 20, wherein the filler particles are selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

22. The article of any one of claims 17 to 21, wherein the binder system comprises less than 20% by weight polytetrafluoroethylene.

23. The article of any one of claims 17 to 22, wherein the binder system is free of polytetrafluoroethylene.

24. The article of any one of claims 17 to 23, wherein the article is freestanding.

25. The article of any one of claims 17 to 24, wherein the fibrillated UHMWPE particles have a median Da of from about 5 microns to about 300 microns.

26. shearing filler particles and UHMWPE particles having a molecular weight of at least about 2,000,000 g / mol, a melt enthalpy of at least 190 J / g, and a bulk density of about 0.04 m / mL to about 0.25 g / mL to form a mixed particle composition in which the filler particles are durably entangled within fibrils formed by the UHMWPE particles; forming the mixed particle composition into an article; wherein the article contains at least about 80% by weight of filler particles.

27. 27. The method of claim 26, wherein the article has a DSC curve with a DSC peak between about 143°C and about 175°C, and the article has a fibrillation rate greater than 0%.

28. 27. The method of claim 25 or 26, comprising conditioning the UHMWPE particles prior to shearing the UHMWPE particles so that the UHMWPE particles have a median Da of from about 5 microns to about 300 microns, or a median sphericity of from about 0.820 to about 0.880, or a median convexity of from about 0.950 to about 0.990, or a median length-to-width ratio of from about 1.50 to about 1.

80.

29. a filler material; and a binder system including fibrillated ultra-high molecular weight polyethylene (UHMWPE) particles; An electrode comprising: the UHMWPE particles exhibit a median Da of about 5 microns to about 300 microns, a median sphericity of about 0.820 to about 0.880, a median convexity of about 0.950 to about 0.990, and a median length-to-width ratio of about 1.50 to about 1.80, and the UHMWPE particles have a DSC peak between about 143°C and about 175°C.

30. 30. The electrode of claim 29, wherein the filler material is at least 90% by weight of the electrode.

31. 31. The electrode of claim 29 or 30, wherein the UHMWPE particles comprise no more than 10% by weight of the electrode.

32. The electrode of any one of claims 29 to 31, wherein the electrode is free-standing.

33. 33. The electrode of any one of claims 29 to 32, wherein the electrode has a DSC curve with a DSC peak at about 143°C to about 175°C, and the electrode has a fibrillation rate greater than 0%.

34. 34. The electrode of any one of claims 29 to 33, wherein the UHMWPE particles have a median Da of about 5 microns to about 300 microns, or a median sphericity of about 0.820 to about 0.880, or a median convexity of about 0.950 to about 0.990, or a median length-to-width ratio of about 1.50 to about 1.

80.

35. 35. The electrode of any one of claims 29 to 34, wherein the binder system comprises less than 20% by weight of polytetrafluoroethylene.

36. The electrode of any one of claims 29 to 34, wherein the binder system does not include polytetrafluoroethylene.

37. a molecular weight of at least about 2,000,000 g / mol; a melting enthalpy of at least 190 J / g; and a bulk density ranging from about 0.04 g / mL to about 0.25 g / mL; Providing ultra-high molecular weight polyethylene (UHMWPE) particles; providing filler particles selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles; dry blending the UHMWPE particles with the filler particles to produce a dry blend article having fibrillated UHMWPE particles therein; and forming the dry mixture into a composite sheet; wherein the filler particles are durably entangled with the fibrillated UHMWPE particles.

38. 38. The method of claim 37, wherein the composite sheet comprises at least 90% by weight of the filler particles.

39. 39. The method of claim 37 or 38, wherein the composite sheet comprises no more than 10% by weight of the fibrillated UHMWPE particles.

40. The method of any one of claims 37 to 39, wherein the composite sheet has a thickness of from about 10 microns to about 500 microns.

41. The method of any one of claims 37 to 40, wherein the composite sheet has a tensile stress at maximum load of about 2,500 kPa to about 7,000 kPa.

42. 42. The method of any one of claims 37 to 41, wherein the composite sheet has a DSC curve with a DSC peak at about 143°C to about 175°C, and the composite sheet has a fibrillation rate greater than 0%.

43. The method of any one of claims 37 to 42, wherein the composite sheet has a tensile strain at maximum load of about 3% to about 9%.

44. The method of any one of claims 37 to 43, wherein the composite sheet has a tensile strain at break of about 5% to about 50%.

45. The method of any one of claims 37 to 44, comprising applying the composite sheet to a conductive substrate.

46. 46. The method of any one of claims 37 to 45, wherein forming the dry mix into the composite sheet comprises one or more of applying pressure, calendering, and heat.

47. 47. The method of any one of claims 37 to 46, wherein the filler particles are selected from at least one of carbon particles, conductive carbon particles, activated carbon particles, graphite particles, carbon black particles, and lithium compound particles.

48. 1. A method for preparing conditioned fibrillizable ultra-high molecular weight polyethylene (UHMWPE) particles for use in a dry electrode process, comprising: providing ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least about 2,000,000 g / mol, a melt enthalpy of at least 190 J / g, and a bulk density of about 0.04 g / mL to about 0.25 g / mL; and and shear mixing the UHMWPE particles to modify the size and shape of the UHMWPE particles, conditioning the UHMWPE particles to have a shape with a median Da of from about 5 to about 300 microns, and a median length to width ratio of from about 1.50 to about 1.80, or a median sphericity of from about 0.820 to about 0.880, or a median convexity of from about 0.950 to about 0.

990.

49. 1. An ultra-high molecular weight polyethylene (UHMWPE) resin comprising ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least about 2,000,000 g / mole, a melt enthalpy of at least 190 J / g, a bulk density of about 0.04 g / mL to about 0.25 g / mL, a median Da of about 5 microns to about 300 microns, a median sphericity of about 0.820 to about 0.880 microns, a median convexity of about 0.950 to about 0.990, and a median length to width ratio of about 1.50 to about 1.

80.

50. 1. A binder system comprising fibrillizable ultra-high molecular weight polyethylene (UHMWPE) particles having a molecular weight of at least about 2,000,000 g / mol, a melting enthalpy of at least 190 J / g, a median Da of from about 5 microns to about 300 microns, a median sphericity of from about 0.820 to about 0.880, a median convexity of from about 0.950 to about 0.990, and a median length to width of from about 1.50 to about 1.

80.

51. 51. The binder system of claim 50, wherein the fibrillizable UHMWPE particles are manipulable for use in a dry electrode process.

52. 1. Use of ultra-high molecular weight polyethylene (UHMWPE) resin particles as a binder in the manufacture of an electrode, wherein the individual UHMWPE particles are a molecular weight of at least 2,000,000 g / mol; a melting enthalpy of at least 190 J / g, and Use, having a bulk density of 0.04 g / mL to 0.25 g / mL.

53. a plurality of filler particles characterized by a filler particle median value Da; Resin particle median Da, a molecular weight of at least 2,000,000 g / mol; a melting enthalpy of at least 190 J / g, and Bulk density of 0.04 g / mL to 0.25 g / mL and ultra-high molecular weight polyethylene (UHMWPE) resin particles having a filler particle median Da to resin particle median Da ratio of 10:1 to 1:

10.

54. 1. A composite binder system comprising filler particles and ultra-high molecular weight polyethylene (UHMWPE) particles, characterized in that the composite binder system has a force gradient of at least 200 N / mm when measured with a capillary rheometer on a test sample under the following conditions:

1. The test sample is a homogeneous mixture of 95% by weight of filler particles and 5% by weight of UHMWPE resin particles, 2. The barrel diameter is 12 mm and the barrel length is 241.3 mm.

3. The maximum test load is 20 kN.

4. Temperature (barrel and die) is 130°C, 5. The tape die reduction ratio is set to 2.

5.

6. The piston speed is 1 mm / sec, and 7. Measure the normal force relative to the piston position and calculate the slope of the line of normal force versus piston position using the following formula: ２ -y １ ) ÷ (x ２ -x １ ) where m = slope and (x １ ,y １ ) = coordinate of the first point on the line of force (N) versus piston position (mm), (x ２ ,y ２ ) = coordinate of a second point on the line of force (N) versus piston position (mm), where the test sample is capable of forming a solid extrudate.

55. A composition comprising ultra-high molecular weight polyethylene (UHMWPE) particles having a compressibility (%) of at least 20% at a normal stress of 15 kPa as measured using a powder rheometer at 22°C.

56. A composition comprising ultra-high molecular weight polyethylene (UHMWPE) particles having a cohesive strength of at least 3 kPa as measured using a powder rheometer at 22°C.

57. A composition comprising ultra-high molecular weight polyethylene (UHMWPE) particles having an unrestrained yield stress (UYS) of at least 10 kPa as measured using a powder rheometer at 22°C.

58. A composition comprising ultra-high molecular weight polyethylene (UHMWPE) particles having an angle of internal friction (AIF) of at least 25° as measured using a powder rheometer at 22°C.

59. A composition comprising conditioned ultra-high molecular weight polyethylene (UHMWPE) particles, which exhibit a percent change in angle of internal friction (AIF) of at least 50% relative to the unconditioned ultra-high molecular weight polyethylene (UHMWPE) particles, as measured using a powder rheometer at 22°C.

60. A composition comprising conditioned ultra-high molecular weight polyethylene (UHMWPE) particles having a percent change in base flow energy (BFE) of at least 10% relative to the unconditioned ultra-high molecular weight polyethylene (UHMWPE) particles.

61. A composition comprising conditioned ultra-high molecular weight polyethylene (UHMWPE) particles having a percent change in specific energy (SE) of at least 20% relative to the UHMWPE particles before conditioning.

62. Use of the composition of any one of claims 55 to 61 in a binder system.

63. 62. Use of the composition of any one of claims 55 to 61 as a binder in forming an anode, a cathode, or a combination thereof.

64. A composition according to any one of claims 55 to 61, and filler particles, A composite binder system comprising:

65. 65. The composite binder system of claim 64 having at least 95% by weight of the filler particles.

66. filler particles, and The composition according to any one of claims 55 to 61, An electrode comprising:

67. 67. The electrode of claim 66, comprising at least 95% by weight of filler particles.

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